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Sample records for coordination polymers incorporating

  1. Porous phosphorescent coordination polymers for oxygen sensing.

    Science.gov (United States)

    Xie, Zhigang; Ma, Liqing; deKrafft, Kathryn E; Jin, Athena; Lin, Wenbin

    2010-01-27

    Phosphorescent cyclometalated iridium tris(2-phenylpyridine) derivatives were designed and incorporated into coordination polymers as tricarboxylate bridging ligands. Three different crystalline coordination polymers were synthesized using a solvothermal technique and were characterized using a variety of methods, including single-crystal X-ray diffraction, PXRD, TGA, IR spectroscopy, gas adsorption measurements, and luminescence measurements. The coordination polymer built from Ir[3-(2-pyridyl)benzoate](3), 1, was found to be highly porous with a nitrogen BET surface area of 764 m(2)/g, whereas the coordination polymers built from Ir[4-(2-pyridyl)benzoate](3), 2 and 3, were nonporous. The (3)MLCT phosphorescence of each of the three coordination polymers was quenched in the presence of O(2). However, only 1 showed quick and reversible luminescence quenching by oxygen, whereas 2 and 3 exhibited gradual and irreversible luminescence quenching by oxygen. The high permanent porosity of 1 allows for rapid diffusion of oxygen through the open channels, leading to efficient and reversible quenching of the (3)MLCT phosphorescence. This work highlights the opportunity of designing highly porous and luminescent coordination polymers for sensing other important analytes.

  2. Composites incorporated a conductive polymer nanofiber network

    Science.gov (United States)

    Pozzo, Lilo Danielle; Newbloom, Gregory

    2017-04-11

    Methods of forming composites that incorporate networks of conductive polymer nanofibers are provided. Networks of less-than conductive polymers are first formed and then doped with a chemical dopant to provide networks of conductive polymers. The networks of conductive polymers are then incorporated into a matrix in order to improve the conductivity of the matrix. The formed composites are useful as conductive coatings for applications including electromagnetic energy management on exterior surfaces of vehicles.

  3. Porphyrin coordination polymer nanospheres and nanorods

    Science.gov (United States)

    Wang, Zhongchun; Shelnutt, John A.; Medforth, Craig J.

    2012-12-04

    A porphyrin coordination polymer nanostructure comprising a network of pyridyl porphyrin molecules and coordinating metal ions coordinatively bound through the pyridyl groups. In some embodiments, the porphyrins are metalloporphyrins. A variety of nanostructures are formed by the network polymer, including nanospheres, polygonal nanostructures, nanorods, and nanofibers, depending on a variety of factors including coordination metal ion, porphyrin type, metal of the metalloporphyrin, and degree of agitation during nanostructure formation. Reduction of coordinating metal ions may be used to form metal nanoparticles on the coordination polymer nanostructure.

  4. Rare earth niobate coordination polymers

    Science.gov (United States)

    Muniz, Collin N.; Patel, Hiral; Fast, Dylan B.; Rohwer, Lauren E. S.; Reinheimer, Eric W.; Dolgos, Michelle; Graham, Matt W.; Nyman, May

    2018-03-01

    Rare-earth (RE) coordination polymers are infinitely tailorable to yield luminescent materials for various applications. Here we described the synthesis of a heterometallic rare-earth coordination compound ((CH3)2SO)3(RE)NbO(C2O4)3((CH3)2SO) = dimethylsulfoxide, DMSO, (C2O2= oxalate), (RE=La, Ce, Pr, Nd, Sm, Eu, Gd, Tb). The structure was obtained from single crystal X-ray diffraction of the La analogue. The Nb˭O and DMSO terminal-bonding character guides assembly of an open framework structure with noncentrosymmetric RE-coordination geometry, and large spacing between the RE centers. A second structure was observed by PXRD for the smaller rare earths (Dy, Ho, Er, Yb); this structure has not yet been determined. The materials were further characterized using FTIR, and photoluminescence measurements. Characteristic excitation and emission transitions were observed for RE = Nd, Sm, Eu, and Tb. Quantum yield (QY) measurements were performed by exciting Eu and Tb analoges at 394 nm (QY 66%) and 464 nm (QY 71%) for Eu; and 370 nm (QY=40%) for Tb. We attribute the high QY and bright luminescence to two main structure-function properties of the system; namely the absence of water in the structure, and absence of concentration quenching.

  5. Adsorption Kinetics in Nanoscale Porous Coordination Polymers

    Energy Technology Data Exchange (ETDEWEB)

    Nune, Satish K.; Thallapally, Praveen K.; McGrail, Benard Peter; Annapureddy, Harsha V. R.; Dang, Liem X.; Mei, Donghai; Karri, Naveen; Alvine, Kyle J.; Olszta, Matthew J.; Arey, Bruce W.; Dohnalkova, Alice

    2015-10-07

    Nanoscale porous coordination polymers were synthesized using simple wet chemical method. The effect of various polymer surfactants on colloidal stability and shape selectivity was investigated. Our results suggest that the nanoparticles exhibited significantly improved adsorption kinetics compared to bulk crystals due to decreased diffusion path lengths and preferred crystal plane interaction.

  6. Stability of complex coacervate core micelles containing metal coordination polymer

    NARCIS (Netherlands)

    Yan, Y.; Keizer, de A.; Cohen Stuart, M.A.; Drechsler, M.; Besseling, N.A.M.

    2008-01-01

    We report on the stability of complex coacervate core micelles, i.e., C3Ms (or PIC, BIC micelles), containing metal coordination polymers. In aqueous solutions these micelles are formed between charged-neutral diblock copolymers and oppositely charged coordination polymers formed from metal ions and

  7. Osmium and cobalt complexes incorporating facially coordinated N ...

    Indian Academy of Sciences (India)

    reactivity. Fascinating chemistry of transition metal complexes incorporating ligands that are capable of binding the metal centre in facial manner, enhanced the interest on the synthesis of new ..... effective core potential functions were used. All energy .... We contemplated to examine the coordination mode of the same ...

  8. Osmium and cobalt complexes incorporating facially coordinated N ...

    Indian Academy of Sciences (India)

    Administrator

    SUPPLEMENTARY MATERIALS. Osmium and cobalt complexes incorporating facially coordinated N,N,O donor azo-imine ligands: Redox and catalytic properties. Poulami Pattanayak, a. Debprasad Patra, a. Jahar Lal Pratihar, a. Andrew Burrows,. Mary F. Mahon b and Surajit Chattopadhyay* a a. Department of Chemistry ...

  9. Osmium and cobalt complexes incorporating facially coordinated N ...

    Indian Academy of Sciences (India)

    Home; Journals; Journal of Chemical Sciences; Volume 125; Issue 1. Osmium and cobalt complexes incorporating facially coordinated N,N,O donor azo-imine ligands: Redox and catalytic properties. Poulami Pattanayak Debprasad Patra Jahar Lal Pratihar Andrew Burrows Mary F Mahon Surajit Chattopadhyay. Volume ...

  10. Synthesis, characterization, and antiplasmodial activity of polymer-incorporated aminoquinolines

    CSIR Research Space (South Africa)

    Aderibigbe, BA

    2014-01-01

    Full Text Available In this research, aminoquinoline compounds were synthesized, characterized and incorporated into water soluble polymers to form conjugates. The conjugates were characterized by X ray Diffraction (XRD), Thermal Gravimetric Analysis (TGA), Scanning...

  11. Polymers incorporating covalently attached organoimido polyoxometalates

    Science.gov (United States)

    Maatta, Eric A.; Moore, Aaron R.

    2004-03-16

    New polyoxometalate compounds and polymers comprising recurring monomers of those compounds are provided. The compounds are formed by replacing at least one oxide of the starting polyoxometalate with an organoimido (NR) group bonded to the polyoxometalate via a triple bond to the nitrogen atom. The R of the (NR) group comprises a reactive functional group which renders the compound readily polymerizable, alone or with other monomers (e.g., divinylbenzene), to form the inventive polymers. Additionally, a countercation (e.g., bis(tetra-n-butylammonium)) can be mixed with the polyoxometalate compounds in order to neutralize the negative charge thereof as well as to make those compounds more soluble in organic solvents.

  12. Two new hexacoordinated coordination polymers of cadmium (II ...

    Indian Academy of Sciences (India)

    Home; Journals; Journal of Chemical Sciences; Volume 128; Issue 9. Two new hexacoordinated coordination polymers of cadmium(II) containing bridging units only: Syntheses, structures and molecular properties. DIPU SUTRADHAR HABIBAR CHOWDHURY SUSHOVAN KONER SUBHASIS ROY BARINDRA KUMAR ...

  13. Nitrogen and oxygen incorporation into glow discharge polymers

    International Nuclear Information System (INIS)

    Engelman, R.A.; Yasuda, H.K.

    1990-01-01

    Several facets of nitrogen incorporation into glow discharge polymers were investigated. First, the deposition behavior for the glow discharge polymerization of a methane/ammonia mixture was studied. The plot of D/FM versus W/FM was found to result in a separate curve for each ammonia flow rate, independent of the methane flow rate. A linear relationship was observed between D/(FM) CH4 and W/FM, indicating that the rate of decomposition of methane is the limiting factor in polymer deposition. The rate of ammonia incorporation into the glow discharge polymer was found to be independent of the power input. Secondly, the ablation of nitrogen from previous glow discharge polymer deposits, and the subsequent incorporation into methane plasma polymers, was investigated. No incorporation of nitrogen occurred due to the exposure of trapped reactive sites to air. In contrast, oxygen was difficult to incorporate into the polymer film during the deposition process, but glow discharge deposits readily oxidized upon exposure to air

  14. Photocatalytic activity of PANI loaded coordination polymer composite materials: Photoresponse region extension and quantum yields enhancement via the loading of PANI nanofibers on surface of coordination polymer

    International Nuclear Information System (INIS)

    Cui, Zhongping; Qi, Ji; Xu, Xinxin; Liu, Lu; Wang, Yi

    2013-01-01

    To enhance photocatalytic property of coordination polymer in visible light region, polyaniline (PANI) loaded coordination polymer photocatalyst was synthesized through in-situ chemical oxidation of aniline on the surface of coordination polymer. The photocatalytic activity of PANI loaded coordination polymer composite material for degradation of Rhodamine B (RhB) was investigated. Compared with pure coordination polymer photocatalyst, which can decompose RhB merely under UV light irradiation, PANI loaded coordination polymer photocatalyst displays more excellent photocatalytic activity in visible light region. Furthermore, PANI loaded coordination polymer photocatalyst exhibits outstanding stability during the degradation of RhB. - Graphical abstract: PANI loaded coordination polymer composite material, which displays excellent photocatalytic activity under visible light was firstly synthesized through in-situ chemical oxidation of aniline on surface of coordination polymer. Display Omitted - Highlights: • This PANI loaded coordination polymer composite material represents the first conductive polymer loaded coordination polymer composite material. • PANI/coordination polymer composite material displays more excellent photocatalytic activity for the degradation of MO in visible light region. • The “combination” of coordination polymer and PANI will enable us to design high-activity, high-stability and visible light driven photocatalyst in the future

  15. Syntheses, structures and properties of two coordination polymers of ...

    Indian Academy of Sciences (India)

    Dipu Sutradhar

    2017-11-10

    Nov 10, 2017 ... Thermally stable compounds 1 and 2 show intraligand 1(π-π∗) fluorescence in DMF solution at room temperature. Keywords. Cadmium(II) coordination polymers; in situ generated Schiff base; dicyanamide/thiocyanate;. X-ray structures; luminescence. 1. Introduction. Construction of different coordination ...

  16. Integrated Photonic Devices Incorporating Low-Loss Fluorinated Polymer Materials

    Directory of Open Access Journals (Sweden)

    Hyung-Jong Lee

    2011-06-01

    Full Text Available Low-loss polymer materials incorporating fluorinated compounds have been utilized for the investigation of various functional optical devices useful for optical communication and optical sensor systems. Since reliability issues concerning the polymer device have been resolved, polymeric waveguide devices have been gradually adopted for commercial application systems. The two most successfully commercialized polymeric integrated optic devices, variable optical attenuators and digital optical switches, are reviewed in this paper. Utilizing unique properties of optical polymers which are not available in other optical materials, novel polymeric optical devices are proposed including widely tunable external cavity lasers and integrated optical current sensors.

  17. A lanthanum pyromellitate coordination polymer with three ...

    Indian Academy of Sciences (India)

    H2O)2(H2BTEC)(BTEC)],. 1, was hydrothermally synthesized and characterized by single crystal X-ray diffraction. The three- dimensional framework is built up from La2O16 dimers connected by carboxylate anions. The polymer exhibits strong ...

  18. Novel Viologen Derivative Based Uranyl Coordination Polymers Featuring Photochromic Behaviors.

    Science.gov (United States)

    Hu, Kong-Qiu; Wu, Qun-Yan; Mei, Lei; Zhang, Xiao-Lin; Ma, Lei; Song, Gang; Chen, Di-Yun; Wang, Yi-Tong; Chai, Zhi-Fang; Shi, Wei-Qun

    2017-12-19

    A series of novel uranyl coordination polymers have been synthesized by hydrothermal reactions. Both complexes 1 and 2 prosess two ipbp - ligands (H 2 ipbpCl=1-(3,5-dicarboxyphenyl)-4,4'-bipyridinium chloride), one uranyl cation, and two coordination water molecules, which can further extend to 2D networks through hydrogen bonding. In complex 1, two sets of equivalent nets are entangled together, resulting in a 2D + 2D → 3D polycatenated framework. In complex 2, the neighbouring equivalent nets interpenetrate each other, forming a twofold interpenetrated network. Complexes 3 and 4 are isomers, and both of them are constructed from (UO 2 ) 2 (OH) 2 dinuclear units, which are connected with four ipbp - ligands. The 3D structures of complexes 3 and 4 are similar along the b axis. Similar to other viologen-based coordination polymers, complexes 3 and 4 exhibit photochromic and thermochromic properties, which are rarely observed in actinide coordination polymers. Unlike the monotonous coordination mode in complexes 1-4, the ipbp - ligands feature a μ 3 -bridge through two kinds of coordination modes in complex 5. Notably, complex 5 presents a unique example in which terminal pyridine nitrogen atom is involved in the coordination. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  19. Cobalt-cadmium bimetallic porphyrin coordination polymers for electrochemistry application

    Science.gov (United States)

    Wang, C. Y.; Cui, G. Y.; Ding, D.; Zhou, B.

    2018-01-01

    In this paper, we used tetra (4-carboxyphenyl) porphyrin (H2TCPP) and metal cadmium, cobalt as reactants to synthesize metal porphyrin coordination polymers that they had different metal ratio. They were expressed as Co1Cd3TCPP, Co1Cd1TCPP, Co3Cd1TCPP, respectively. The results were characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM) and inductively coupled plasma atomic emission spectrometer (ICP). Herein, a series of metal porphyrin coordination polymers has multiple metal active centers and constructs electrochemistry sensors. In order to increase the conductivity, multi-walled carbon nanotubes (MWCNTs) can be used to modify the electrodes. The polymer/MWCNTs/GCE electrode was studied by cyclic voltammetry and chronoamperometry as sensor for sodium nitrite. The performance of Co1Cd1TCPP/MWCNTs/GCE electrode is best, the sensitivity for sodium nitrite is 350.95 mA M-1 cm-2 and the. The results indicate that metal porphyrin coordination polymers have excellent performance. It also enriches the application of metal porphyrin coordination polymer in electrochemistry sensor.

  20. Assembling one-dimensional coordination polymers into ...

    Indian Academy of Sciences (India)

    ... analyses of these complexes reveal that the one-dimensional networks observed here are of three types: simple linear chain, chains with wavy nature and chains containing cavities. The self-complementary amide groups of the ligands assembled these coordination networks into higher dimensional architectures via N-H ...

  1. Reversible Mechanochemistry of a PdII Coordination Polymer

    NARCIS (Netherlands)

    Paulusse, Jos Marie Johannes; Sijbesma, Rint P.

    2004-01-01

    Breaking up and making up: The ultrasonic cleavage of high-molecular-weight linear coordination polymers of phosphane telechelic polytetrahydrofuran and palladium dichloride in dilute solution is a reversible process (see picture). Sonication for 1 h led to a decrease in the weight-averaged

  2. Strategies, linkers and coordination polymers for high-performance sorbents

    Science.gov (United States)

    Matzger, Adam J.; Wong-Foy, Antek G.; Lebel, Oliver

    2015-09-15

    A linking ligand compound includes three bidentate chemical moieties distributed about a central chemical moiety. Another linking ligand compound includes a bidentate linking ligand and a monodentate chemical moiety. Coordination polymers include a plurality of metal clusters linked together by residues of the linking ligand compounds.

  3. Syntheses, structures and properties of two coordination polymers of ...

    Indian Academy of Sciences (India)

    Home; Journals; Journal of Chemical Sciences; Volume 129; Issue 12. Syntheses, structures and properties of two coordination polymers of Cadmium(II) pseudohalide containing an in situ generated bidentate Schiff base: Control of dimensionality by varying pseudohalides. REGULAR ARTICLE Volume 129 Issue 12 ...

  4. White-light phosphorescence from binary coordination polymer nanoparticles

    International Nuclear Information System (INIS)

    Qin, Lijie; Zhu, Yachao; Yang, Hong; Ding, Liang; Sun, Feng; Shi, Mei; Yang, Shiping

    2013-01-01

    Phosphorescent nanoscale coordination polymer nanoparticles (NCPs) were conveniently synthesized by phosphorescent carboxyl-functionalized iridium complexes as a building block and rare earth Y(III) ions as metallic nodes. They reveal to be uniform nanospheres with average diameter around 200 nm. Multi-color emission from blue to orange was obtained by tuning the ratios of two iridium complexes with energy transfer between them. Furthermore, the white-light emission with CIE coordinates of (0.319, 0.388) was performed. - Highlights: ► Phosphorescent nanoscale coordination polymer nanoparticles (NCPs) were conveniently synthesized. ► The phosphorescent carboxyl-functionalized iridium complex was a building block with rare earth Y(III) ions as metallic nodes. ► Multi-color emission from blue to orange was obtained

  5. Mesoscopic superstructures of flexible porous coordination polymers synthesizedviacoordination replication.

    Science.gov (United States)

    Sumida, Kenji; Moitra, Nirmalya; Reboul, Julien; Fukumoto, Shotaro; Nakanishi, Kazuki; Kanamori, Kazuyoshi; Furukawa, Shuhei; Kitagawa, Susumu

    2015-10-01

    The coordination replication technique is employed for the direct conversion of a macro- and mesoporous Cu(OH) 2 -polyacrylamide composite to three-dimensional superstructures consisting of the flexible porous coordination polymers, Cu 2 (bdc) 2 (MeOH) 2 and Cu 2 (bdc) 2 (bpy) (bdc 2- = 1,4-benzenedicarboxylate, bpy = 4,4'-bipyridine). Detailed characterization of the replicated systems reveals that the structuralization plays an important role in determining the adsorptive properties of the replicated systems, and that the immobilization of the crystals within a higher-order architecture also affects its structural and dynamic properties. The polyacrylamide polymer is also found to be crucial for maintaining the structuralization of the monolithic systems, and in providing the mechanical robustness required for manual handling. In all, the results discussed here demonstrate a significant expansion in the scope of the coordination replication strategy, and further confirms its utility as a highly versatile platform for the preparation of functional three-dimensional superstructures of porous coordination polymers.

  6. Unusual Transformation from a Solvent-Stabilized 1D Coordination Polymer to a Metal-Organic Framework (MOF)-Like Cross-Linked 3D Coordination Polymer.

    Science.gov (United States)

    Lee, Seung-Chul; Choi, Eun-Young; Lee, Sang-Beom; Kim, Sang-Wook; Kwon, O-Pil

    2015-10-26

    An unusual 1D-to-3D transformation of a coordination polymer based on organic linkers containing highly polar push-pull π-conjugated side chains is reported. The coordination polymers are synthesized from zinc nitrate and an organic linker, namely, 2,5-bis{4-[1-(4-nitrophenyl)pyrrolidin-2-yl]butoxy}terephthalic acid, which possesses highly polar (4-nitrophenyl)pyrrolidine groups, with high dipole moments of about 7 D. The coordination polymers exhibit an unusual transformation from a soluble, solvent-stabilized 1D coordination polymer into an insoluble, metal-organic framework (MOF)-like 3D coordination polymer. The coordination polymer exhibits good film-forming ability, and the MOF-like films are insoluble in conventional organic solvents. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  7. 3d and 4d coordination complexes and coordination polymers involving electroactive tetrathiafulvalene containing ligands

    OpenAIRE

    Pointillart , Fabrice; Golhen , Stéphane; Cador , Olivier; Ouahab , Lahcène

    2013-01-01

    International audience; The "through bond" approach has been recently developed to increase the interaction between the mobile π and localized d electrons in multifunctional molecular materials involving tetrathiafulvalene-based ligands. This article reviews the 3d and 4d coordination complexes and polymers elaborated from a library of tetrathiafulvalene derivatives containing ligands obtained recently in our group. The different synthetic ways of the complexes are highlighted as well as thei...

  8. Alkaline earth-based coordination polymers derived from a cyclotriphosphazene-functionalized hexacarboxylate

    International Nuclear Information System (INIS)

    Ling, Yajing; Bai, Dongjie; Feng, Yunlong; He, Yabing

    2016-01-01

    earth-based coordination polymers were constructed from a semirigid cyclotriphosphazene-functionalized hexacarboxylate exhibiting different inorganic nodes as well as distinct ligand conformations relying on the metal ions, which presents the first example of such a ligand incorporated into alkaline earth–based coordination polymers. - Highlights: • Three alkaline earth-based coordination polymers were synthesized. • The three compounds exhibit different inorganic nodes and ligand conformations. • The three compounds are photoluminscent in the solid state.

  9. Alkaline earth-based coordination polymers derived from a cyclotriphosphazene-functionalized hexacarboxylate

    Energy Technology Data Exchange (ETDEWEB)

    Ling, Yajing; Bai, Dongjie; Feng, Yunlong; He, Yabing, E-mail: heyabing@zjnu.cn

    2016-10-15

    topologies. - Graphical abstract: Three alkaline earth-based coordination polymers were constructed from a semirigid cyclotriphosphazene-functionalized hexacarboxylate exhibiting different inorganic nodes as well as distinct ligand conformations relying on the metal ions, which presents the first example of such a ligand incorporated into alkaline earth–based coordination polymers. - Highlights: • Three alkaline earth-based coordination polymers were synthesized. • The three compounds exhibit different inorganic nodes and ligand conformations. • The three compounds are photoluminscent in the solid state.

  10. Plasma deposition of polymer composite films incorporating nanocellulose whiskers

    Science.gov (United States)

    Samyn, P.; Airoudj, A.; Laborie, M.-P.; Mathew, A. P.; Roucoules, V.

    2011-11-01

    In a trend for sustainable engineering and functionalization of surfaces, we explore the possibilities of gas phase processes to deposit nanocomposite films. From an analysis of pulsed plasma polymerization of maleic anhydride in the presence of nanocellulose whiskers, it seems that thin nanocomposite films can be deposited with various patterns. By specifically modifying plasma parameters such as total power, duty cycle, and monomer gas pressure, the nanocellulose whiskers are either incorporated into a buckled polymer film or single nanocellulose whiskers are deposited on top of a polymeric film. The density of the latter can be controlled by modifying the exact positioning of the substrate in the reactor. The resulting morphologies are evaluated by optical microscopy, AFM, contact angle measurements and ellipsometry.

  11. Extended structures of two coordination polymers based on 1,10 ...

    Indian Academy of Sciences (India)

    quinoxaline) by hydrothermal processing and structural characterization by ele- mental analysis, thermogravimetric analysis and single-crystal X-ray diffraction. The coordination polymers 1 and 2 have 1D chains formed via coordination bonds ...

  12. Osmium and cobalt complexes incorporating facially coordinated N ...

    Indian Academy of Sciences (India)

    Home; Journals; Journal of Chemical Sciences; Volume 125; Issue 1. Osmium and cobalt complexes incorporating ... Mary F Mahon2 Surajit Chattopadhyay1. Department of Chemistry, University of Kalyani, Kalyani 741235, India; Department of Inorganic Chemistry, University of Bath, Claverton Down, Bath, BA27AY, UK ...

  13. Solid-state polymerisation via [2+2] cycloaddition reaction involving coordination polymers.

    Science.gov (United States)

    Medishetty, Raghavender; Park, In-Hyeok; Lee, Shim Sung; Vittal, Jagadese J

    2016-03-14

    Highly crystalline metal ions containing organic polymers are potentially useful to manipulate the magnetic and optical properties to make advanced multifunctional materials. However, it is challenging to synthesise monocrystalline metal complexes of organic polymers and single-phase hybrid materials made up of both coordination and organic polymers by traditional solution crystallisation. This requires an entirely different approach in the solid-state by thermal or photo polymerisation of the ligands. Among the photochemical methods available, [2+2] cycloaddition reaction has been recently employed to generate cyclobutane based coordination polymers from the metal complexes. Cyclobutane polymers have also been integrated into coordination polymers in this way. Recent advancements in the construction of polymeric chains of cyclobutane rings through photo-dimerisation reaction in the monocrystalline solids containing metal complexes, coordination polymers and metal-organic framework structures are discussed here.

  14. Lanthanide Coordination Polymer Nanosheet Aggregates: Solvothermal Synthesis and Downconversion Luminescence

    Directory of Open Access Journals (Sweden)

    Rui-Rui Su

    2016-01-01

    Full Text Available A lanthanide coordination polymers (CPs nanostructure (1 has been synthesized via a facile template-free solvothermal strategy using DMF as solvent and 2-methyl benzoic acid (2-MeBAH as ligands. The products are characterized by powder X-ray diffraction (PXRD, scanning electron microscopy (SEM, elemental analyses (EA, and downward luminescence. Product 1 built from Tb3+ and 2-MeBAH has one-dimensional structure which is connected by trinuclear second building units (SBUs. Downward luminescence shows that sample 1 exhibits characteristic transitions of the Tb3+ ion at 489, 544, 583, and 621 nm, and the strongest peak is at 544 nm ascribed to the transition of D45→F57 of Tb3+.

  15. Gas confinement in compartmentalized coordination polymers for highly selective sorption.

    Science.gov (United States)

    Giménez-Marqués, Mónica; Calvo Galve, Néstor; Palomino, Miguel; Valencia, Susana; Rey, Fernando; Sastre, Germán; Vitórica-Yrezábal, Iñigo J; Jiménez-Ruiz, Mónica; Rodríguez-Velamazán, J Alberto; González, Miguel A; Jordá, José L; Coronado, Eugenio; Espallargas, Guillermo Mínguez

    2017-04-01

    Discrimination between different gases is an essential aspect for industrial and environmental applications involving sensing and separation. Several classes of porous materials have been used in this context, including zeolites and more recently MOFs. However, to reach high selectivities for the separation of gas mixtures is a challenging task that often requires the understanding of the specific interactions established between the porous framework and the gases. Here we propose an approach to obtain an enhanced selectivity based on the use of compartmentalized coordination polymers, named CCP-1 and CCP-2 , which are crystalline materials comprising isolated discrete cavities. These compartmentalized materials are excellent candidates for the selective separation of CO 2 from methane and nitrogen. A complete understanding of the sorption process is accomplished with the use of complementary experimental techniques including X-ray diffraction, adsorption studies, inelastic- and quasi-elastic neutron scattering, magnetic measurements and molecular dynamics calculations.

  16. Incorporation and Effects of Nanoparticles in a Supramolecular Polymer

    Science.gov (United States)

    2016-05-01

    polymers provide potential innovative applications in coatings, adhesives, fuel cells, and biosensors due to retention of physical and mechanical properties...Supramolecular polymers provide potential innovative applications in coatings, adhesives, fuel cells, and biosensors due to retention of physical and

  17. A novel Mn(II) oxalato-bridged 2D coordination polymer: synthesis ...

    Indian Academy of Sciences (India)

    Hiba Sehimi

    2018-02-28

    Feb 28, 2018 ... Keywords. 2D coordination polymer; manganese; oxalate; magnetism. 1. Introduction. Coordination polymers (CPs) are of rising interest because of their fascinating topologies and dimension- ality associated with both structural and functional ver- satility. Various attempts to build high-dimensional CPs.

  18. Reversible, High Molecular Weight Palladium and Platinum Coordination Polymers Based on Phosphorus Ligands

    NARCIS (Netherlands)

    Paulusse, Jos Marie Johannes; Huijbers, Jeroen P.J.; Sijbesma, Rint P.

    2005-01-01

    A general strategy for the preparation and characterization of high molecular weight coordination polymers based on bifunctional phosphorus ligands and palladium or platinum dichloride is described. Metal-to-ligand stoichiometry is of key importance for the formation of linear coordination polymers

  19. Supramolecular coordination polymer formed from artificial light-harvesting dendrimer.

    Science.gov (United States)

    Lee, Hosoowi; Jeong, Young-Hwan; Kim, Joo-Ho; Kim, Inhye; Lee, Eunji; Jang, Woo-Dong

    2015-09-30

    We report the formation of supramolecular coordination polymers formed from multiporphyrin dendrimers (PZnPM; M = FB or Cu), composed of the focal freebase porphyrin (PFB) or cupper porphyrin (PCu) with eight zinc porphyrin (PZn) wings, and multipyridyl porphyrins (PyPM; M = FB or Cu), PFB or PCu with eight pyridyl groups, through multiple axial coordination interactions of pyridyl groups to PZns. UV-vis absorption spectra were recorded upon titration of PyPFB to PZnPFB. Differential spectra, obtained by subtracting the absorption of PZnPFB without guest addition as well as the absorption of PyPFB, exhibited clear isosbestic points with saturation binding at 1 equiv addition of PyPFB to PZnPFB. Job's plot analysis also indicated 1:1 stoichiometry for the saturation binding. The apparent association constant between PZnPFB and PyPFB (2.91 × 10(6) M(-1)), estimated by isothermal titration calorimetry, was high enough for fibrous assemblies to form at micromolar concentrations. The formation of a fibrous assembly from PZnPFB and PyPFB was visualized by atomic force microscopy and transmission electron microscopy (TEM). When a 1:1 mixture solution of PZnPFB and PyPFB (20 μM) in toluene was cast onto mica, fibrous assemblies with regular height (ca. 2 nm) were observed. TEM images obtained from 1:1 mixture solution of PZnPFB and PyPFB (0.1 wt %) in toluene clearly showed the formation of nanofibers with a regular diameter of ca. 6 nm. Fluorescence emission measurement of PZnPM indicated efficient intramolecular energy transfer from PZn to the focal PFB or PCu. By the formation of supramolecular coordination polymers, the intramolecular energy transfer changed to intermolecular energy transfer from PZnPM to PyPM. When the nonfluorescent PyPCu was titrated to fluorescent PZnPFB, fluorescence emission from the focal PFB was gradually decreased. By the titration of fluorescent PyPFB to nonfluorescent PZnPCu, fluorescence emission from PFB in PyPFB was gradually increased

  20. Polymer incorporation method affects the physical stability of amorphous indomethacin in aqueous suspension

    DEFF Research Database (Denmark)

    Surwase, S A; Itkonen, L; Aaltonen, J

    2015-01-01

    methylcellulose (HPMC) and Soluplus® (SP)) were used and included in the suspensions either as a solid dispersion (SD) with IND or dissolved in the suspension medium prior to the addition of amorphous IND. The total concentrations of both IND and the polymer in the suspensions were kept the same for both methods......This study reports the potential of different polymers and polymer incorporation methods to inhibit crystallisation and maintain supersaturation of amorphous indomethacin (IND) in aqueous suspensions during storage. Three different polymers (poly(vinyl pyrrolidone) (PVP), hydroxypropyl...... of polymer incorporation. All the polymers (with both incorporation methods) inhibited crystallisation of the amorphous IND. The SDs were better than the predissolved polymer solutions at inhibiting crystallisation. The SDs were also better at maintaining drug supersaturation. SP showed a higher IND...

  1. A multi-functional coordination polymer coexisting spontaneous chirality resolution and weak ferromagnetism

    International Nuclear Information System (INIS)

    Li, Xiu-Hua; Zhang, Qi; Hu, Ping

    2014-01-01

    A multifunctional homochiral coordination polymer, [Co(H 2 O)(BDC)(4,4′-BPY)]∙3H 2 O (1) (H 2 BDC=1,2-benzenedicarboxylate and 4,4′-BPY=4,4′-bipyridine), has been successfully isolated from Co(II) ions and mixed ligands (1,2-benzenedicarboxylate and 4,4′-bipyridine). Complex 1, which exhibits spontaneous chirality resolution and weak ferromagnetism, is built by chiral helices interconnected via end-to-end 4,4′-BPY bridges into a two-dimensional (2D) layer structure. - Graphical abstract: A 2D cobalt coordination polymer compound showing spontaneous chirality resolution and weak ferromagnetism. - Highlights: • A new 2D cobalt mix-ligand coordination polymer complex has been synthesized. • The cobalt coordination polymer complex shows spontaneous chirality resolution in solid state. • The cobalt coordination polymer complex displays dominant and weak intrachain ferromagnetic interactions

  2. Wire Insulation Incorporating Self-Healing Polymers (WIISP) Project

    Data.gov (United States)

    National Aeronautics and Space Administration — NextGen and Virginia Tech are developing a self-healing material for wire insulation using a class of ionomeric polymers. These ionomers exhibit self-healing...

  3. Wire Insulation Incorporating Self-Healing Polymers (WIISP), Phase II

    Data.gov (United States)

    National Aeronautics and Space Administration — NextGen and Virginia Tech are developing a self-healing material for wire insulation using a class of ionomeric polymers. These ionomers exhibit self-healing...

  4. Multifunctional Composites Obtained by Incorporating Nanocrystals into Decorated PVK Polymers

    Directory of Open Access Journals (Sweden)

    Haizhu Sun

    2007-01-01

    Full Text Available Poly(vinylcarbazole (PVK was decorated with surfactant group to achieve amphiphilic polymer with luminescent property. The composition and properties of the polymers were systematically investigated using FTIR, EA, TGA, UV-Vis, and PL characterizations. Different CdTe nanocrystals (NCs prepared in aqueous medium were directly transferred to organic phase using the PVK-based polymers. The quantum yield of NCs in the composites had been improved by 50% compared with their parent aqueous solution due to the short distance from carbazole moieties to NCs, which facilitated the Förster resonant energy transfer (FRET between them. Moreover, efficient electron transfer at the interface of NCs and polymers had been confirmed which also indicated the application in photovoltaic cell for such composites.

  5. A new experimental procedure for incorporation of model contaminants in polymer hosts

    NARCIS (Netherlands)

    Papaspyrides, C.D.; Voultzatis, Y.; Pavlidou, S.; Tsenoglou, C.; Dole, P.; Feigenbaum, A.; Paseiro, P.; Pastorelli, S.; Cruz Garcia, C. de la; Hankemeier, T.; Aucejo, S.

    2005-01-01

    A new experimental procedure for incorporation of model contaminants in polymers was developed as part of a general scheme for testing the efficiency of functional barriers in food packaging. The aim was to progressively pollute polymers in a controlled fashion up to a high level in the range of

  6. Linking homogeneous and heterogeneous enantioselective catalysis through a self-assembled coordination polymer.

    Science.gov (United States)

    García, José I; López-Sánchez, Beatriz; Mayoral, José A

    2008-11-06

    Combining the advantages of homogeneous and heterogeneous enantioselective catalysis is possible through self-supported copper coordination polymers, based on a new kind of ditopic chiral ligand bearing two azabis(oxazoline) moieties. When the coordination polymer is used to catalyze a cyclopropanation reaction, it becomes soluble in reaction conditions but precipitates after reaction completion, allowing easy recovery and efficient reuse in the same reaction up to 14 times.

  7. m-Carboranylphosphinate as Versatile Building Blocks To Design all Inorganic Coordination Polymers.

    Science.gov (United States)

    Oleshkevich, Elena; Viñas, Clara; Romero, Isabel; Choquesillo-Lazarte, Duane; Haukka, Matti; Teixidor, Francesc

    2017-05-15

    The first examples of coordination polymers of manganese(II) and a nickel(II) complex with a purely inorganic carboranylphosphinate ligand are reported, together with its exhaustive characterization. X-ray analysis revealed 1D polymeric chains with carboranylphosphinate ligands bridging two manganese(II) centers. The reactivity of polymer 1 with water and Lewis bases has also been studied.

  8. Organometallic Polymers.

    Science.gov (United States)

    Carraher, Charles E., Jr.

    1981-01-01

    Reactions utilized to incorporate a metal-containing moiety into a polymer chain (addition, condensation, and coordination) are considered, emphasizing that these reactions also apply to smaller molecules. (JN)

  9. Novel Inorganic Coordination Polymers Based on Cadmium Oxalates

    Science.gov (United States)

    Prasad, P. A.; Neeraj, S.; Vaidhyanathan, R.; Natarajan, Srinivasan

    2002-06-01

    Three new cadmium oxalate coordination polymers, I-III, with extended layered structures have been synthesized in the presence of imidazole. While I was prepared by the reaction between imidazolium oxalate and Cd, II and III were synthesized from their constituents using hydrothermal methods. [Cd(C2O4)(C3N2H4)]∞ (I): monoclinic, space group P21/c (no. 14), a=8.7093(1) Å, b=9.9477(3) Å, c=8.4352 Å, β=93.796(1)°, Z=4; [Cd(C2O4)2(C3N2H4)3(H2O)]∞ (II): monoclinic, space group P21/c (no. 14), a=7.8614(2) Å, b=14.9332(3) Å, c=15.9153(4) Å β=94.587(1)°, Z=4; [Cd(C2O4)2(C3N2H4)3(H2O)]∞ (III): monoclinic, space group P21/c (no. 14), a=11.844(2) Å, b=9.066(1) Å, c=18.583(2) Å, β=103.84(2)°, Z=4. While the structure of I is made from CdO5N distorted octahedra linked with oxalate, II and III are built-up from CdO6N, CdO5N2 distorted pentagonal bi-pyramids connected to oxalate units. The framework formulas of II and III are identical and their structures closely related. In all the cases, the networking between the Cd-O/N polyhedra and oxalates give rise to layered architectures with the amine molecules pointing in a direction perpendicular to the layers (in the inter-lamellar region). The difference in the linkages between the oxalates and the Cd atoms in I-III, produces unusual Cd-O-Cd one-dimensional chains, which have been observed for the first time.

  10. Fine-tuning optimal porous coordination polymers using functional alkyl groups for CH4 purification

    NARCIS (Netherlands)

    Cheng, F.; Li, Q.; Duan, J.; Hosono, N.; Noro, S.-I.; Krishna, R.; Lyu, H.; Kusaka, S.; Jin, W.; Kitagawa, S.

    2017-01-01

    Nano-porous coordination polymers (nano-PCPs), as a new class of crystalline material, have become a lucrative topic in coordination chemistry due to the facile tunability of their functional pore environments. However, elucidating the pathways for the rational design and preparation of nano-PCPs

  11. Extended structures of two coordination polymers based on 1,10 ...

    Indian Academy of Sciences (India)

    metal ions play a critical role in the framework construction of the two coordination polymers. Meanwhile, natural bond orbital (NBO) analysis was performed by the PBE0/LANL2DZ method in Gaussian 09 program. The calculated results show the obvious covalent interaction between the coordinated atoms and metal ions.

  12. A two-dimensional yttrium phthalate coordination polymer, [Y4(H2O ...

    Indian Academy of Sciences (India)

    Unknown

    - lic acid (1,2-BDC) and NaOH gives rise to a new yttrium phthalate coordination polymer, [Y4(H2O)2(C8H4O4)6]∞, I. The Y ions in I are present in four different coordination environments with respect to the oxygen atoms (CN6 = octahedral,.

  13. Studies on dielectric properties of ferrocenylhydrazone coordinated polymers irradiated by γ-rays

    International Nuclear Information System (INIS)

    Lin Yun; Chen Jie; Lin Zhanru

    2007-01-01

    The three ferrocenylhydrazone coordinated metal polymers were synthesized (PZM). The effect of the 60 Co γ irradiation on microwave dielectric properties and their temperature-dielectric properties were studies. It has been found that the dielectric parameters (ε', tgδ) of coordinated polymers increase along with the absorbed doses and coordinated metals in order Cu, Co, Ni, However, the dependent curves of dielectric parameters on arise-down temperature are universal. On the other hand, the small changes in chemical structure before and after irradiation were confirmed by IR differential spectrometry and SEM. It is possible to make such coordinated polymers as a multifunctional polymeric material with optical, electric and magnetic properties, which may be potentially used in microwave communication. (authors)

  14. Nanofibers extraction from palm mesocarp fiber for biodegradable polymers incorporation

    International Nuclear Information System (INIS)

    Kuana, Vanessa A.; Rodrigues, Vanessa B.; Takahashi, Marcio C.; Campos, Adriana de; Sena Neto, Alfredo R.; Mattoso, Luiz H.C.; Marconcini, Jose M.

    2015-01-01

    The palm mesocarp fibers are residues produced by the palm oil industries. The objective of this paper is to determine an efficient treatment to extract crystal cellulose nanofibers from the palm mesocarp fibers to be incorporated in biodegradable polymeric composites. The fibers were saponified, bleached and analyzed with thermal gravimetric analysis, X-ray diffraction, Fourier transform infrared spectroscopy and scanning electron microscopy. (author)

  15. New generation fiber reinforced polymer composites incorporating carbon nanotubes

    Science.gov (United States)

    Soliman, Eslam

    The last five decades observed an increasing use of fiber reinforced polymer (FRP) composites as alternative construction materials for aerospace and infrastructure. The high specific strength of FRP attracted its use as non-corrosive reinforcement. However, FRP materials were characterized with a relatively low ductility and low shear strength compared with steel reinforcement. On the other hand, carbon nanotubes (CNTs) have been introduced in the last decade as a material with minimal defect that is capable of increasing the mechanical properties of polymer matrices. This dissertation reports experimental investigations on the use of multi-walled carbon nanotubes (MWCNTs) to produce a new generation of FRP composites. The experiments showed significant improvements in the flexure properties of the nanocomposite when functionalized MWCNTs were used. In addition, MWCNTs were used to produce FRP composites in order to examine static, dynamic, and creep behavior. The MWCNTs improved the off-axis tension, off-axis flexure, FRP lap shear joint responses. In addition, they reduced the creep of FRP-concrete interface, enhanced the fracture toughness, and altered the impact resistance significantly. In general, the MWCNTs are found to affect the behaviour of the FRP composites when matrix failure dominates the behaviour. The improvement in the mechanical response with the addition of low contents of MWCNTs would benefit many industrial and military applications such as strengthening structures using FRP composites, composite pipelines, aircrafts, and armoured vehicles.

  16. A multi-functional coordination polymer coexisting spontaneous chirality resolution and weak ferromagnetism

    Energy Technology Data Exchange (ETDEWEB)

    Li, Xiu-Hua, E-mail: xhli.univ@gmail.com [College of Chemistry and Chemical Engineering, Fujian Normal University, Fuzhou, 350117 Fujian (China); Zhang, Qi [School of Life Science, Changchun Normal University, Changchun, 130032 Jilin (China); Hu, Ping [Southampton Management School, University of Southampton, Highfield, Southampton SO17 1BJ (United Kingdom)

    2014-10-15

    A multifunctional homochiral coordination polymer, [Co(H{sub 2}O)(BDC)(4,4′-BPY)]∙3H{sub 2}O (1) (H{sub 2}BDC=1,2-benzenedicarboxylate and 4,4′-BPY=4,4′-bipyridine), has been successfully isolated from Co(II) ions and mixed ligands (1,2-benzenedicarboxylate and 4,4′-bipyridine). Complex 1, which exhibits spontaneous chirality resolution and weak ferromagnetism, is built by chiral helices interconnected via end-to-end 4,4′-BPY bridges into a two-dimensional (2D) layer structure. - Graphical abstract: A 2D cobalt coordination polymer compound showing spontaneous chirality resolution and weak ferromagnetism. - Highlights: • A new 2D cobalt mix-ligand coordination polymer complex has been synthesized. • The cobalt coordination polymer complex shows spontaneous chirality resolution in solid state. • The cobalt coordination polymer complex displays dominant and weak intrachain ferromagnetic interactions.

  17. Room temperature synthesis of a Zn(II) metal-organic coordination polymer for dye removal

    Energy Technology Data Exchange (ETDEWEB)

    Abbasi, Alireza, E-mail: aabbasi@khayam.ut.ac.ir [School of Chemistry, College of Science, University of Tehran, Tehran (Iran, Islamic Republic of); Gharib, Maniya; Najafi, Mahnaz [School of Chemistry, College of Science, University of Tehran, Tehran (Iran, Islamic Republic of); Janczak, Jan [Institute of Low Temperature and Structure Research, Polish Academy of Sciences, PO Box 1410, 50-950 Wrocław (Poland)

    2016-03-15

    A new one-dimensional (1D) coordination polymer, [Zn(4,4′-bpy)(H{sub 2}O){sub 4}](ADC)·4H{sub 2}O (1) (4,4′-bpy=4,4′-bipyridine and H{sub 2}ADC=acetylenedicarboxylic acid), was synthesized at room temperature. The crystal structure of the coordination polymer was determined by single-crystal X-ray diffraction analysis. Compound 1 was also characterized by FT-IR, powder X-ray diffraction (PXRD) and thermogravimetric analysis (TGA). The catalytic activity of 1 was evaluated in the color removal of Bismarck brown as a representative of dye pollutant in water under mild conditions. Coordination polymer 1 exhibited good catalytic activity and stability in the decolorization of Bismarck brown and could be easily recovered and reused for at least three cycles. - Graphical abstract: A new 1D coordination polymer as catalyst for the degradation of Bismarck brown aqueous solution. - Highlights: • A 1D coordination polymer has been synthesized at room temperature. • The prepared compound was utilized for color removal of Bismarck brown dye. • Good catalytic activity and stability in the dye decolorization has been found.

  18. Incorporation of tritium contaminated oil in cement using an absorbent polymer

    International Nuclear Information System (INIS)

    Goes, Marcos Maciel de; Marumo, Julio Takehiro; Isiki, Vera Lucia Keiko

    2002-01-01

    This paper describes a study carried out to determine whether a absorbent polymer can be used to pretreat tritiated vacuum pump oils, before solidification in cement matrix. The experiments were conducted with samples prepared with simulated waste, absorbent polymer, portland cement and silica fume, in some cases, and evaluating the performance according to compressive strength, workability and bleeding. Despite the low quantity of oil incorporated, this study showed that it can be a feasible method, since it provided a stable product. (author)

  19. Cationic zinc (II) dimers and one dimensional coordination polymer ...

    Indian Academy of Sciences (India)

    Home; Journals; Journal of Chemical Sciences; Volume 126; Issue 5 ... Special issue on Chemical Crystallography Volume 126 Issue 5 September 2014 pp 1409-1415 ... These new molecules, dimers and polymer, were characterized by FT-IR, NMR, UV-vis, fluorescent and single crystal X-ray diffraction techniques.

  20. Room temperature synthesis of a Zn(II) metal-organic coordination polymer for dye removal

    Science.gov (United States)

    Abbasi, Alireza; Gharib, Maniya; Najafi, Mahnaz; Janczak, Jan

    2016-03-01

    A new one-dimensional (1D) coordination polymer, [Zn(4,4‧-bpy)(H2O)4](ADC)·4H2O (1) (4,4‧-bpy=4,4‧-bipyridine and H2ADC=acetylenedicarboxylic acid), was synthesized at room temperature. The crystal structure of the coordination polymer was determined by single-crystal X-ray diffraction analysis. Compound 1 was also characterized by FT-IR, powder X-ray diffraction (PXRD) and thermogravimetric analysis (TGA). The catalytic activity of 1 was evaluated in the color removal of Bismarck brown as a representative of dye pollutant in water under mild conditions. Coordination polymer 1 exhibited good catalytic activity and stability in the decolorization of Bismarck brown and could be easily recovered and reused for at least three cycles.

  1. Ion conductivity and transport by porous coordination polymers and metal-organic frameworks.

    Science.gov (United States)

    Horike, Satoshi; Umeyama, Daiki; Kitagawa, Susumu

    2013-11-19

    Ion conduction and transport in solids are both interesting and useful and are found in widely distinct materials, from those in battery-related technologies to those in biological systems. Scientists have approached the synthesis of ion-conductive compounds in a variety of ways, in the areas of organic and inorganic chemistry. Recently, based on their ion-conducting behavior, porous coordination polymers (PCPs) and metal-organic frameworks (MOFs) have been recognized for their easy design and the dynamic behavior of the ionic components in the structures. These PCP/MOFs consist of metal ions (or clusters) and organic ligands structured via coordination bonds. They could have highly concentrated mobile ions with dynamic behavior, and their characteristics have inspired the design of a new class of ion conductors and transporters. In this Account, we describe the state-of-the-art of studies of ion conductivity by PCP/MOFs and nonporous coordination polymers (CPs) and offer future perspectives. PCP/MOF structures tend to have high hydrophilicity and guest-accessible voids, and scientists have reported many water-mediated proton (H(+)) conductivities. Chemical modification of organic ligands can change the hydrated H(+) conductivity over a wide range. On the other hand, the designable structures also permit water-free (anhydrous) H(+) conductivity. The incorporation of protic guests such as imidazole and 1,2,4-triazole into the microchannels of PCP/MOFs promotes the dynamic motion of guest molecules, resulting in high H(+) conduction without water. Not only the host-guest systems, but the embedding of protic organic groups on CPs also results in inherent H(+) conductivity. We have observed high H(+) conductivities under anhydrous conditions and in the intermediate temperature region of organic and inorganic conductors. The keys to successful construction are highly mobile ionic species and appropriate intervals of ion-hopping sites in the structures. Lithium (Li

  2. Rational Design of Coordination Polymers with Flexible Oxyethylene Side Chains

    International Nuclear Information System (INIS)

    Choi, Eun Young; Gao, Chunji; Lee, Suck Hyun; Kwon, O Pil

    2012-01-01

    We rationally designed and synthesized metallopolymers with organic 1,4-benzenedicarboxylic acid (BDC) linkers with different lengths of oxyethylene side chains in order to examine the influence of side chains on the coordination characteristics. While in a previous report the BDC linkers with alkyl side chains were found to form three-dimensional (3D) isoreticular metal-organic framework (IRMOF) structures or one-dimensional (1D) coordination polymeric structures with short -O(CH 2 ) 6 CH 3 or long -O(CH 2 ) 9 CH 3 side chains, respectively, new BDC linkers with oxyethylene side chains of the same lengths, -(OCH 2 CH 2 ) 2 CH 3 and -(OCH 2 CH 2 ) 3 CH 3 , form only 3D IRMOF structures. This result is attributed to the higher flexibility and smaller volume of oxyethylene side chains compared to alkyl side chains

  3. A one-dimensional barium (II) coordination polymer with a ...

    Indian Academy of Sciences (India)

    The polymeric structure is based on a dimeric unit and consists of three water molecules coordinated to a central Ba(II) and two unique 2-nitrobenzoate (2-nba) anions, one of which (2-2-nba-O,O,O-NO2) functions as a tridentate ligand and is linked to a Ba(II) through the oxygen atom of the -NO2 group and forms a ...

  4. Polyacrylic acid polymer brushes as substrates for the incorporation of anthraquinone derivatives. Unprecedented application of decorated polymer brushes on organocatalysis

    Science.gov (United States)

    Ruiz-Muelle, Ana Belén; Contreras-Cáceres, Rafael; Oña-Burgos, Pascual; Rodríguez-Dieguez, Antonio; López-Romero, Juan Manuel; Fernández, Ignacio

    2018-01-01

    The synthesis of amino-terminated anthraquinone derivatives and their incorporation onto polymer brushes for the fabrication of silicon-based nanometric functional coatings are described for the first time. The general process involves the covalent grafting of anthraquinone 1 onto two different polymer-brushes by amidation reactions. They are composed by amino- and carboxy-terminated poly(acrylic acid) chains (PAA-NH2- and PAA-COOH, respectively) tethered by one end to an underlying silicon oxide (SiO2) substrate in a polymer brush configuration. A third substrate is fabricated by UV induced hydrosilylation reaction using undecenoic acid as adsorbate on hydrogen-terminated Si(111) surfaces. One- and two-dimensional nuclear magnetic resonance (NMR), FT-IR, MS and X-ray diffraction (XRD) were used to characterize anthraquinone 1. Ellipsometric and X-ray photoelectron spectroscopy (XPS) measurements demonstrated the presence of the polymer brushes on the silicon wafers, and atomic force microscopy (AFM) was used to study its surface morphology. The covalent linkage between anthraquinone and polymer brushes was proven by XPS and confocal fluorescence microscopy. The resulting surfaces were assayed in the heterogenous organocatalytic transformation of (1H)-indole into 3-benzyl indole with moderate yields but with high recyclability.

  5. Coordination chemistry of 6-thioguanine derivatives with cobalt: toward formation of electrical conductive one-dimensional coordination polymers.

    Science.gov (United States)

    Amo-Ochoa, Pilar; Alexandre, Simone S; Hribesh, Samira; Galindo, Miguel A; Castillo, Oscar; Gómez-García, Carlos J; Pike, Andrew R; Soler, José M; Houlton, Andrew; Zamora, Félix; Harrington, Ross W; Clegg, William

    2013-05-06

    In this work we have synthetized and characterized by X-ray diffraction five cobalt complexes with 6-thioguanine (6-ThioGH), 6-thioguanosine (6-ThioGuoH), or 2'-deoxy-6-thioguanosine (2'-d-6-ThioGuoH) ligands. In all cases, these ligands coordinate to cobalt via N7 and S6 forming a chelate ring. However, independently of reagents ratio, 6-ThioGH provided monodimensional cobalt(II) coordination polymers, in which the 6-ThioG(-) acts as bridging ligand. However, for 2'-d-6-ThioGuoH and 6-ThioGuoH, the structure directing effect of the sugar residue gives rise to mononuclear cobalt complexes which form extensive H-bond interactions to generate 3D supramolecular networks. Furthermore, with 2'-d-6-ThioGuoH the cobalt ion remains in the divalent state, whereas with 6-ThioGuoH oxidation occurs and Co(III) is found. The electrical and magnetic properties of the coordination polymers isolated have been studied and the results discussed with the aid of DFT calculations, in the context of molecular wires.

  6. Influence of the supramolecular order on the electrical properties of 1D coordination polymers based materials.

    Science.gov (United States)

    Musumeci, Chiara; Osella, Silvio; Ferlauto, Laura; Niedzialek, Dorota; Grisanti, Luca; Bonacchi, Sara; Jouaiti, Abdelaziz; Milita, Silvia; Ciesielski, Artur; Beljonne, David; Hosseini, Mir Wais; Samorì, Paolo

    2016-01-28

    The generation, under self-assembly conditions, of coordination polymers on surface based combinations of a terpyridine-antracene-pyridine based tecton and Co(II) or Pd(II) cations is primarily governed by the coordination geometry of the metal center (octahedral and square planar respectively). While the octahedral Co(II) based polymer self-assembles in insulating films exhibiting randomly oriented crystalline domains, the planarity of Pd(II) based polymers leads to the formation of conductive π-π stacked fibrillar structures exhibiting anisotropically oriented domains. In the latter case, the favorable Pd-Pd and anthracene-anthracene wavefunction overlaps along the fiber direction are responsible for the large electronic couplings between adjacent chains, whereas small electronic couplings are instead found along individual polymer chains. These results provide important guidelines for the design of conductive metal coordination polymers, highlighting the fundamental role of both intra- as well as inter-chain interactions, thus opening up new perspectives towards their application in functional devices.

  7. Building-up novel coordination polymer with Zn(II) porphyrin dimer ...

    Indian Academy of Sciences (India)

    Building-up novel coordination polymer with Zn(II) porphyrin dimer: Synthesis, structures, surface morphology and effect of axial ligands. SK ASIF IKBAL, SANFAORI BRAHMA, AVINASH DHAMIJA and SANKAR PRASAD RATH. ∗. Department of Chemistry, Indian Institute of Technology Kanpur, Kanpur 208 016, India.

  8. coordination polymers derived from two different bis-pyridyl-bis-am

    Indian Academy of Sciences (India)

    Self-assembly, structures and properties of three new Ni(II) coordination polymers derived from two different bis-pyridyl-bis-amide ligands and two aromatic polycarboxylates. HONGYAN LIN. ∗. , JUNJUN SUN, GUOCHENG LIU. ∗. , XIANG WANG and PANWEN CHEN. Department of Chemistry, Bohai University, Jinzhou ...

  9. A rational route to SCM materials based on a 1-D cobalt selenocyanato coordination polymer.

    Science.gov (United States)

    Boeckmann, Jan; Näther, Christian

    2011-07-07

    Thermal annealing of a discrete complex with terminal SeCN anions and monodentate coligands enforces the formation of a 1D cobalt selenocyanato coordination polymer that shows slow relaxation of the magnetization. Therefore, this approach offers a rational route to 1D materials that might show single chain magnetic behaviour. This journal is © The Royal Society of Chemistry 2011

  10. Building-up novel coordination polymer with Zn (II) porphyrin dimer ...

    Indian Academy of Sciences (India)

    ... to the best of our knowledge, the first structural report of 1D-coordination polymer with porphyrin dimer. Solution structures of the complexes along with binding studies in solution between 1 and L have also been investigated. The morphology of the polymeric complex 1·L2 on silicon wafer surface was examined by Atomic ...

  11. coordination polymers derived from two different bis-pyridyl-bis-am

    Indian Academy of Sciences (India)

    Sci. Vol. 129, No. 1, January 2017, pp. 9–20. c Indian Academy of Sciences. DOI 10.1007/s12039-016-1213-y. REGULAR ARTICLE. Self-assembly, structures and properties of three new Ni(II) coordination polymers derived from two different bis-pyridyl-bis-amide ligands and two aromatic polycarboxylates. HONGYAN LIN.

  12. Crystal Engineering: Synthesis and Structural Analysis of Coordination Polymers with Wavelike Properties

    Directory of Open Access Journals (Sweden)

    Matasebia T. Munie

    2011-10-01

    Full Text Available Supramolecular coordination polymers with wavelike structures have been synthesized by self-assembly and their structures analyzed using the sine trigonometric function. Slow evaporation of a methylene chloride-methanol solution of a 1:1 molar mixture of [M(tmhd2], where M = Co or Ni, and quinoxaline; a 1:2:1 molar mixture of [M(acac2], where M = Co or Ni, 2,2,6,6-tetramethyl-3,5-heptadione and quinoxaline; or a 1:2:1 molar mixture of [Co(acac2], dibenzoylmethane, and quinoxaline, yielded the crystalline coordination polymers. In the presence of the nitrogenous base, ligand scrambling occurs yielding the most insoluble product. The synthesis and structures of the following wavelike polymers are reported: trans-[Co(DBM2(qox]n·nH2O (2, trans-[Co(tmhd2(qox]n (3, trans-[Ni(tmhd2(qox]n (4, where DBM− = dibenzoylmethanate, tmhd− = 2,2,6,6-tetramethyl-3,5-heptadionate, and qox = quinoxaline. The wavelike structures are generated by intramolecular steric interactions and crystal packing forces between the chains. Some of the tert-butyl groups show a two-fold disorder. The sine function, φ = A sin 2πx/λ, where φ = distance (Ǻ along the polymer backbone, λ = wavelength (Ǻ, A = amplitude (Ǻ, x = distance (Ǻ along the polymer axis, provides a method to approximate and visualize the polymer structures.

  13. Crystal structures of coordination polymers from CaI2 and proline

    Directory of Open Access Journals (Sweden)

    Kevin Lamberts

    2015-06-01

    Full Text Available Completing our reports concerning the reaction products from calcium halides and the amino acid proline, two different solids were found for the reaction of l- and dl-proline with CaI2. The enantiopure amino acid yields the one-dimensional coordination polymer catena-poly[[aqua-μ3-l-proline-tetra-μ2-l-proline-dicalcium] tetraiodide 1.7-hydrate], {[Ca2(C5H9NO25(H2O]I4·1.7H2O}n, (1, with two independent Ca2+ cations in characteristic seven- and eightfold coordination. Five symmetry-independent zwitterionic l-proline molecules bridge the metal sites into a cationic polymer. Racemic proline forms with Ca2+ cations heterochiral chains of the one-dimensional polymer catena-poly[[diaquadi-μ2-dl-proline-calcium] diiodide], {[Ca(C5H9NO22(H2O2]I2}n, (2. The centrosymmetric structure is built by one Ca2+ cation that is bridged towards its symmetry equivalents by two zwitterionic proline molecules. In both structures, the iodide ions remain non-coordinating and hydrogen bonds are formed between these counter-anions, the amino groups, coordinating and co-crystallized water molecules. While the overall composition of (1 and (2 is in line with other structures from calcium halides and amino acids, the diversity of the carboxylate coordination geometry is quite surprising.

  14. Anion-Controlled Architecture and Photochromism of Naphthalene Diimide-Based Coordination Polymers

    Directory of Open Access Journals (Sweden)

    Jian-Jun Liu

    2018-02-01

    Full Text Available Three new cadmium coordination polymers, namely [Cd(NO32(DPNDI(CH3OH]·CH3OH (1, [Cd(SCN2(DPNDI] (2, and [Cd(DPNDI2(DMF2]·2ClO4 (3 (DPNDI = N,N-di(4-pyridyl-1,4,5,8-naphthalene diimide, DMF = N,N-dimethylformamide have been synthesized by reactions of DPNDI with Cd(NO32, Cd(SCN2, and Cd(ClO42, respectively. Compound 1 is a one-dimensional coordination polymer with strong lone pair-π interactions between the coordinated NO3− anions and the imide ring of DPNDI; while 2 is a two-dimensional network with a (4, 4 net topology. In the case of 3, due to the presence of uncoordinated perchlorate counter ions, it exhibits a non-interpenetrated square-grid coordination polymer containing one-dimensional rhomboid channels. The structural diversity in these compounds is attributed to different coordination abilities and geometries of counter anions. Due to the presence of electron-deficient NDI moiety, the photochromic behavior of these compounds was studied. Interestingly, only compounds 1 and 3 exhibit color changes under light irradiation. The influence of the anions on the photochromism process of the NDI-based materials has been discussed.

  15. Coordination polymers from a highly flexible alkyldiamine-derived ligand: structure, magnetism and gas adsorption studies.

    Science.gov (United States)

    Hawes, Chris S; Chilton, Nicholas F; Moubaraki, Boujemaa; Knowles, Gregory P; Chaffee, Alan L; Murray, Keith S; Batten, Stuart R; Turner, David R

    2015-10-28

    The synthesis and structural, magnetic and gas adsorption properties of a series of coordination polymer materials prepared from a new, highly flexible and internally functional tetrakis-carboxybenzyl ligand H4L derived from 1,2-diaminoethane have been examined. The compound poly-[Ni3(HL)2(OH2)4]·2DMF·2H2O 1, a two-dimensional coordination polymer, contains aqua- and carboxylato-bridged trinuclear Ni(II) clusters, the magnetic behaviour of which can be well described through experimental fitting and ab initio modelling to a ferromagnetically coupled trimer with a positive axial zero-field splitting parameter D. Compound poly-[Zn2L]·2DMF·3H2O 2, a three-dimensional coordination polymer displaying frl topology, contains large and well-defined solvent channels, which are shown to collapse on solvent exchange or drying. Compound poly-[Zn2(L)(DMSO)4]·3DMSO·3H2O 3, a highly solvated two-dimensional coordination polymer, displayed poor stability characteristics, however a structurally related material poly-[Zn2(L)(bpe)(DMSO)2]·DMSO·3H2O 4 was prepared under similar synthetic conditions by including the 1,2-bis(4-pyridyl)ethylene bpe co-ligand. Compound 4, containing small one-dimensional solvent channels, shows excellent structural resilience to solvent exchange and evacuation, and the evacuated material displays selective adsorption of CO2 over N2 at 273 K in the pressure range 0-1 atm. Each of the coordination polymers displays subtle differences in the conformation and binding mode of the ligand species, with switching between two distinct conformers (X-shaped and H-shaped), as well as a variable protonation state of the central core, with significant effects on the resulting network structures and physical properties of the materials.

  16. Multifunctionality of organometallic quinonoid metal complexes: surface chemistry, coordination polymers, and catalysts.

    Science.gov (United States)

    Kim, Sang Bok; Pike, Robert D; Sweigart, Dwight A

    2013-11-19

    Quinonoid metal complexes have potential applications in surface chemistry, coordination polymers, and catalysts. Although quinonoid manganese tricarbonyl complexes have been used as secondary building units (SBUs) in the formation of novel metal-organometallic coordination networks and polymers, the potentially wider applications of these versatile linkers have not yet been recognized. In this Account, we focus on these diverse new applications of quinonoid metal complexes, and report on the variety of quinonoid metal complexes that we have synthesized. Through the use of [(η(6)-hydroquinone)Mn(CO)3](+), we are able to modify the surface of Fe3O4 and FePt nanoparticles (NPs). This process occurs either by the replacement of oleylamine with neutral [(η(5)-semiquinone)Mn(CO)3] at the NP surface, or by the binding of anionic [(η(4)-quinone)Mn(CO)3](-) upon further deprotonation of [(η(5)-semiquinone)Mn(CO)3] at the NP surface. We have demonstrated chemistry at the intersection of surface-modified NPs and coordination polymers through the growth of organometallic coordination polymers onto the surface modified Fe3O4 NPs. The resulting magnetic NP/organometallic coordination polymer hybrid material exhibited both the unique superparamagnetic behavior associated with Fe3O4 NPs and the paramagnetism attributable to the metal nodes, depending upon the magnetic range examined. By the use of functionalized [(η(5)-semiquinone)Mn(CO)3] complexes, we attained the formation of an organometallic monolayer on the surface of highly ordered pyrolitic graphite (HOPG). The resulting organometallic monolayer was not simply a random array of manganese atoms on the surface, but rather consisted of an alternating "up and down" spatial arrangement of Mn atoms extending from the HOPG surface due to hydrogen bonding of the quinonoid complexes. We also showed that the topology of metal atoms on the surface could be controlled through the use of quinonoid metal complexes. A quinonoid

  17. Porous coordination polymer with flexibility imparted by coordinatively changeable lithium ions on the pore surface.

    Science.gov (United States)

    Xie, Lin-Hua; Lin, Jian-Bin; Liu, Xiao-Min; Wang, Yu; Zhang, Wei-Xiong; Zhang, Jie-Peng; Chen, Xiao-Ming

    2010-02-01

    Solvothermal reactions of equimolar zinc acetate, lithium acetate, and 1,3,5-benzenetricarboxylic acid (H(3)btc) in different mixed solvents yielded isostructural three-dimensional frameworks [LiZn(btc)(cG)].lG [cG and lG denote coordinated and lattice guests, respectively; cG = (nmp)(0.5)(H(2)O)(0.5), lG = (EtOH)(0.5) (1a); cG = H(2)O, lG = EtOH (1b); nmp = N-methyl-2-pyrrolidone] with one-dimensional channels occupied by guest molecules and solvent-coordinated, extrusive Li(+) ions. Thermogravimetry analyses and powder X-ray diffraction measurements revealed that both 1a and 1b can lose all lattice and coordinated guests to form a desolvated phase [LiZn(btc)] (MCF-27, 1) and almost retains the original framework structure. Gas adsorption measurements on 1 confirmed its permanent porosity but suggested a structural transformation from 1a/1b to 1. It is noteworthy that only 1a can undergo a single-crystal to single-crystal (SCSC) transformation into 1 upon desolvation. The crystal structure of 1 revealed that the Li(+) ions were retracted into the channel walls via complementary coordination to the carboxylate oxygen atoms in the framework rather than being exposed on the pore surface. Single-crystal X-ray diffraction analyses were also performed for N(2)- and CO(2)-loaded samples of 1, revealing that the framework remained unchanged when the gases were adsorbed. Although the gas molecules could not be modeled, the residue electrons inside the channels demonstrated that the retracted Li(+) ions still behave as the primary interacting site for CO(2) molecules. Nevertheless, solvent molecules such as H(2)O can readily compete with the framework oxygen atom to retrieve the extrusive Li(+) ions, accompanying the reverse structural transformation, i.e., from 1 to 1a/1b.

  18. Neutron radiation shielding properties of polymer incorporated self compacting concrete mixes.

    Science.gov (United States)

    Malkapur, Santhosh M; Divakar, L; Narasimhan, Mattur C; Karkera, Narayana B; Goverdhan, P; Sathian, V; Prasad, N K

    2017-07-01

    In this work, the neutron radiation shielding characteristics of a class of novel polymer-incorporated self-compacting concrete (PISCC) mixes are evaluated. Pulverized high density polyethylene (HDPE) material was used, at three different reference volumes, as a partial replacement to river sand in conventional concrete mixes. By such partial replacement of sand with polymer, additional hydrogen contents are incorporated in these concrete mixes and their effect on the neutron radiation shielding properties are studied. It has been observed from the initial set of experiments that there is a definite trend of reductions in the neutron flux and dose transmission factor values in these PISCC mixes vis-à-vis ordinary concrete mix. Also, the fact that quite similar enhanced shielding results are recorded even when reprocessed HDPE material is used in lieu of the virgin HDPE attracts further attention. Copyright © 2017 Elsevier Ltd. All rights reserved.

  19. A General Model of Sensitized Luminescence in Lanthanide-Based Coordination Polymers and Metal-Organic Framework Materials.

    Science.gov (United States)

    Einkauf, Jeffrey D; Clark, Jessica M; Paulive, Alec; Tanner, Garrett P; de Lill, Daniel T

    2017-05-15

    Luminescent lanthanides containing coordination polymers and metal-organic frameworks hold great potential in many applications due to their distinctive spectroscopic properties. While the ability to design coordination polymers for specific functions is often mentioned as a major benefit bestowed on these compounds, the lack of a meaningful understanding of the luminescence in lanthanide coordination polymers remains a significant challenge toward functional design. Currently, the study of these compounds is based on the antenna effect as derived from molecular systems, where organic antennae are used to facilitate lanthanide-centered luminescence. This molecular-based approach does not take into account the unique features of extended network solids, particularly the formation of band structure. While guidelines for the antenna effect are well established, they require modification before being applied to coordination polymers. A series of nine coordination polymers with varying topologies and organic linkers were studied to investigate the accuracy of the antenna effect in coordination polymer systems. By comparing a molecular-based approach to a band-based one, it was determined that the band structure that occurs in aggregated organic solids needs to be considered when evaluating the luminescence of lanthanide coordination polymers.

  20. Syntheses, structures and photoelectric properties of a series of Cd(II)/Zn(II) coordination polymers and coordination supramolecules

    International Nuclear Information System (INIS)

    Jin Jing; Han Xiao; Meng Qin; Li Dan; Chi Yuxian; Niu Shuyun

    2013-01-01

    Five Cd(II)/Zn(II) complexes [Cd(1,2-bdc)(pz) 2 (H 2 O)] n (1), [Cd1Cd2(btec)(H 2 O) 6 ] n (2), [Cd(3,4-pdc) (H 2 O)] n (3), [Zn(2,5-pdc)(H 2 O) 4 ]·2H 2 O (4) and { [Zn(2,5-pdc)(H 2 O) 2 ]·H 2 O} n (5) (H 2 bdc=1,2-benzenedicarboxylic acid, pz=pyrazole, H 4 btec=1,2,4,5-benzenetetracarboxylic acid, H 2 pdc=pyridine-dicarboxylic acid) were hydrothermally synthesized and characterized by single-crystal X-ray diffraction, surface photovoltage spectroscopy, XRD, TG analysis, IR and UV–vis spectra and elemental analysis. Structural analyses show that complexes 1–3 are 1D, 2D and 3D Cd(II) coordination polymers, respectively. Complex 4 is a mononuclear Zn(II) complex. Complex 5 is a 3D Zn(II) coordination polymer. The surface photoelectric properties of complexes were investigated by SPS. The results indicate that all complexes exhibit photoelectric responses in the range of 300–600 nm, which reveals that they all possess certain photoelectric conversion properties. By the comparative analyses, it can be found that the species and coordination micro-environment of central metal ion, the species and property of ligands affect the intensity and scope of photoelectric response. - Graphical abstract: Five Cd(II)/Zn(II) complexes have been hydrothermally synthesized and characterized. The photoelectric properties were studied with SPS. The species and coordination micro-environment of central metal ion, the species and property of ligands all affect the photoelectric responses. Highlights: ► Five Cd/Zn complexes have been synthesized and characterized. ► The SPS results indicate they possess obvious photoelectric conversion property. ► The species and coordination environment of central metal ion affect SPS. ► The species and property of ligands affect SPS. ► By the energy-band theory and the crystal filed theory, the SPS are analyzed and assigned.

  1. Temperature Stability and Bioadhesive Properties of Δ9-Tetrahydrocannabinol Incorporated Hydroxypropylcellulose Polymer Matrix Systems

    Science.gov (United States)

    Repka, Michael A.; Munjal, Manish; ElSohly, Mahmoud A.; Ross, Samir A.

    2010-01-01

    The purpose of this study was to determine and compare the bioadhesive profiles of hydroxypropylcellulose (HPC) polymer matrices as a function of Δ9-tetrahydrocannabinol (THC) content. In addition, the effect of processing temperature on the stability of THC and its extent of degradation to cannabinol (CBN) was investigated. A hot-melt cast molding method was used to prepare HPC polymer matrix systems incorporated with THC at 0, 4, 8, and 16 percent. Bioadhesive measurements including peak adhesive force, area under the curve, and elongation at adhesive failure were recorded utilizing the TA.XT2i Texture Analyzer™. Data obtained from these tests at various contact time intervals suggested that the incorporation of THC led to an increase in the bioadhesive strength of the HPC polymer matrices. To determine the stability of THC and the resulting CBN content in the matrices, three different processing temperatures were utilized (120, 160, and 200°C). Post-production High Performance Liquid Chromotography (HPLC) analysis revealed that the processed systems contained at least 94% of THC and the relative percent formation of CBN was 0.5% at 120°C and 0.4% at 160°C compared to 1.6% at 200°C. These findings indicate that the cannabinoid may be a plausible candidate for incorporation into systems utilizing hot-melt extrusion techniques for the development of an effective mucoadhesive transmucosal matrix system for delivery of THC. PMID:16455601

  2. Revised mechanism of d-alanine incorporation into cell wall polymers in Gram-positive bacteria

    Science.gov (United States)

    Reichmann, Nathalie T.; Cassona, Carolina Picarra

    2013-01-01

    Teichoic acids (TAs) are important for growth, biofilm formation, adhesion and virulence of Gram-positive bacterial pathogens. The chemical structures of the TAs vary between bacteria, though they typically consist of zwitterionic polymers that are anchored to either the peptidoglycan layer as in the case of wall teichoic acid (WTA) or the cell membrane and named lipoteichoic acid (LTA). The polymers are modified with d-alanines and a lack of this decoration leads to increased susceptibility to cationic antimicrobial peptides. Four proteins, DltA–D, are essential for the incorporation of d-alanines into cell wall polymers and it has been established that DltA transfers d-alanines in the cytoplasm of the cell onto the carrier protein DltC. However, two conflicting models have been proposed for the remainder of the mechanism. Using a cellular protein localization and membrane topology analysis, we show here that DltC does not traverse the membrane and that DltD is anchored to the outside of the cell. These data are in agreement with the originally proposed model for d-alanine incorporation through a process that has been proposed to proceed via a d-alanine undecaprenyl phosphate membrane intermediate. Furthermore, we found that WTA isolated from a Staphylococcus aureus strain lacking LTA contains only a small amount of d-alanine, indicating that LTA has a role, either direct or indirect, in the efficient d-alanine incorporation into WTA in living cells. PMID:23858088

  3. Incidental Polymorphism, Non-Isomorphic and Isomorphic Substitution in Calcium-Valine Coordination Polymers

    Directory of Open Access Journals (Sweden)

    Kevin Lamberts

    2015-05-01

    Full Text Available Five coordination polymers with the stoichiometry CaX2(valine2(H2O2 (X = Cl, Br were obtained from the corresponding calcium halides and either racemic and enantiopure valine. In all cases the zwitterionic amino acid is exclusively O coordinated and the halides act as counteranions for the resulting one-dimensional cationic chains. The enantiopure chloride shows dimorphism; both forms differ in connectivity from the bromide. In contrast to this structural variability for L-valine, the derivatives of the racemic amino acid are isomorphous.

  4. Synthesis, characterisation and thermal degradation behaviour of some coordination polymers by using TG–DTG and DTA techniques

    Directory of Open Access Journals (Sweden)

    Ratiram Gomaji Chaudhary

    2015-07-01

    Full Text Available The four chelate polymer complexes commonly called as coordination polymers of Mn(II, Co(II, Ni(II and Cu(II ions with fbpmpc (fbpmpc = fumaroyl bis (paramethoxyphenylcarbamide were synthesized and characterised by elemental analyses, infrared spectroscopy, diffuse reflectance, magnetic moment susceptibility, thermal analysis, X-ray diffraction, electrical conductivity and scanning electron microscopy technique (SEM. SEM investigations of coordination polymers were found in different shapes and sizes, though they are synthesized from a single ligand. Each metal ion is coordinated by a bis (bidentate manner through oxygen atom of the carboxylato group and the nitrogen atom of an amide group of ligand and two aqua ligands by coordinated bond which formed 6-member heterocyclic ring. In the present article, the main aim of research study is to find out the comparative studies of coordination polymers such as thermogravimetry (TG, derivative thermogravimetry (DTG, differential thermal analysis (DTA, electrical conductivity and morphology behaviour. Furthermore, the electrical conductivities of chelating ligand and coordination polymers were determined in the solid state powder form. The electrical conductivities measurements of undoped and doped ligand, coordination polymers were carried out at room temperature by the four probe technique using an electrometer. Thermal degradation studies of the coordination polymers have been carried out from a non-isothermal condition under nitrogen atmosphere at a heating rate of 10 °C min−1. The decomposition steps and thermal stabilities of these complexes were confirmed by thermal analysis techniques (TG/DTG/DTA. The thermal studies inferred the presence of crystallized water in all coordination polymers, whereas coordinated water was found in Ni(II and Cu(II ions.

  5. Synthesis, structure, luminescence and photocatalytic properties of an uranyl-2,5-pyridinedicarboxylate coordination polymer

    Science.gov (United States)

    Si, Zhen-Xiu; Xu, Wei; Zheng, Yue-Qing

    2016-07-01

    An uranium coordination polymer, namely [(UO2(pydc)(H2O)]·H2O (1) (H2pydc=2,5-pyridinedicarboxylic acid), has been obtained by hydrothermal method and characterized by X-ray single crystal structure determination. Structural analysis reveals that complex 1 exhibits 1D chain coordination polymer, in which UO22+ ions are bridged by 2,5-pyridinedicarboxylate ligands and the chains are connected into a 3D supramolecular network by O-H···O hydrogen bond interactions and π-π stacking interactions. The photocatalytic properties of 1 for degradation of methylene blue (MB), Rhodamine B (RhB) and methyl orange (MO) under Hg-lamp irradiation have been performed, and the amount of the catalyst as well as Hg-lamp irradiation with different power on the photodegradation efficiency of MB have been investigated. Elemental analyses, infrared spectroscopy, TG-DTA analyses and luminescence properties were also discussed.

  6. A new three-dimensional bis(benzimidazole)-based cadmium(II) coordination polymer

    Science.gov (United States)

    Hao, Shao Yun; Hou, Suo Xia; Hao, Zeng Chuan; Cui, Guang Hua

    2018-01-01

    A new coordination polymer (CP), formulated as [Cd(L)(DCTP)]n (1) (L = 1,1‧-(1,4-butanediyl)bis(2-methylbenzimidazole), H2DCTP = 2,5-dichloroterephthalic acid), was synthesized under hydrothermal conditions and the performance as luminescent probe was also investigated. Single-crystal X-ray diffraction reveals CP 1 is a 3D 3-fold interpenetrated dia network with large well-defined pores. It is found that CP 1 revealed highly sensitive luminescence sensing for Fe3 + ions in acetonitrile solution with a high quenching efficiency of KSV = 2541.238 L·mol- 1 and a low detection limit of 3.2 μM (S/N = 3). Moreover, the photocatalytic efficiency of 1 for degradation of methylene blue could reach 82.8% after 135 min. Therefore, this coordination polymer could be viewed as multifunctional material for selectively sensing Fe3 + ions and effectively degrading dyes.

  7. Synthesis of late transition nickel(II) coordination polymer and their catalysis for olefinic polymerization

    Science.gov (United States)

    Chenfei, Xu; Zhang, Danfeng

    2017-09-01

    It was illustrated in this paper the successful synthesization of one α-diimine ligand and one new polycondensate ligand. The structure of the ligand was characterized by 1H NMR spectrum, and the structure of the polycondensate ligand was characterized by Thermogravimetric Analysis (TGA) and Element Analysis. Then these two ligands reacted with (DME)NiBr2 for the purpose of preparing α-diimine nickel complex and nickel coordination polymer characterized by Element Analysis and X-ray Photoelectron Spectroscopy (XPS). Then these two catalysts were adopted to facilitate ethylene polymerization and to compare the difference between them. It was found that the activities from nickel coordination polymer/MAO reached 106(g/molNi·h) and the molecule weights were about 105.

  8. Superconductivity in a copper(II)-based coordination polymer with perfect kagome structure

    Energy Technology Data Exchange (ETDEWEB)

    Huang, Xing; Liu, Liyao; Xu, Wei; Zhu, Daoben [Beijing National Laboratory for Molecular Sciences, Key Laboratory of Organic Solids, Institute of Chemistry, Chinese Academy of Sciences, Beijing (China); University of Chinese Academy of Sciences, Beijing (China); Zhang, Shuai [Beijing National Laboratory for Condensed Matter Physics, Institute of Physics, Chinese Academy of Sciences, Beijing (China); Yu, Lei [Department of Chemistry, University of Kentucky, Lexington, KY (United States); Chen, Genfu [Beijing National Laboratory for Condensed Matter Physics, Institute of Physics, Chinese Academy of Sciences, Beijing (China); University of Chinese Academy of Sciences, Beijing (China); Collaborative Innovation Center of Quantum Matter, Beijing (China)

    2018-01-02

    A highly crystalline copper(II) benzenehexathiolate coordination polymer (Cu-BHT) has been prepared. The two-dimensional kagome structure has been confirmed by powder X-ray diffraction, high-resolution transmission electron microscopy, and high-resolution scanning transmission electron microscopy. The as-prepared sample exhibits bulk superconductivity at about 0.25 K, which is confirmed by the zero resistivity, AC magnetic susceptibility, and specific heat measurements. Another diamagnetic transition at about 3 K suggests that there is a second superconducting phase that may be associated with a single layer or few layers of Cu-BHT. It is the first time that superconductivity has been observed in a coordination polymer. (copyright 2018 Wiley-VCH Verlag GmbH and Co. KGaA, Weinheim)

  9. New twists and turns for actinide chemistry: organometallic infinite coordination polymers of thorium diazide

    International Nuclear Information System (INIS)

    Monreal, Marisa J.; Seaman, Lani A.; Goff, George S.; Michalczyk, Ryszard; Morris, David E.; Scott, Brian L.; Kiplinger, Jaqueline L.

    2016-01-01

    Two organometallic 1D infinite coordination polymers and two organometallic monometallic complexes of thorium diazide have been synthesized and characterized. Steric control of these self-assembled arrays, which are dense in thorium and nitrogen, has also been demonstrated: infinite chains can be circumvented by using steric bulk either at the metallocene or with a donor ligand in the wedge. (copyright 2016 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

  10. New Cu(II) coordination polymer by chiral tridentate Schiff base ligand

    Science.gov (United States)

    Messai, Amel; Bilge, Duygu; Bilge, Metin; Parlak, Cemal

    2017-06-01

    The present research reports the synthesis, X-ray, magnetic and electronic properties for novel coordination polymer based upon copper (II) with chiral tridentate Schiff base ligand synthesized at condensation of acetylacetone and L-leucine amino acid. The investigation was also conducted by quantum mechanical calculations. The large energy gap indicates a high kinetic stability. Magnetic measurement gives predominant antiferromagnetic interactions within the chain. Results reveals further insight into copper(II) chiral tridentate Schiff base complexes.

  11. Homochiral coordination polymers with helixes and metal clusters based on lactate derivatives

    Energy Technology Data Exchange (ETDEWEB)

    Xu, Zhong-Xuan, E-mail: xuzhongxuan4201@163.com [Department of Chemistry, Zunyi Normal College, Zunyi, Guizhou 563002 (China); Ma, Yu-Lu [School of Chemical Science and Technology, Yunnan University, Kunming 650091 (China); Lv, Guo-ling [Department of Chemistry, Zunyi Normal College, Zunyi, Guizhou 563002 (China)

    2017-05-15

    Utilizing the lactic acid derivatives (R)-4-(1-carboxyethoxy)benzoic acid (denoted: (R)-H{sub 2}CBA) and (S)-4-(1-carboxyethoxy)benzoic acid (denoted: (S)-H{sub 2}CBA)as chiral linkers to self-assemble with 4, 4′-bipyridine (denoted: BIP) and Cd(II) ions, a couple of three-dimensional homochiral coordination polymers, namely [Cd{sub 3}((R)-CBA){sub 3} (BIP){sub 2}(H{sub 2}O)]·xGuest (1-D) and [Cd{sub 3}((S)-CBA){sub 3}(BIP){sub 2}(H{sub 2}O)]·xGuest (1-L), have been synthesized under solvothermal reaction condition. Single crystal X-ray diffraction analysis reveals the two complexes contain single helical chains based on enantiopure ligands and cadmium clusters. Moreover, some physical characteristics such as PXRD, thermal stability, solid-state circular dichroism (CD) and luminescent were also investigated. - Graphical abstract: Utilizing enantiomeric lactic acid derivatives (R)-H{sub 2}CBA and (S)-H{sub 2}CBA to assemble with Cd{sup 2+} ions and ancillary BIP ligands, a couple of 3D homochiral coordination polymers with metal clusters and helical chains have been prepared by hydrothermal reaction. - Highlights: • Chiral lactic acid derivative. • Enantiomeric coordination polymer. • Helical chain. • Trinuclear cadmium cluster.

  12. Diverse lanthanide coordination polymers tuned by the flexibility of ligands and the lanthanide contraction effect: syntheses, structures and luminescence.

    Science.gov (United States)

    Zhou, Xiaoyan; Guo, Yanling; Shi, Zhaohua; Song, Xueqin; Tang, Xiaoliang; Hu, Xiong; Zhu, Zhentong; Li, Pengxuan; Liu, Weisheng

    2012-02-14

    Two new flexible exo-bidentate ligands were designed and synthesized, incorporating different backbone chain lengths bearing two salicylamide arms, namely 2,2'-(2,2'-oxybis(ethane-2,1-diyl)bis(oxy))bis(N-benzylbenzamide) (L(I)) and 2,2'-(2,2'-(ethane-1,2-diylbis(oxy))bis(ethane-2,1-diyl))bis(oxy)bis(N-benzylbenzamide) (L(II)). These two structurally related ligands are used as building blocks for constructing diverse lanthanide polymers with luminescent properties. Among two series of lanthanide nitrate complexes which have been characterized by elemental analysis, TGA analysis, X-ray powder diffraction, and IR spectroscopy, ten new coordination polymers have been determined using X-ray diffraction analysis. All the coordination polymers exhibit the same metal-to-ligand molar ratio of 2 : 3. L(I), as a bridging ligand, reacts with lanthanide nitrates forming two different types of 2D coordination complexes: herringbone framework {[Ln(2)(NO(3))(6)(L(I))(3)·mC(4)H(8)O(2)](∞) (Ln = La (1), and Pr (2), m = 1, 2)} as type I,; and honeycomb framework {[Ln(2)(NO(3))(6)(L(I))(3)·nCH(3)OH](∞) (Ln = Nd (3), Eu (4), Tb (5), and Er (6), n = 0 or 3)} as type II, which change according to the decrease in radius of the lanthanide. For L(II), two distinct structure types of 1D ladder-like coordination complexes were formed with decreasing lanthanide radii: [Ln(2)(NO(3))(6)(L(II))(3)·2C(4)H(8)O(2)](∞) (Ln = La (7), Pr (8), Nd (9)) as type III, [Ln(2)(NO(3))(6)(L(I))(3)·mC(4)H(8)O(2)·nCH(3)OH](∞) (Ln = Eu (10), Tb (11), and Er (12), m, n = 2 or 0) as type IV. The progressive structural variation from the 2D supramolecular framework to 1D ladder-like frameworks is attributed to the varying chain length of the backbone group in the flexible ligands. The photophysical properties of trivalent Sm, Eu, Tb, and Dy complexes at room temperature were also investigated in detail.

  13. Role of N-Donor Sterics on the Coordination Environment and Dimensionality of Uranyl Thiophenedicarboxylate Coordination Polymers

    Energy Technology Data Exchange (ETDEWEB)

    Thangavelu, Sonia G. [Department; Butcher, Ray J. [Department; Cahill, Christopher L. [Department

    2015-06-09

    Thiophene 2,5-dicarboxylic acid (TDC) was reacted with uranyl acetate dihydrate and one (or none) of six N-donor chelating ligands (2,2'-bipyridine (BPY), 4,4'-dimethyl-2,2'-bipyridine (4-MeBPY), 5,5'-dimethyl-2,2'-bipyridine (5-MeBPY), 6,6'-dimethyl-2,2'-bipyridine (6-MeBPY), 4,4',6,6'-tetramethyl-2,2'-bipyridine (4,6-MeBPY), and tetrakis(2-pyridyl)pyrazine (TPPZ) to result in the crystallization of seven uranyl coordination polymers, which were characterized by their crystal structures and luminescence properties. The seven coordination polymers, Na2[(UO2)2(C6H2O4S)3]·4H2O (1), [(UO2)4(C6H2O4S)5(C10H8N2)2]·C10H10N2·3H2O (2), [(UO2)(C6H2O4S)(C12H12N3)] (3), [(UO2)(C6H2O4S)(C12H12N3)]·H2O (4), [(UO2)2(C6H2O4S)3]·(C12H14N2)·5H2O (5), [(UO2)3(CH3CO2)(C6H2O4S)4](C14H17N2)3·(C14H16N2)·H2O (6), and [(UO2)2(C6H2O4S)3](C24H18N6) (7), consist of either uranyl hexagonal bipyramidal or pentagonal bipyramidal coordination geometries. In all structures, structural variations in the local and global structures of 1–7 are influenced by the positions (or number) of methyl groups or pyridyl rings on the N-donor species, thus resulting in a wide diversity of structures ranging from single chains, double chains, or 2-D sheets. Direct coordination of N-donor ligands to uranyl centers is observed in the chain structures of 2–4 using BPY, 4-MeBPY, and 5-MeBPY, whereas the N-donor species participate as guests (as either neutral or charge balancing species) in the chain and sheet structures of 5–7 using 6-MeBPY, 4,6-MeBPY, and TPPZ, respectively. Compound 1 is the only structure that does not contain any N-donor ligands and thus crystallizes as a 2-D interpenetrating sheet. The luminescent properties of 1–7 are influenced by the direct coordination or noncoordination of N-donor species to uranyl centers. Compounds 2–4 exhibit typical UO22+ emission upon direct coordination of N-donors, but its absence is observed in 1

  14. Heterobimetallic coordination polymers involving 3d metal complexes and heavier transition metals cyanometallates

    Energy Technology Data Exchange (ETDEWEB)

    Peresypkina, Eugenia V. [Nikolaev Institute of Inorganic Chemistry, SB RAS, Novosibirsk 630090 (Russian Federation); Samsonenko, Denis G. [Nikolaev Institute of Inorganic Chemistry, SB RAS, Novosibirsk 630090 (Russian Federation); Novosibirsk State University, Novosibirsk 630090 (Russian Federation); Vostrikova, Kira E., E-mail: vosk@niic.nsc.ru [Nikolaev Institute of Inorganic Chemistry, SB RAS, Novosibirsk 630090 (Russian Federation); LMI, Université Claude Bernard Lyon 1, 69622 Villeurbanne Cedex (France)

    2015-04-15

    The results of the first steps in the design of coordination polymers based on penta- and heptacyanometallates of heavier d transitions metals are presented. The 2D structure of the coordination polymers: [(Mn(acacen)){sub 2}Ru(NO)(CN){sub 5}]{sub n} and two complexes composed of different cyanorhenates, [Ni(cyclam)]{sub 2}[ReO(OH)(CN){sub 4}](ClO{sub 4}){sub 2}(H{sub 2}O){sub 1.25} and [Cu(cyclam)]{sub 2}[Re(CN){sub 7}](H{sub 2}O){sub 12}, was confirmed by single crystal XRD study, the rhenium oxidation state having been proved by the magnetic measurements. An amorphism of [M(cyclam)]{sub 3}[Re(CN){sub 7}]{sub 2} (M=Ni, Cu) polymers does not allow to define strictly their dimensionality and to model anisotropic magnetic behavior of the compounds. However, with high probability a honey-comb like layer structure could be expected for [M(cyclam)]{sub 3}[Re(CN){sub 7}]{sub 2} complexes, studied in this work, because such an arrangement is the most common among the bimetallic assemblies of hexa- and octacyanometallates with a ratio [M(cyclam)]/[M(CN){sub n}]=3/2. For the first time was prepared and fully characterized a precursor (n-Bu{sub 4}N){sub 2}[Ru(NO)(CN){sub 5}], soluble in organic media. - Graphical abstract: The very first results in the design of 2D coordination polymers based on penta- and heptacyanometallates of 4d and5d transitions metals are presented. - Highlights: • Design of coordination polymers based on penta- and heptacyanometallates. • New Ru and Re cyanide based heterobimetallic coordination complexes. • Hydrolysis and ox/red processes involving [Re(CN){sub 7}]{sup 3+} during crystallization. • High magnetic anisotropy of [M(cyclam)]{sub 3}[Re(CN){sub 7}]{sub 2}(H{sub 2}O){sub n}, M=Cu, Ni, complexes.

  15. Syntheses, structures and luminescent properties of lanthanide coordination polymers assembled from imidazophenanthroline derivative and oxalate ligands

    Energy Technology Data Exchange (ETDEWEB)

    Zhao, Hui; Sun, Xiao-Xia; Hu, Huai-Ming, E-mail: ChemHu1@NWU.EDU.CN; An, Ran; Yang, Meng-Lin; Xue, Ganglin

    2017-01-15

    Nine new lanthanide coordination polymers, namely, [Ln(Hsfpip)(ox){sub 0.5}(H{sub 2}O)]{sub n}·2n(H{sub 2}O) ((Ln=Eu (1), Tb (2), Dy (3), Ho (4), Er (5), Yb (6), Y(7)), [Ln(H{sub 2}sfpip)(ox)(H{sub 2}O){sub 4}]{sub n}·2n(H{sub 2}O) (Ln=Nd (8) Sm (9)), [H{sub 2}ox=oxalic acid, H{sub 3}sfpip=2-(2,4-disulfophenyl)imidazo(4,5-f)(1,10)-phenanthroline] have been synthesized under hydrothermal conditions and characterized by IR spectra, elemental analysis, powder X-ray diffraction and single crystal X-ray diffraction. When sodium oxalate is added, the reactions of lanthanide ions with H{sub 3}sfpip resulted in two types of structures. Compounds 1–7 are obtained at pH 5.0 and exhibit 3D tfz-d networks with ox{sup 2−} anions as linkers to bridge the adjacent layers. Compounds 8–9 are obtained at pH 2.0, and display a 1D chain which is further extended to a 3D supramolecular framework through intermolecular hydrogen bonds and π-π interactions. The structural variation from compounds 1–7 to 8–9 can attribute to the pH effect on construction of lanthanide coordination polymers. Moreover, the thermal stabilities and luminescence properties of 1–9 were also investigated. - Graphical abstract: Nine new lanthanide coordination polymers have been synthesized under hydrothermal conditions. Compounds 1–7 exhibit a 3D tfz-d network. Compounds 8–9 display a 1D chain structure. The structural variation from compounds 1–7 to 8–9 can attribute to the pH effect on construction of lanthanide coordination polymers. - Highlights: • Nine lanthanide coordination polymers were prepared under hydrothermal conditions. • Their crystal structures have been determined. • The luminescence and thermal stabilities were studied in the solid state.

  16. Synthesis, structure and fluorescence properties of a novel 3D Sr(II) coordination polymer

    Science.gov (United States)

    Tan, Yu-Hui; Xu, Qing; Gu, Zhi-Feng; Gao, Ji-Xing; Wang, Bin; Liu, Yi; Yang, Chang-Shan; Tang, Yun-Zhi

    2016-09-01

    Solvothermal reaction of 2,2‧-bipyridine-5,5‧-dicarboxylic acid (H2bpdc) and SrCl2 affords a novel coordination polymer [Sr(Hbpdc)2]n1. X-ray structure determination shows that 1 exhibits a novel three-dimensional network. The unique Sr II cation sits on a two-fold axis and coordinated by four O-atom donors from four Hbptc- ligands and four N-atom donors from two Hbptc- ligands in distorted dodecahedral geometry. In 1 each Sr II cation connects to six different Hbptc- ligands and each Hbptc- ligand bridges three different Sr II cations which results in the formation of a three-dimensional polymeric structure. Corresponding to the free ligand, the fluorescent emission of complex 1 display remarkable "Einstain" shifts, which may be attributed to the coordination interaction of Sr atoms, thus reduce the rigidity of pyridyl rings.

  17. A new nanocomposite polymer electrolyte based on poly(vinyl alcohol) incorporating hypergrafted nano-silica

    KAUST Repository

    Hu, Xian-Lei

    2012-01-01

    Solid-state nanocomposite polymer electrolytes based on poly(vinyl alcohol)(PVA) incorporating hyperbranched poly(amine-ester) (HBPAE) grafted nano-silica (denoted as SiO2-g-HBPAE) have been prepared and investigated. Through surface pretreatment of nanoparticles, followed by Michael-addition and a self-condensation process, hyperbranched poly(amine-ester) was directly polymerized from the surface of nano-silica. Then the hypergrafted nanoparticles were added to PVA matrix, and blended with lithium perchlorate via mold casting method to fabricate nanocomposite polymer electrolytes. By introducing hypergrafted nanoparticles, ionic conductivity of solid composite is improved significantly at the testing temperature. Hypergrafted nano-silica may act as solid plasticizer, promoting lithium salt dissociation in the matrix as well as improving segmental motion of matrix. In addition, tensile testing shows that such materials are soft and tough even at room temperature. From the dielectric spectra of nanocomposite polymer electrolyte as the function of temperature, it can be deduced that Arrhenius behavior appears depending on the content of hypergrafted nano-silica and concentration of lithium perchlorate. At a loading of 15 wt% hypergrafted nano-silica and 54 wt% lithium perchlorate, promising ionic conductivities of PVA nanocomposite polymer electrolyte are achieved, about 1.51 × 10 -4 S cm-1 at 25 °C and 1.36 × 10-3 S cm-1 at 100 °C. © The Royal Society of Chemistry.

  18. Thermostability and photophysical properties of mixed-ligand carboxylate/benzimidazole Zn(II)-coordination polymers

    Energy Technology Data Exchange (ETDEWEB)

    Barros, Bráulio Silva, E-mail: brauliobarros@ect.ufrn.br [School of Science and Technology, Federal University of Rio Grande do Norte (UFRN), Campus Universitário Lagoa Nova, 59078-970 Natal, RN (Brazil); Chojnacki, Jaroslaw [Department of Inorganic Chemistry, Chemical Faculty, Gdansk University of Technology, G. Narutowicza 11/12, 80-233 Gdansk (Poland); Macêdo Soares, Antonia Alice; Kulesza, Joanna; Lourenço da Luz, Leonis; Júnior, Severino Alves [Department of Fundamental Chemistry, Federal University of Pernambuco (UFPE), Av. Prof. Moraes Rego, 1235 – Cidade Universitária, 50670-901 Recife, PE (Brazil)

    2015-07-15

    The reaction between Zn(NO{sub 3}){sub 2}·6H{sub 2}O or Zn(CH{sub 3}COO){sub 2}·2H{sub 2}O and isophthalic acid (1,3-H{sub 2}bdc) in the presence of benzimidazole (Hbzim) in dimethylformamide (DMF)/ethanol (EtOH)/H{sub 2}O solvent mixture at room temperature yielded two structurally different coordination polymers: [Zn{sub 2}(1,3-bdc){sub 2}(Hbzim){sub 2}] (1) and [Zn{sub 2}(1,3-bdc)(bzim){sub 2}] (2). (1) is a 2D-layered framework with a molecule of benzimidazole coordinated to the Zn center, whereas (2) is a 3D framework with benzimidazolate species acting as a co-ligand and bridging two Zn(II) ions. Reactions performed at 90 °C led to the formation of coordination polymers structurally similar to (2), independently of the Zn(II) source used. In the absence of benzimidazole, the reaction between ZnAc{sub 2}.2H{sub 2}O and 1,3-H{sub 2}bdc at 90 °C resulted in the formation of (3), a 3D coordination polymer Zn(HCOO){sub 3}(Me{sub 2}NH{sub 2}{sup +}). It was observed that the thermostability and the photophysical properties of (1) and (2) are strongly dependent on the coordination modes and packing of benzimidazole in the solid state. These materials present photoluminescence in the wide range of the spectrum, from UV to IR. A full understanding of a physical process occurring in these intriguing systems, including complete energy level diagrams with possible transitions were provided. - Graphical abstract: Display Omitted - Highlights: • Structurally different Zn(II)-coordination polymers were prepared. • The formation of frameworks was counter anion and temperature dependent. • Photoluminescence in the wide range of the spectrum, from UV to IR was observed. • Thermostability and luminescence depended on bzim packing in the structure.

  19. Self-assembly of metal-organic coordination polymers constructed from a bent dicarboxylate ligand: diversity of coordination modes, structures, and gas adsorption.

    Science.gov (United States)

    Yang, Wenbin; Lin, Xiang; Blake, Alexander J; Wilson, Claire; Hubberstey, Peter; Champness, Neil R; Schröder, Martin

    2009-12-07

    We have synthesized five new metal-organic coordination polymers incorporating the bent ligand H(2)hfipbb [4,4'-(hexafluoroisopropylidene)bis(benzoic acid)] with different transition metal ions and co-ligands via solvothermal reactions to give [Zn(2)(hfipbb)(2)(py)(2)] x DMF (1), [Zn(2)(hfipbb)(2)(4,4'-bipy)(H(2)O)] (2), [Zn(2)(hfipbb)(2)(bpdab)].2DMF (3), [Cd(2)(hfipbb)(2)(DMF)(2)] x 2 DMF (4), and [Co(hfipbb)(dpp)] x MeOH (5) (py = pyridine, 4,4'-bipy = 4,4'-bipyridine, bpdab = 1,4-bis(4-pyridyl)-2,3-diaza-1,3-butadiene, dpp = 1,3-di(4-pyridyl)propane). Compound 1 displays a 2-fold 2D-->2D parallel interpenetrated layer network with one-dimensional (1D) helical channels, while 3 exhibits a three-dimensional pillared helical-layer open framework of alpha-Po topology based upon binuclear paddlewheel units. In compounds 2 and 5, binuclear motifs with double carboxylate bridges are linked by hfipbb(2-) ligands into a 1D ribbon, which are further assembled into two-dimensional non-interpenetrated (4,4) layers via bipyridyl co-ligands. However, the different bridging modes of hfipbb(2-) ligands and the different disposition of the coordinated co-ligands around metal ions result in subtle differences in the final architecture. Thus, 2 is based on a binuclear cluster node, double-stranded hfipbb(2-) linkers, and single-stranded 4,4'-bipy linkers, while 5 is based on a binuclear cluster node and hfipbb(2-) and dpp linkers which are both double-stranded. Among these compounds, the Cd(II) complex 4 is possibly the most interesting because it represents a rare example in which metal centers are linked by carboxylate groups into infinite chains further joined together by hfipbb(2-) spacers to form a 2D network with tubular helical channels. All these coordination polymers exhibit low solvent-accessible volumes. Both 3 and 4 retain structural integrity and permanent microporosity upon evacuation of guest molecules, with hydrogen uptakes of 0.57 and 0.78 wt %, respectively, at

  20. Formation of Gd coordination polymer with 1D chains mediated by Bronsted acidic ionic liquids

    Energy Technology Data Exchange (ETDEWEB)

    Luo, Qianqian; Han, Ying [Key Laboratory of Polar Materials and Devices, Ministry of Education, East China Normal University, Shanghai (China); Lin, Hechun, E-mail: hclin@ee.ecnu.edu.cn [Key Laboratory of Polar Materials and Devices, Ministry of Education, East China Normal University, Shanghai (China); Zhang, Yuanyuan; Duan, Chungang [Key Laboratory of Polar Materials and Devices, Ministry of Education, East China Normal University, Shanghai (China); Peng, Hui, E-mail: hpeng@ee.ecnu.edu.cn [Key Laboratory of Polar Materials and Devices, Ministry of Education, East China Normal University, Shanghai (China); Collaborative Innovation Center of Extreme Optics, Shanxi University, Taiyuan, Shanxi 030006 (China)

    2017-03-15

    One dimensional coordination polymer Gd[(SO{sub 4})(NO{sub 3})(C{sub 2}H{sub 6}SO){sub 2}] (1) is prepared through the mediation of Bronsted acid ionic liquid, which crystallized in the monoclinic space of C2/c. In this polymer, adjacent Gd atoms are linked by two SO{sub 4}{sup 2-} ions to generate a 1-D chain, and all oxygen atoms in SO{sub 4}{sup 2-} groups are connected to three nearest Gd atoms in µ{sup 3}:η{sup 1}:η{sup 1}:η{sup 2} fashion. Gd, S and N from SO{sub 4}{sup 2-} and NO{sub 3}{sup -} are precisely coplanar. The planar is coordinated by a pair of DMSO molecules, which is parallel and linked by hydrogen bonding to form a three-dimensional supramolecular network. Magnetic susceptibility measurement of 1 reveals weak antiferromagnetic interactions between the Gd (III) ions. It exhibits relatively large magneto-caloric effect with –ΔS{sub m}=28.8 J Kg{sup −1} K{sup −1} for ΔH=7 T. - Graphical abstract: Coordination polymer Gd[(SO{sub 4})(NO{sub 3})(C{sub 2}H{sub 6}SO){sub 2}] was obtained mediated by Bronsted acid Ionic Liquid, which presents a 1-D chains collected by SO{sub 4}{sup 2-} groups. Magnetic susceptibility of the polymer reveals weak antiferromagnetic interactions between the Gd(III) ions with the relatively large magneto-caloric effect of –ΔS{sub m}=28.8 J Kg{sup −1} K{sup −1} for ΔH= 7T.

  1. Structure and performance of polymer-derived bulk ceramics determined by method of filler incorporation

    Science.gov (United States)

    Konegger, T.; Schneider, P.; Bauer, V.; Amsüss, A.; Liersch, A.

    2013-12-01

    The effect of four distinct methods of incorporating fillers into a preceramic polymer matrix was investigated with respect to the structural and mechanical properties of the resulting materials. Investigations were conducted with a polysiloxane/Al2O3/ZrO2 model system used as a precursor for mullite/ZrO2 composites. A quantitative evaluation of the uniformity of filler distribution was obtained by employing a novel image analysis. While solvent-free mixing led to a heterogeneous distribution of constituents resulting in limited mechanical property values, a strong improvement of material homogeneity and properties was obtained by using solvent-assisted methods. The results demonstrate the importance of the processing route on final characteristics of polymer-derived ceramics.

  2. Novel 1D coordination polymer {Tm(Piv)3}n: Synthesis, structure, magnetic properties and thermal behavior

    International Nuclear Information System (INIS)

    Fomina, Irina; Dobrokhotova, Zhanna; Aleksandrov, Grygory; Emelina, Anna; Bykov, Mikhail; Malkerova, Irina; Bogomyakov, Artem; Puntus, Lada; Novotortsev, Vladimir; Eremenko, Igor

    2012-01-01

    The new 1D coordination polymer {Tm(Piv) 3 } n (1), where Piv=OOCBu t− , was synthesized in high yield (>95%) by the reaction of thulium acetate with pivalic acid in air at 100 °S. According to the X-ray diffraction data, the metal atoms in compound 1 are in an octahedral ligand environment unusual for lanthanides. The magnetic and luminescence properties of polymer 1, it’s the solid-phase thermal decomposition in air and under argon, and the thermal behavior in the temperature range of −50…+50 °S were investigated. The vaporization process of complex 1 was studied by the Knudsen effusion method combined with mass-spectrometric analysis of the gas-phase composition in the temperature range of 570–680 K. - Graphical Abstract: Novel 1D coordination polymer {Tm(Piv) 3 } n was synthesized and studied by X-ray diffraction. The magnetic, luminescence properties, the thermal behavior and the volatility for the compound {Tm(Piv) 3 } n were investigated.▪ Highlights: ► We synthesized the coordination polymer {Tm(Piv) 3 } n . ► Tm atoms in polymer have the coordination number 6. ► Polymer exhibits blue-color emission at room temperature. ► Polymer shows high thermal stability and volatility. ► Polymer has no phase transitions in the range of −50…+50 °S.

  3. Enhancing relative permittivity by incorporating PDMS-PEG multiblock copolymers in binary polymer blends

    DEFF Research Database (Denmark)

    A Razak, Aliff Hisyam; Szabo, Peter; Skov, Anne Ladegaard

    Polydimethylsiloxane (PDMS) elastomers are well-known to be soft and highly stretchable, yet they never achieve maximum elongation when utilised as dielectric elastomers, simply because their dielectric permittivity remains rather low. Conversely, polyethyleneglycols (PEG) are not stretchable......, but they do possess high permittivity. Combining two such polymers in a block copolymer allows for further crosslinking and presents the possibility of substantial improvements in the actuation response of the resulting dielectric elastomer – if carefully designed. The objective is to synthesise a PDMS......, the discontinuity in PEG can be acquired and the relative permittivity (ε’) is significantly enhanced (60%) with 5wt% of PDMS-PEG block copolymer incorporated into the silicone elastomer....

  4. Four unexpected lanthanide coordination polymers involving in situ reaction of solvent N, N-Dimethylformamide

    International Nuclear Information System (INIS)

    Jin, Jun-Cheng; Tong, Wen-Quan; Fu, Ai-Yun; Xie, Cheng-Gen; Chang, Wen-Gui; Wu, Ju; Xu, Guang-Nian; Zhang, Ya-Nan; Li, Jun; Li, Yong; Yang, Peng-Qi

    2015-01-01

    Four unexpected 2D lanthanide coordination polymers have been synthesized through in situ reactions of DMF solvent under solvothermal conditions. The isostructural complexes 1–3 contain four types of 2 1 helical chains. While the Nd(III) ions are bridged through μ 2 -HIDC 2− and oxalate to form a 2D sheet along the bc plane without helical character in 4. Therefore, complex 1 exhibits bright red solid-state phosphorescence upon exposure to UV radiation at room temperature. - Graphical abstract: Four unexpected 2D lanthanide coordination polymers have been synthesized through in situ reactions of solvent DMF to formate acid or oxalic acid under solvothermal conditions. The isostructural complexes 1–3 contain four types of different 2 1 helical chains in the 2D layer and 1 exhibits bright red solid-state phosphorescence upon UV radiation. - Highlights: • Four unexpected 2D lanthanide coordination compounds have been synthesized through in situ reactions under solvothermal conditions. • The complexes 1–3 contain four types of 2 1 helical chains in the layer. • Complex 1 exhibits bright red solid-state phosphorescence upon exposure to UV radiation at room temperature

  5. Two new coordination polymers based on tartaric acid ligand: Syntheses, crystal structure and thermal stability

    Energy Technology Data Exchange (ETDEWEB)

    Chen, Fei-Yan; Lan, You-Zhao, E-mail: sky37@zjnu.cn; Han, Min-Min; Feng, Yun-Long, E-mail: lyzhao@zjnu.cn [Zhejiang Normal University, Zhejiang Key Laboratory for Reactive Chemistry on Solid Surfaces, Institute of Physical Chemistry (China)

    2016-09-15

    Two new coordination polymers [Cd{sub 3}(D-Tar){sub 3}]{sub n} (1) and [Pb(meso-Tar)]{sub n} (2) (H{sub 2}Tar = tartaric acid) have been synthesized by hydrothermal reaction and characterized by single crystal X-ray diffraction analysis and IR spectra. 1 crystallizes in the C222{sub 1} chiral space group and shows a 3D (4,4)-connected net with the (4.6.8{sup 4}){sub 4}(4.6{sup 2}.8{sup 2}.10)(4.6{sup 2}.8{sup 3})(4.6{sup 3}.8{sup 2})(4.6{sup 3}.8{sup 2}){sub 4}(4.8{sup 5}){sub 2} topology. 2 possesses a 3D (4,4)-connected net with the (4{sup 3}.6{sup 2}.8) topology. In addition, the thermogravimetric analyses (TGA) results for polymers are discussed.

  6. A polythreaded Ag(I) coordination polymer: A rare three-dimensional Pseudo-polyrotaxana constructed from the same components

    Energy Technology Data Exchange (ETDEWEB)

    Im, Han Su; Lee, Eunji; Lee, Shim Sung; Kim, Tae Ho; Park, Ki Min [Research Institute of Natural Science and Dept. of Chemistry, Gyeongsang National University, Jinju (Korea, Republic of); Moon, Suk Hee [Dept. of Food and Nutrition, Kyungnam College of Information and Technology, Busan (Korea, Republic of)

    2017-01-15

    In supramolecular chemistry, a lot of mechanically poly-threaded coordination polymers, such as polyrotaxanes, based on self-assembly of organic ligands and transition metal ions have attracted great attention over the past two decades because of their fascinating architectures as well as their potential application in material science. Among them, 1D + 2D → 3D pseudo-polyrotaxane constructed by the penetration of 1D coordination polymer chains into 1D channels formed by parallel stacking of 2D porous coordination layers is a quite rare topology. Until now, only a few examples of 1D + 2D → 3D pseudo-polyrotaxanes have been reported.

  7. Comparison of selenophene and thienothiophene incorporation into pentacyclic lactam-based conjugated polymers for organic solar cells

    KAUST Repository

    Kroon, Renee

    2015-09-08

    In this work, we compare the effect of incorporating selenophene versus thienothiophene spacers into pentacyclic lactam-based conjugated polymers for organic solar cells. The two cyclic lactam-based copolymers were obtained via a new synthetic method for the lactam moiety. Selenophene incorporation results in a broader and red-shifted optical absorption while retaining a deep highest occupied molecular orbital level, whereas thienothienophene incorporation results in a blue-shifted optical absorption. Additionally, grazing-incidence wide angle X-ray scattering data indicates edge- and face-on solid state order for the selenophene-based polymer as compared to the thienothiophene-based polymer, which orders predominantly edge-on with respect to the substrate. In polymer:PCBM bulk heterojunction solar cells both materials show a similar open-circuit voltage of ∼0.80-0.84 V, however the selenophene-based polymer displays a higher fill factor of ∼0.70 vs. ∼0.65. This is due to the partial face-on backbone orientation of the selenophene-based polymer, leading to a higher hole mobility, as confirmed by single-carrier diode measurements, and a concomitantly higher fill factor. Combined with improved spectral coverage of the selenophene-based polymer, as confirmed by quantum efficiency experiments, it offers a larger short-circuit current density of ∼12 mA cm. Despite the relatively low molecular weight of both materials, a very robust power conversion efficiency ∼7% is achieved for the selenophene-based polymer, while the thienothiophene-based polymer demonstrates only a moderate maximum PCE of ∼5.5%. Hence, the favorable effects of selenophene incorporation on the photovoltaic performance of pentacyclic lactam-based conjugated polymers are clearly demonstrated.

  8. Largely enhanced thermal and mechanical properties of polymer nanocomposites via incorporating C60@graphene nanocarbon hybrid

    Science.gov (United States)

    Song, Ping'an; Liu, Lina; Huang, Guobo; Yu, Youming; Guo, Qipeng

    2013-12-01

    Although considerable progress has been achieved to create advanced polymer nanocomposites using nanocarbons including fullerene (C60) and graphene, it remains a major challenge to effectively disperse them in a polymer matrix and to fully exert their extraordinary properties. Here we report a novel approach to fabricate the C60@graphene nanocarbon hybrid (C60: ˜47.9 wt%, graphene: ˜35.1%) via three-step reactions. The presence of C60 on a graphene sheet surface can effectively prevent the aggregation of the latter which in turn helps the dispersion of the former in a polymer matrix during melt-processing. C60@graphene is found to be uniformly dispersed in a polypropylene (PP) matrix. Compared with pristine C60 or graphene, C60@graphene further improves the thermal stability and mechanical properties of PP. The incorporation of 2.0 wt% C60@graphene (relative to PP) can remarkably increase the initial degradation temperature by around 59 ° C and simultaneously enhance the tensile strength and Young’s modulus by 67% and 76%, respectively, all of which are higher than those of corresponding PP/C60 (graphene) nanocomposites. These significant performance improvements are mainly due to the free-radical-trapping effect of C60, and the thermal barrier and reinforcing effects of graphene nanosheets as well as the effective stress load transfer. This work provides a new methodology to design multifunctional nanohybrids for creating advanced materials.

  9. Largely enhanced thermal and mechanical properties of polymer nanocomposites via incorporating C60@graphene nanocarbon hybrid

    International Nuclear Information System (INIS)

    Song, Ping’an; Liu, Lina; Yu, Youming; Huang, Guobo; Guo, Qipeng

    2013-01-01

    Although considerable progress has been achieved to create advanced polymer nanocomposites using nanocarbons including fullerene (C 60 ) and graphene, it remains a major challenge to effectively disperse them in a polymer matrix and to fully exert their extraordinary properties. Here we report a novel approach to fabricate the C 60 @graphene nanocarbon hybrid (C 60 : ∼47.9 wt%, graphene: ∼35.1%) via three-step reactions. The presence of C 60 on a graphene sheet surface can effectively prevent the aggregation of the latter which in turn helps the dispersion of the former in a polymer matrix during melt-processing. C 60 @graphene is found to be uniformly dispersed in a polypropylene (PP) matrix. Compared with pristine C 60 or graphene, C 60 @graphene further improves the thermal stability and mechanical properties of PP. The incorporation of 2.0 wt% C 60 @graphene (relative to PP) can remarkably increase the initial degradation temperature by around 59 ° C and simultaneously enhance the tensile strength and Young’s modulus by 67% and 76%, respectively, all of which are higher than those of corresponding PP/C 60 (graphene) nanocomposites. These significant performance improvements are mainly due to the free-radical-trapping effect of C 60 , and the thermal barrier and reinforcing effects of graphene nanosheets as well as the effective stress load transfer. This work provides a new methodology to design multifunctional nanohybrids for creating advanced materials. (paper)

  10. Two multi-dimensional frameworks constructed from zinc coordination polymers with pyridine carboxylic acids

    International Nuclear Information System (INIS)

    Guo Yuanyuan; Ma Pengtao; Wang Jingping; Niu Jingyang

    2011-01-01

    Two novel zinc coordination polymers [Zn 2 (H 2 O)L(MoO 4 )] n (1) and [Zn 4 (PO 4 ) 2 L'(H 2 O)] n (2) (H 2 L=2,2'-bipyridine-6.6'-dicarboxylic acid, H 2 L'=2,2'-bipyridine-4,4'-dicarboxylic acid) have been hydrothermally synthesized and characterized by elemental analyses, IR spectra, UV spectra, single-crystal X-ray diffraction and thermogravimetric analyses. Structural analyses indicate that 1 represents a 2-D sheet structure built by dimeric [Zn 2 L(H 2 O)] 2+ units and MoO 4 2- groups whereas 2 displays an interesting 3-D framework constructed by tetranuclear zinc clusters, L' 2- ligands and PO 4 3- groups. Examination of UV spectra suggests that both 1 and 2 can stably exist in the pH range of 2.45-5.45 and 3.01-8.55 in aqueous solution, respectively. The room-temperature solid-state photoluminescence of 1 and 2 are derived from the intra-ligands π-π* transitions of H 2 L and H 2 L' ligands and the ligand-to-metal-charge-transfer transitions. - Graphical Abstract: Two new transition metal coordination polymers, namely, [Zn 2 (H 2 O)L 1 (MoO 4 )] n (1), [Zn 4 (PO 4 ) 2 L 2 (H 2 O)] n (2) (H 2 L 1 =2,2'-bipyridine-6,6'-dicarboxylic acid, H 2 L 2 =2,2'-bipyridine-4,4'-dicarboxylic acid) have been hydrothermally synthesized. 1 represents a 2-D sheet structure while 2 represents 3-D network. Highlights: →Two new transition metal coordination polymers have been hydrothermally synthesized. → The two compounds have been characterized by elemental analyses, IR, UV spectra, single-crystal X-ray diffraction, thermogravimetric analyses and photoluminescence. → Compound 1 represents a 2-D sheet structure while 2 represents 3-D network.

  11. Syntheses, crystal structures, and properties of new metal-5-bromonicotinate coordination polymers

    Energy Technology Data Exchange (ETDEWEB)

    Li, Wenjie [College of Chemistry and Molecular Engineering, Zhengzhou University, Zhengzhou 450052 (China); Li, Guoting [Department of Environmental and Municipal Engineering, North China University of Water Conservancy and Electric Power, Zhengzhou 450011 (China); Lv, Lulu; Zhao, Hong [College of Chemistry and Molecular Engineering, Zhengzhou University, Zhengzhou 450052 (China); Wu, Benlai, E-mail: wbl@zzu.edu.cn [College of Chemistry and Molecular Engineering, Zhengzhou University, Zhengzhou 450052 (China)

    2015-05-15

    Four metal–5-bromonicotinate (Brnic) coordination polymers [Fe(Brnic){sub 2}(H{sub 2}O){sub 2}]{sub n} (1), [Ni(Brnic){sub 2}]{sub n} (2), [Ni(Brnic)(bpy)(H{sub 2}O){sub 2}]{sub n}·n(Brnic)·4.5nH{sub 2}O (3), and [Co{sub 2}(Brnic){sub 3}(bpy){sub 2}(OH)]{sub n}·nH{sub 2}O (4) have been synthesized and structurally characterized (bpy=4,4′-bipyridine). Complex 1 has corrugated (4,4) sheets formed by μ-Brnic ligands and planar nodes Fe(II). As for 2–4, they all built up from Brnic-bridged dinuclear subunits, but have very different structure features. Complex 2 is a twin-like polymer with (4,4) layers formed by twin paddle-wheel [Ni{sub 2}(Brnic){sub 4}] subunits. Through the bridge coordination of bpy ligands with dinuclear rings [Ni{sub 2}(Brnic){sub 2}] and trigons [Co{sub 2}(Brnic){sub 3}(OH)], 6{sup 3}-topological cationic layers with nanosized grids of 3 and chiral ladder-type double chains of 4 formed, respectively. Notably, halogen-related interactions play an important role in the formation of 3D metallosupermolecules 1–4. The thermostabilities of all compounds have been discussed in detail. Moreover, the magnetic investigations of 2 and 4 indicate that there exist antiferromagnetic interactions in the paddle-wheel [Ni{sub 2}(Brnic){sub 4}] and trigon [Co{sub 2}(Brnic){sub 3}(OH)] cores, respectively. - Highlights: • Four novel metal–5-bromonicotinate coordination polymers have been synthesized. • Notably, halogen-related interactions play an important role in the formation of 3D metallosupermolecules. • Antiferromagnetic interactions in nickel(II) paddle-wheel and cobalt(II) trigon cores were observed.

  12. Luminescent lanthanide coordination polymers synthesized via in-situ hydrolysis of dimethyl-3,4-furandicarboxylate

    Energy Technology Data Exchange (ETDEWEB)

    Greig, Natalie E.; Einkauf, Jeffrey D.; Clark, Jessica M.; Corcoran, Eric J.; Karram, Joseph P.; Kent, Charles A.; Eugene, Vadine E. [Department of Chemistry & Biochemistry, Florida Atlantic University, 777 Glades Road, Boca Raton, FL 33431 (United States); Chan, Benny C. [Department of Chemistry, The College of New Jersey, 2000 Pennington Road, Ewing, NJ 08628 (United States); Lill, Daniel T. de, E-mail: ddelill@fau.edu [Department of Chemistry & Biochemistry, Florida Atlantic University, 777 Glades Road, Boca Raton, FL 33431 (United States)

    2015-05-15

    Dimethyl-3,4-furandicarboxylate undergoes hydrolysis under hydrothermal conditions with lanthanide (Ln) ions to form two-dimensional coordination polymers, [Ln(C{sub 6}H{sub 2}O{sub 5})(C{sub 6}H{sub 3}O{sub 5})(H{sub 2}O)]{sub n} (Ln=Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu). The resulting materials exhibit luminescent properties with quantum yields and lifetimes for the Eu(III) and Tb(III) compounds of 1.1±0.3% and 0.387±0.0001 ms, and 3.3±0.8% and 0.769±0.006 ms, respectively. Energy values for the singlet and triplet states were determined for dimethyl-3,4-furandicarboxylate and 3,4-furandicarboxylic acid. Excited state dynamics and structural features are examined to explicate the reported quantum yields. A series of other FDC structures is briefly presented. - Graphical abstract: A new two-dimensional coordination polymer derived from the in-situ hydrolysis of a furan dimethyl ester with lanthanide(III) ions was obtained in order to study its photophysical behavior when constructed from trivalent Eu and Tb. Quantum yields, lifetime measurements, and singlet/triplet state energies values were obtained. The nature of the material's excited state dynamics is examined and correlated to its structure in order to explain the overall luminescent efficiency of the system. - Highlights: • A new lanthanide–furandicarboxylate coordination polymer is presented. • Eu and Tb compounds display luminescent properties, albeit with low quantum yields. • Photophysical behavior explained through the compound's triplet state and structure. • Nonradiative deactivation of luminescence through high-energy oscillators was noted. • Molecular modeling of the organic moiety was conducted.

  13. Stretchable supercapacitors based on highly stretchable ionic liquid incorporated polymer electrolyte

    Energy Technology Data Exchange (ETDEWEB)

    Tamilarasan, P.; Ramaprabhu, S., E-mail: ramp@iitm.ac.in

    2014-11-14

    Mechanical stability of electrolyte in all-solid-state supercapacitor attains immense attention as it addresses safety aspects. In this study, we have demonstrated, the fabrication of stretchable supercapacitor based on stretchable electrolyte and hydrogen exfoliated graphene electrode. We synthesized ionic liquid incorporated stretchable Poly(methyl methacrylate) electrolyte which plays dual role as electrolyte and stretchable support for electrode material. The molecular vibration studies show composite nature of the electrolyte. At least four-fold stretchability has been observed along with good ionic conductivity (0.78 mS cm{sup −1} at 28 °C) for this polymer electrolyte. This stretchable supercapacitor shows a low equivalent series resistance (16 Ω) due to the compatibility at electrode–electrolyte interface. The performance of the device has been determined under strain as well. - Highlights: • A stretchable supercapacitor has been fabricated using stretchable electrolyte. • Here ionic liquid incorporated polymer plays dual role as electrolyte and stretchable support. • The developed device shows low equivalent series resistance. • The device has specific capacitance of 83 F g{sup −1}, at the specific current of 2.67 A g{sup −1}. • The energy density and power density of 25.7 Wh kg{sup −1} and 35.2 kW kg{sup −1}, respectively.

  14. Surfactant Incorporated Co Nanoparticles Polymer Composites with Uniform Dispersion and Double Percolation

    Directory of Open Access Journals (Sweden)

    Tajamal Hussain

    2017-01-01

    Full Text Available Series of Cobalt nanoparticles incorporated polymethylmethacrylate composites in the presence and absence of dodecyl-benzene-sulphonic acid (DBSA-CoNPs/PMMA and CoNPs/PMMA, resp. were synthesized by solution mixing methodology. UV-visible and FTIR techniques were used to confirm the formation of nanocomposite. UV-visible spectra of the composites showed the incorporation of filler particles in the polymer matrix. On the other hand, FTIR spectra indicated the physical interaction between the two phases of the composite. Moreover, the electrical nature of the composites was studied by plotting graphs between electrical conductivity (measured using LCR meter at 100 kHz and contents of the filler particles as introduced in the polymer matrix. An increase in electrical conductivity was first observed with increasing filler concentration up to the critical percolation threshold value (0.5% for DBSA-CoNPs/PMMA and 1% for CoNPs/PMMA, which then dropped upon further increments in the filler content. However, at higher concentrations, a second jump in the conductivity was observed in case of DBSA-CoNPs/PMMA composites.

  15. Assessment of geraniol-incorporated polymers to control Aedes albopictus (Diptera: culicidae

    Directory of Open Access Journals (Sweden)

    Chuaycharoensuk T.

    2012-11-01

    Full Text Available Effective control of mosquito borne diseases has proven extremely difficult with both vector and pathogen remaining entrenched and expanding in many disease endemic areas. When lacking an effective vaccine, vector control methods targeting both larval habitats and adult mosquito populations remain the primary strategy for reducing risk. Aedes albopictus from Thailand was used as a reference baseline for evaluation of natural insecticides incorporated in polymer disks and pellets and tested both in laboratory and field conditions. In laboratory and field tests, the highest larval mortality was obtained with disks or pellets containing IKHC (Insect Killer Highly Concentrate from Fulltec AG Company. This product is reputed to contain geraniol as an active ingredient. With pellets, high mortality of Ae. albopictus larvae (92% was observed in presence of 1 g of pellets per 500 ml of water at day 1st, and the mortality was 100% at day 1st for larvae in presence of 5 or 10 g of pellets. Fulltec AG Company has not accepted to give us the exact composition of their IKHC product. Therefore, we cannot recommend it, but the principle of using monoterpenes like geraniol, incorporated into polymer disks or pellets as natural larvicide needs more attention as it could be considered as a powerful alternative in mosquito vector control.

  16. A simple way of improving graphite nanoplatelets (GNP for their incorporation into a polymer matrix

    Directory of Open Access Journals (Sweden)

    H. Persson

    2012-02-01

    Full Text Available A simple method of solvent exfoliation/refining of direct-graphite nanoplatelets for their better incorporation into a polymer matrix is presented. We demonstrate the method for polystyrene. The method relies on sonication in N-methyl-2-pyrrolidone solvent, with surfactant assistance. A small amount of polystyrene is added to the solvent in order to increase the viscosity, this enhancing the exfoliation process and resulting in formation of a polymeric layer on graphene for its better incorporation in the polymer matrix. Polystyrene-coated thin graphene stacks form a stable dispersion, while thicker graphite nanoplatelets settle out. Thus bulk separation of thin and thick graphene stacks takes place. The polystyrene-coated thin graphene stacks are studied using Transmission Electron Microscopy in two ways: (i we calculate the number of graphene layers forming thin graphene stacks, and (ii we employ Selected Area Diffraction to confirm our image analysis results by checking the intensity ratio (1100 and (2100 deflections in the diffraction patterns. Five layers is found to be the cut-off number, that is there are no stacks >5 layers, and 3 layer stacks are dominantly present. The average largest in-plane dimension is found to be approximately 2.5 µm (reduction by 50%.

  17. Selective Adsorption of CO2 from Light Gas Mixtures Using a Structurally Dynamic Porous Coordination Polymer**

    Energy Technology Data Exchange (ETDEWEB)

    Kristi L. Kauffman, Jeffrey T. Culp, Andrew J. Allen, Laura Espinal, Winnie Wong-Ng, Thomas D.

    2010-01-01

    The selective adsorption of CO{sub 2} from mixtures with N{sub 2}, CH{sub 4}, and N{sub 2}O in a dynamic porous coordination polymer (see monomer structure) was evaluated by ATR-FTIR spectroscopy, GC, and SANS. All three techniques indicate highly selective adsorption of CO{sub 2} from CO{sub 2}/CH{sub 4} and CO{sub 2}/N{sub 2} mixtures at 30 C, with no selectivity observed for the CO{sub 2}/N{sub 2}O system.

  18. Homo- and heterodinuclear coordination polymers based on a tritopic cyclam bis-terpyridine unit: Structure and rheological properties

    Energy Technology Data Exchange (ETDEWEB)

    Qu, Li; Fan, Jiangxia; Ren, Yong; Xiong, Kun [State Key Laboratory Cultivation Base for Nonmetal Composites and Functional Materials, School of Materials Science and Engineering, Southwest University of Science and Technology, Mianyang 621010 (China); Yan, Minhao, E-mail: yanminhao@swust.edu.cn [State Key Laboratory Cultivation Base for Nonmetal Composites and Functional Materials, School of Materials Science and Engineering, Southwest University of Science and Technology, Mianyang 621010 (China); Tuo, Xianguo, E-mail: tuoxg@swust.edu.cn [Laboratory of National Defense for Radioactive Waste and Environmental Security, Southwest University of Science and Technology, Mianyang 621010 (China); Terech, Pierre [SPrAM, UMR CEA/CNRS/UJF-Grenoble 1, INAC, Grenoble F-38054 (France); Royal, Guy [Université Joseph Fourier Grenoble I, Département de Chimie Moléculaire, UMR CNRS-5250, Institut de Chimie Moléculaire de Grenoble, FR CNRS-2607, BP 53, 38041 Grenoble Cedex 9 (France)

    2015-03-01

    An innovative coordination polymer based on a tritopic ligand having the bis-terpyridine cyclam (CHTT) unit is explored. Homo- or heteronuclear 1D coordination polymers can be formed with bivalent metal ions such as Co(II) and Ni(II) in solvent DMF. Creep-recovery curves of the (Co{sup II}){sub 2}CHTT gels formed from 1D coordination polymers were analyzed with the Burgers model and demonstrated an original self-healing property, unusual in the class of molecular gels. The influence of the metal type was studied through the structural features using small-angle neutron scattering (SANS) experiments. In gels, the corresponding network involves genuine fibers (R ≈ 35 Å), bundles of these fibers and also a fraction of finite size aggregates (rods with aspect ratio f ≈ 3–5). We found that the distribution of these latter structural components is sensitive to the metal ions type. Such tritopic 1D coordination polymers exhibit a range of original structural features and a facile control of the developed structures in solutions and gels by tuning their thermodynamic parameters. The versatility associated to the intrinsic dynamic ability of the systems should pave the way to original properties for molecular devices. - Graphical abstract: A tritopic ligand with a bis-terpyridine cyclam (CHTT) unit can form homo- and heterobinuclear coordination polymers with bivalent metal ions in DMF. Gels exhibit a remarkable self-healing property while structures of solutions and gels are studied by small-angle neutron scattering. - Highlights: • Homo- and heteronuclear coordination polymers based on innovative tritopic ligand. • The gels formed from the coordination polymers demonstrated self-healing property. • Influence of the metal type was studied through the structural properties by SANS. • Versatility of the singular system present original properties for molecular device.

  19. Hybrid conducting polymer materials incorporating poly-oxo-metalates for extraction of actinides; Materiaux polymeres conducteurs hybrides incorporant des polyoxometallates pour l'extraction d'actinides

    Energy Technology Data Exchange (ETDEWEB)

    Racimor, D

    2003-09-15

    The preparation and characterization of hybrid conducting polymers incorporating poly-oxo-metalates for extracting actinides is discussed. A study of the coordination of various lanthanide cations (Ce(III), Ce(IV), Nd(III)) by the mono-vacant poly-oxo-metalate {alpha}{sub 2}-[P{sub 2}W{sub 17}O{sub 61}]{sup 10-} showed significant differences according to the cation.. Various {alpha}-A-[PW{sub 9}O{sub 34}(RPO){sub 2}]{sup 5-} hybrids were synthesized and their affinity for actinides or lanthanides was demonstrated through complexation. The first hybrid poly-oxo-metallic lanthanide complexes were then synthesized, as was the first hybrid functionalized with a pyrrole group. The electro-polymerization conditions of this pyrrole remain still to be optimized. Poly-pyrrole materials incorporating {alpha}{sub 2}-[P{sub 2}W{sub 17}O{sub 61}]{sup 10-} or its neodymium or cerium complexes as doping agents proved to be the first conducting polymer incorporating poly-oxo-metalates capable of extracting plutonium from nitric acid. (author)

  20. Lanthanide coordination polymers with tetrafluoroterephthalate as a bridging ligand: thermal and optical properties.

    Science.gov (United States)

    Seidel, Christiane; Lorbeer, Chantal; Cybińska, Joanna; Mudring, Anja-Verena; Ruschewitz, Uwe

    2012-04-16

    By slow diffusion of triethylamine into a solution of 2,3,5,6-tetrafluoroterephthalic acid (H2tfBDC) and the respective lanthanide salt in EtOH/DMF single crystals of seven nonporous coordination polymers, (∞)(2)[Ln(tfBDC)(NO(3))(DMF)(2)]·DMF (Ln(3+) = Ce, Pr, Nd, Sm, Dy, Er, Yb; C2/c, Z = 8) have been obtained. In the crystal structures, two-dimensional square grids are found, which are composed of binuclear lanthanide nodes connected by tfBDC(2-) as a linking ligand. The coordination sphere of each lanthanide cation is completed by a nitrate anion and two DMF molecules (CN = 9). This crystal structure is unprecedented in the crystal chemistry of coordination polymers based on nonfluorinated terephthalate (BDC(2-)) as a bridging ligand; as for tfBDC(2-), a nonplanar conformation of the ligand is energetically more favorable, whereas for BDC(2-), a planar conformation is preferred. Differential thermal analysis/thermogravimetric analysis (DTA/TGA) investigations reveal that the noncoordinating DMF molecule is released first at temperatures of 100-200 °C. Subsequent endothermal weight losses correspond to the release of the coordinating DMF molecules. Between 350 and 400 °C, a strong exothermal weight loss is found, which is probably due to a decomposition of the tfBDC(2-) ligand. The residues could not be identified. The emission spectra of the (∞)(2)[Ln(tfBDC)(NO(3))(DMF)(2)]·DMF compounds reveal intense emission in the visible region of light for Pr, Sm, and Dy with colors from orange, orange-red, to warm white. © 2012 American Chemical Society

  1. Smart lanthanide coordination polymer fluorescence probe for mercury(II) determination

    Energy Technology Data Exchange (ETDEWEB)

    Liu, Baoxia [Henan Key Laboratory Cultivation Base of Nanobiological Analytical Chemistry, College of Chemistry and Chemical Engineering, Shangqiu Normal University, Shangqiu 476000 (China); Huang, Yankai [Henan Key Laboratory Cultivation Base of Nanobiological Analytical Chemistry, College of Chemistry and Chemical Engineering, Shangqiu Normal University, Shangqiu 476000 (China); College of Chemistry and Molecular Engineering, Zhengzhou University, Zhengzhou 450001 (China); Zhu, Xu; Hao, Yuanqiang [Henan Key Laboratory Cultivation Base of Nanobiological Analytical Chemistry, College of Chemistry and Chemical Engineering, Shangqiu Normal University, Shangqiu 476000 (China); Ding, Yujie [College of Biochemical Engineering, Anhui Polytechnic University, Wuhu 241000 (China); Wei, Wei; Wang, Qi [Henan Key Laboratory Cultivation Base of Nanobiological Analytical Chemistry, College of Chemistry and Chemical Engineering, Shangqiu Normal University, Shangqiu 476000 (China); Qu, Peng, E-mail: qupeng0212@163.com [Henan Key Laboratory Cultivation Base of Nanobiological Analytical Chemistry, College of Chemistry and Chemical Engineering, Shangqiu Normal University, Shangqiu 476000 (China); College of Chemistry and Molecular Engineering, Zhengzhou University, Zhengzhou 450001 (China); Xu, Maotian, E-mail: xumaotian@sqnc.edu.cn [Henan Key Laboratory Cultivation Base of Nanobiological Analytical Chemistry, College of Chemistry and Chemical Engineering, Shangqiu Normal University, Shangqiu 476000 (China); College of Chemistry and Molecular Engineering, Zhengzhou University, Zhengzhou 450001 (China)

    2016-03-17

    Lanthanide coordination polymers (LCPs) have recently emerged as attractive biosensor materials due to their flexible components, high tailorable properties and unique luminescence features. In this work, we designed a smart LCP probe of Tb-CIP/AMP {(CIP, ciprofloxacin) (AMP, adenosine monophosphate)} for Hg{sup 2+} detection by using lanthanide ions as metal nodes, CIP as ligand molecule, and AMP as bridging linker and recognition unit. Tb-CIP/AMP emits strong green luminescence due to the inclusion of AMP, which withdraws the coordinated water molecules and shields Tb{sup 3+} from the quenching effect of O–H vibration in water molecules. The subsequent addition of Hg{sup 2+} into Tb-CIP/AMP can strongly quench the fluorescence because of the specific coordination interaction between AMP and Hg{sup 2+}. As a kind of Hg{sup 2+} nanosensor, the probe exhibited excellent selectivity for Hg{sup 2+} and high sensitivity with detection limit of 0.16 nM. In addition, the probe has long fluorescence lifetime up to millisecond and has been applied to detect Hg{sup 2+} in drinking water and human urine samples with satisfactory results. We envision that our strategy, in the future, could be extended to the designation of other LCP-based hypersensitive time-gated luminescence assays in biological media and biomedical imaging. - Highlights: • Lanthanide coordination polymer of Tb-CIP/AMP was synthesized via a simple self-assembly process. • AMP was employed as a bifunctional molecule for both fluorescence sensitization and target recognition. • Hypersensitive detection of Hg{sup 2+} was achieved based on time-resolved spectroscopy.

  2. Smart lanthanide coordination polymer fluorescence probe for mercury(II) determination

    International Nuclear Information System (INIS)

    Liu, Baoxia; Huang, Yankai; Zhu, Xu; Hao, Yuanqiang; Ding, Yujie; Wei, Wei; Wang, Qi; Qu, Peng; Xu, Maotian

    2016-01-01

    Lanthanide coordination polymers (LCPs) have recently emerged as attractive biosensor materials due to their flexible components, high tailorable properties and unique luminescence features. In this work, we designed a smart LCP probe of Tb-CIP/AMP {(CIP, ciprofloxacin) (AMP, adenosine monophosphate)} for Hg 2+ detection by using lanthanide ions as metal nodes, CIP as ligand molecule, and AMP as bridging linker and recognition unit. Tb-CIP/AMP emits strong green luminescence due to the inclusion of AMP, which withdraws the coordinated water molecules and shields Tb 3+ from the quenching effect of O–H vibration in water molecules. The subsequent addition of Hg 2+ into Tb-CIP/AMP can strongly quench the fluorescence because of the specific coordination interaction between AMP and Hg 2+ . As a kind of Hg 2+ nanosensor, the probe exhibited excellent selectivity for Hg 2+ and high sensitivity with detection limit of 0.16 nM. In addition, the probe has long fluorescence lifetime up to millisecond and has been applied to detect Hg 2+ in drinking water and human urine samples with satisfactory results. We envision that our strategy, in the future, could be extended to the designation of other LCP-based hypersensitive time-gated luminescence assays in biological media and biomedical imaging. - Highlights: • Lanthanide coordination polymer of Tb-CIP/AMP was synthesized via a simple self-assembly process. • AMP was employed as a bifunctional molecule for both fluorescence sensitization and target recognition. • Hypersensitive detection of Hg 2+ was achieved based on time-resolved spectroscopy.

  3. Pyrolysis of Helical Coordination Polymers for Metal-Sulfide-Based Helices with Broadband Chiroptical Activity.

    Science.gov (United States)

    Hirai, Kenji; Yeom, Bongjun; Sada, Kazuki

    2017-06-27

    Fabrication of chiroptical materials with broadband response in the visible light region is vital to fully realize their potential applications. One way to achieve broadband chiroptical activity is to fabricate chiral nanostructures from materials that exhibit broadband absorption in the visible light region. However, the compounds used for chiroptical materials have predominantly been limited to materials with narrowband spectral response. Here, we synthesize Ag 2 S-based nanohelices derived from helical coordination polymers. The right- and left-handed coordination helices used as precursors are prepared from l- and d-glutathione with Ag + and a small amount of Cu 2+ . The pyrolysis of the coordination helices yields right- and left-handed helices of Cu 0.12 Ag 1.94 S/C, which exhibit chiroptical activity spanning the entire visible light region. Finite element method simulations substantiate that the broadband chiroptical activity is attributed to synergistic broadband light absorption and light scattering. Furthermore, another series of Cu 0.10 Ag 1.90 S/C nanohelices are synthesized by choosing the l- or d-Glu-Cys as starting materials. The pitch length of nanohelicies is controlled by changing the peptides, which alters their chiroptical properties. The pyrolysis of coordination helices enables one to fabricate helical Ag 2 S-based materials that enable broadband chiroptical activity but have not been explored owing to the lack of synthetic routes.

  4. Log-gamma directed polymer with one free end via coordinate Bethe Ansatz

    Science.gov (United States)

    Grange, Pascal

    2017-07-01

    The discrete polymer model with random Boltzmann weights with homogeneous inverse gamma distribution, introduced by Seppäläinen, is studied in the case of a polymer with one fixed and one free end. The model with two fixed ends has been integrated by Thiery and Le Doussal, using coordinate Bethe Ansatz techniques and an analytic-continuation prescription. The probability distribution of the free energy has been obtained through the replica method, even though the moments of the partition sum do not exist at all orders due to the fat tail in the distribution of Boltzmann weights. To extend this approach to the polymer with one free end, we argue that the contribution to the partition sums in the thermodynamic limit is localised on parity-invariant string states. This situation is analogous to the case of the continuum polymer with one free end, related to the Kardar-Parisi-Zhang equation with flat boundary conditions and solved by Le Doussal and Calabrese. The expansion of the generating function of the partition sum in terms of numbers of strings can also be transposed to the log-gamma polymer model, with the induced Fredholm determinant structure. We derive the large-time limit of the rescaled cumulative distribution function, and relate it to the GOE Tracy-Widom distribution. The derivation is conjectural in the sense that it assumes completeness of a family of string states, and expressions of their norms, already useful in the fixed-end problem, and extends heuristically the order of moments of the partition sum to the complex plane.

  5. Aromatic carboxylate effect on dimensionality of three bis(benzimidazole)-based cobalt(II) coordination polymers: Syntheses, structures and properties

    International Nuclear Information System (INIS)

    Zhang, Ju-Wen; Gong, Chun-Hua; Hou, Li-Li; Tian, Ai-Xiang; Wang, Xiu-Li

    2013-01-01

    Three new metal-organic coordination polymers [Co(4-bbc) 2 (bbbm)] (1), [Co(3,5-pdc)(bbbm)]·2H 2 O (2) and [Co(1,4-ndc)(bbbm)] (3) (4-Hbbc=4-bromobenzoic acid, 3,5-H 2 pdc=3,5-pyridinedicarboxylic acid, 1,4-H 2 ndc=1,4-naphthalenedicarboxylic acid and bbbm=1,1-(1,4-butanediyl)bis-1H-benzimidazole) were hydrothermally synthesized and structurally characterized. Polymer 1 is a 1D chain formed by the bbbm ligands and Co II ions. Polymer 2 exhibits a 2D network with a (3·4·5)(3 2 ·4·5·6 2 ·7 4 ) topology. Polymer 3 possesses a 3D three-fold interpenetrating framework. The versatile structures of title polymers indicate that the aromatic carboxylates have an important influence on the dimensionality of 1–3. Moreover, the thermal stability, electrochemical and luminescent properties of 1–3 were investigated. - graphical abstract: Three bis(benzimidazole)-based cobalt(II) coordination polymers tuned by aromatic carboxylates were hydrothermally synthesized and structurally characterized. The aromatic carboxylates play a key role in the dimensionality of three polymers. The electrochemical and luminescent properties of three polymers were investigated. Display Omitted - Highlights: • Three bis(benzimidazole)-based cobalt(II) coordination polymers tuned by aromatic carboxylates were obtained. • The aromatic carboxylates have an important influence on the dimensionality of three polymers. • The electrochemical and luminescent properties of three polymers were investigated

  6. Synthesis, Crystal Structure and Luminescent Property of A Novel Cd(II) Coordination Polymer with Bis-imidazole Ligand

    Energy Technology Data Exchange (ETDEWEB)

    Zhou, Yong Hong [Huaibei Normal Univ., Huaibei (China)

    2013-04-15

    The key to the successful design of metal-organic coordination polymers is the judicious selection of organic ligand. Recently, polydentate aromatic nitrogen heterocyclic ligands with five-membered rings have been well-studied in the construction of supramolecular structure for their N-coordinated sites apt to coordinating to transition metals. Similar to six-membered N-heterocyclic ligands, the azole-based five-membered N-heterocyclic ligands, such as imidazoles, triazoles and tetrazoles have been extensively employed in the construction of various coordination polymers with diverse topologies and interesting properties. The bis(azole) ligands in which N-donor azole rings (imidazole, triazole, or tetrazole) are separated by alkyl, (CH{sub 2}){sub n}, spacers are good choices for flexible bridging ligands. The conformational flexibility of the spacers makes the ligands adaptable to various coordination networks with one-, two-, and three dimensional structures.

  7. A New 1D Chained Coordination Polymer: Synthesis, Crystal Structure, Antitumor Activity and Luminescent Property

    Directory of Open Access Journals (Sweden)

    Xi-Shi Tai

    2015-11-01

    Full Text Available A new 1D chained coordination polymer of Zn(II, {[Zn(L2(4,4′-bipy]·(H2O}n(1 (HL = N-acetyl-l-phenylalanine; 4,4′-bipy = 4,4′-bipyridine has been synthesized and characterized by elemental analysis, IR and X-ray single crystal diffraction analysis. Theresults show that each asymmetric unit of Zn(II complex belongs to monoclinic, space group P21 with a = 11.421(2 Å, b = 9.2213(17 Å, c = 15.188(3 Å,β = 106.112(3°, V = 1536.7(5 Å3, Z = 2, Dc = 1.444 g·cm−3, µ = 0.857 mm−1, F(000 = 696, and final R1 = 0.0439, ωR2 = 0.1013. The molecules form one-dimensional chained structure by its the bridging 4,4′-bipyridine ligands. The antitumor activities and luminescent properties of Zn(II coordination polymer have also been investigated.

  8. Copper coordination polymers constructed from thiazole-5-carboxylic acid: Synthesis, crystal structures, and structural transformation

    Energy Technology Data Exchange (ETDEWEB)

    Meundaeng, Natthaya; Rujiwatra, Apinpus [Department of Chemistry, Faculty of Science, Chiang Mai University, Chiang Mai 50200 (Thailand); Prior, Timothy J., E-mail: t.prior@hull.ac.uk [Chemistry, University of Hull, Kingston upon Hull HU6 7RX (United Kingdom)

    2017-01-15

    We have successfully prepared crystals of thiazole-5-carboxylic acid (5-Htza) (L) and three new thiazole-5-carboxylate-based Cu{sup 2+} coordination polymers with different dimensionality, namely, 1D [Cu{sub 2}(5-tza){sub 2}(1,10-phenanthroline){sub 2}(NO{sub 3}){sub 2}] (1), 2D [Cu(5-tza){sub 2}(MeOH){sub 2}] (2), and 3D [Cu(5-tza){sub 2}]·H{sub 2}O (3). These have been characterized by single crystal X-ray diffraction and thermogravimetry. Interestingly, the 2D network structure of 2 can directly transform into the 3D framework of 3 upon removal of methanol molecules at room temperature. 2 can also undergo structural transformation to produce the same 2D network present in the known [Cu(5-tza){sub 2}]·1.5H{sub 2}O upon heat treatment for 2 h. This 2D network can adsorb water and convert to 3 upon exposure to air. - Highlights: • Rare examples of coordination polymers of thiazole-5-carboxylic acid were prepared. • Non-covalent interactions play a key role on the assembly of the complexes in solid state. • Structural transformation of a 2D framework to a 3D upon removal of methanol is observed.

  9. Enantiopure Chiral Coordination Polymers Based on Polynuclear Paddlewheel Helices and Arsenyl Tartrate

    Directory of Open Access Journals (Sweden)

    Ángela Valentín-Pérez

    2018-03-01

    Full Text Available Herein, we report the preparation of chiral, one-dimensional coordination polymers based on trinuclear paddlewheel helices [M3(dpa4]2+ (M = Co(II and Ni(II; dpa = the anion of 2,2′-dipyridylamine. Enantiomeric resolution of a racemic mixture of [M3(dpa4]2+ complexes was achieved by chiral recognition of the respective enantiomer by [Δ-As2(tartrate2]2− or [Λ-As2(tartrate2]2− in N,N-dimethylformamide (DMF, affording crystalline coordination polymers formed from [(Δ-Co3(dpa4(Λ-As2(tartrate2]·3DMF (Δ-1, [(Λ-Co3(dpa4(Δ-As2(tartrate2]·3DMF (Λ-1, [(Δ-Ni3(dpa4(Λ-As2(tartrate2]·(4 − nDMF∙nEt2O (Δ-2 or [(Λ-Ni3(dpa4(Δ-As2(tartrate2]·(4 − nDMF∙nEt2O (Λ-2 repeating units. UV-visible circular dichroism spectra of the complexes in DMF solutions demonstrate the efficient isolation of optically active species. The helicoidal [M3(dpa4]2+ units that were obtained display high stability towards racemization as shown by the absence of an evolution of the dichroic signals after several days at room temperature and only a small decrease of the signal after 3 h at 80 °C.

  10. Synthesis of f metal coordination polymers: properties and conversion into inorganic solids

    International Nuclear Information System (INIS)

    Demars, Thomas

    2012-01-01

    Coordination polymers (CP) are of great academic and industrial interest due to flexible structure and composition and offer prospects for original chemical (catalysis, soft-hard materials conversion..) and physical properties (magnetism, optics..). The major interest of these studies is to check the transfer of the structure, meso-structure and composition from the CP to the ceramic via a thermal treatment. In this context, this thesis describes studies on conversion of coordination polymers obtained by self-assembly of 4f and 5f metal ions with 2,5-dihydroxy-1,4-benzoquinone (DHBQ). Aqueous and anhydrous synthetic ways were developed, which yielded different kinds of CPs (4f, 4f-4f, 4f-5f); solid solutions were obtained with the mixed compounds. The products were characterized and their behaviour under thermal treatment was studied. The main results show that the DHBQ-based precursors obtained by aqueous way have a micrometric meso-structure, formed by the assembly of micro-crystalline subunits which all posses the same crystallographic structure. The study of the assembly of the meso-structure allowed controlling the morphology of the elementary grain (cylinder, cube, disk...) with very good size distribution. The implementation of anhydrous systems in a controlled atmosphere allowed yielded a wider range of micro-structural parameters (surface area, porosity...). For all CP-type compounds, the thermal conversion to ceramic has barely altered the morphology of the materials. The microstructural aspects could be controlled via the method of synthesis. (author) [fr

  11. Highly Sensitive Detection of UV Radiation Using a Uranium Coordination Polymer.

    Science.gov (United States)

    Liu, Wei; Dai, Xing; Xie, Jian; Silver, Mark A; Zhang, Duo; Wang, Yanlong; Cai, Yawen; Diwu, Juan; Wang, Jian; Zhou, Ruhong; Chai, Zhifang; Wang, Shuao

    2018-02-07

    The accurate detection of UV radiation is required in a wide range of chemical industries and environmental or biological related applications. Conventional methods taking advantage of semiconductor photodetectors suffer from several drawbacks such as sophisticated synthesis and manufacturing procedure, not being able to measure the accumulated UV dosage as well as high defect density in the material. Searching for new strategies or materials serving as precise UV dosage sensor with extremely low detection limit is still highly desirable. In this work, a radiation resistant uranium coordination polymer [UO 2 (L)(DMF)] (L = 5-nitroisophthalic acid, DMF = N,N-dimethylformamide, denoted as compound 1) was successfully synthesized through mild solvothermal method and investigated as a unique UV probe with the detection limit of 2.4 × 10 -7 J. On the basis of the UV dosage dependent luminescence spectra, EPR analysis, single crystal structure investigation, and the DFT calculation, the UV-induced radical quenching mechanism was confirmed. Importantly, the generated radicals are of significant stability which offers the opportunity for measuring the accumulated UV radiation dosage. Furthermore, the powder material of compound 1 was further upgraded into membrane material without loss in luminescence intensity to investigate the real application potentials. To the best of our knowledge, compound 1 represents the most sensitive coordination polymer based UV dosage probe reported to date.

  12. Coordination polymers: trapping of radionuclides and chemistry of tetravalent actinides (Th, U) carboxylates

    International Nuclear Information System (INIS)

    Falaise, Clement

    2014-01-01

    The use of nuclear energy obviously raises the question of the presence of radionuclides in the environment. Currently, their mitigation is a major issue associated with nuclear chemistry. This thesis focuses on both the trapping of radionuclides by porous solids called Metal-Organic Frameworks (MOF) and the crystal chemistry of the carboxylate of tetravalent actinides (AnIV). The academic knowledge of the reactivity of carboxylate of AnIV could help the understanding of actinides speciation in environment. We focused on the sequestration of iodine by aluminum based MOF. The functionalization (electron-donor group) of the MOF drastically enhances the iodine capture capacity. The removal of light actinides (Th and U) from aqueous solution was also investigated as well as the stability of (Al)-MOF under γ radiation. More than twenty coordination polymers based on tetravalent actinides have been synthesized and characterized by single crystal X-ray diffraction. The use of controlled hydrolysis promotes the formation of coordination polymers exhibiting polynuclear cluster ([U 4 ], [Th 6 ], [U 6 ] and [U 38 ]). In order to understand the formation of the largest cluster, the ex-situ study of the solvo-thermal synthesis of compound {U 38 } has also been investigated. (author)

  13. Multifunctional Aromatic Carboxylic Acids as Versatile Building Blocks for Hydrothermal Design of Coordination Polymers

    Directory of Open Access Journals (Sweden)

    Jinzhong Gu

    2018-02-01

    Full Text Available Selected recent examples of coordination polymers (CPs or metal-organic frameworks (MOFs constructed from different multifunctional carboxylic acids with phenyl-pyridine or biphenyl cores have been discussed. Despite being still little explored in crystal engineering research, such types of semi-rigid, thermally stable, multifunctional and versatile carboxylic acid building blocks have become very promising toward the hydrothermal synthesis of metal-organic architectures possessing distinct structural features, topologies, and functional properties. Thus, the main aim of this mini-review has been to motivate further research toward the synthesis and application of coordination polymers assembled from polycarboxylic acids with phenyl-pyridine or biphenyl cores. The importance of different reaction parameters and hydrothermal conditions on the generation and structural types of CPs or MOFs has also been highlighted. The influence of the type of main di- or tricarboxylate ligand, nature of metal node, stoichiometry and molar ratio of reagents, temperature, and presence of auxiliary ligands or templates has been showcased. Selected examples of highly porous or luminescent CPs, compounds with unusual magnetic properties, and frameworks for selective sensing applications have been described.

  14. Coordination Polymers and Metal Organic Frameworks Derived from 1,2,4-Triazole Amino Acid Linkers

    Directory of Open Access Journals (Sweden)

    Yann Garcia

    2011-10-01

    Full Text Available The perceptible appearance of biomolecules as prospective building blocks in the architecture of coordination polymers (CPs and metal-organic frameworks (MOFs are redolent of their inclusion in the synthon/tecton library of reticular chemistry. In this frame, for the first time a synthetic strategy has been established for amine derivatization in amino acids into 1,2,4-triazoles. A set of novel 1,2,4-triazole derivatized amino acids were introduced as superlative precursors in the design of 1D coordination polymers, 2D chiral helicates and 3D metal-organic frameworks. Applications associated with these compounds are diverse and include gas adsorption-porosity partitioning, soft sacrificial matrix for morphology and phase selective cadmium oxide synthesis, FeII spin crossover materials, zinc-b-lactamases inhibitors, logistics for generation of chiral/non-centrosymmetric networks; and thus led to a foundation of a new family of functional CPs and MOFs that are reviewed in this invited contribution.

  15. 1D helical cadmium coordination polymers containing hydrazide ligand: The role of solvent and molar ratio

    Science.gov (United States)

    Notash, Behrouz

    2018-03-01

    Three new cadmium coordination polymers, [Cd(L)(NO3)2CH3OH]n, 1, {[Cd(L)2(NO3)]NO3}n, 2 and {[Cd(L)2(NO3)]NO3.H2O}n3, which L is nicotinohydrazide have been synthesized and characterized by spectroscopic methods as well as single crystal X-ray diffraction. Compounds 1-3 have been synthesized by changing solvent and metal-to-ligand ratio. X-ray crystallography showed that compounds 1-3 have different 1D helical structural motif. Semi-flexible nature of L ligand causes to syn-syn conformation which leading to form 1D helical chains coordination polymers. Compounds 2 and 3 were synthesized under the same reaction conditions with similar molar ratio, but using different solvent system. These compounds are pseudopolymorph which differs in the presence or absence of water molecule in their crystal packing. Hirshfeld surface analysis of the structures 1-3 have been performed and find the percent of participation of intermolecular interactions in the crystal packing of compounds.

  16. Homochiral coordination polymers constructed from aminocarboxylate derivates: Effect of bipyridine on the amidation reaction

    International Nuclear Information System (INIS)

    Chen Jianshan; Sheng Tianlu; Hu Shengmin; Xiang Shengchang; Fu Ruibiao; Zhu Qilong; Wu Xintao

    2012-01-01

    Using aminocarboxylate derivates (S)-N-(4-cyanobenzoic)-glutamic acid (denoted as cbg, 1a) and (S)-N-(4-nitrobenzoic)-glutamic acid (denoted as nbg, 1b) as chiral ligands, five new homochiral coordination polymers formulated as [Cu(cbg)(H 2 O) 2 ] n (3), [Cu(cbop) 2 (4,4′-bipy)(H 2 O)] n (4) (cbop=(S)-N-(4-cyanobenzoic)-5-oxoproline, 4,4′-bipy=4,4′-bipyridine), {[Cu(nbop) 2 (4,4′-bipy)]·4H 2 O} n (5) (nbop=(S)-N-(4-nitrobenzoic)-5-oxoproline), {[Cd(nbop) 2 (4,4′-bipy)]·2H 2 O} n (6), and [Ni(nbop) 2 (4,4′-bipy)(H 2 O) 2 ] n (7) have been hydrothermally synthesized and structurally characterized. Single-crystal X-ray diffraction study reveals that the original chirality of aminocarboxylate derivates is maintained in all these complexes. Complexes 3, 4, and 7 are one-dimensional infinite chain coordination polymers, while complexes 5 and 6 possess two-dimensional network structures. In situ cyclization of 1a and 1b was taken place in the formation of complexes 4–7, which may be due to the competition of 4,4′-bipyridine with chiral ligands during the coordination process. Preliminary optical behavior investigation indicates that ligands 1a, 1b, and complexes 6, 7 are nonlinear optical active. - Graphical abstract: Using aminocarboxylate derivates as chiral ligands, five new homochiral coordination polymers possessing second harmonic generation activities have been hydrothermally synthesized. Highlights: ► Two new chiral aminocarboxylate derivates were firstly synthesized. ► Five new homochiral metal organic complexes were obtained hydrothermally based on these ligands. ► Intramolecular amidation was taken place on the aminocarboxylate derivates during the formation of these complexes. ► In situ amidation may be due to the impact of 4,4′-bipyridine. ► The homochiral complexes are nonlinear optical active.

  17. Flexible Porous Coordination Polymers from Divergent Photoluminescent 4-Oxo-1,8-naphthalimide Ligands.

    Science.gov (United States)

    Hawes, Chris S; Byrne, Kevin; Schmitt, Wolfgang; Gunnlaugsson, Thorfinnur

    2016-11-07

    Two new luminescent ditopic naphthalimide-derived ligands, N-(4-cyanophenylmethylene)-4-(4-cyanophenoxy)-1,8-naphthalimide (L3) and N-(4-carboxyphenylmethylene)-4-(4-carboxyphenoxy)-1,8-naphthalimide (H 2 L4), have been prepared, and their coordination chemistry has been explored in the synthesis of three new coordination polymer materials. Complex poly-[Ag(L3) 2 ]BF 4 ·4.5H 2 O·0.5THF (1) is a 3-fold 2D → 2D parallel interpenetrated coordination polymer in which three interwoven sheets define inter- and intralayer channels containing anions and solvent molecules. Molecules of L3 interact in 1 through dominant head-to-head π-π stacking interactions, in an opposite aggregation mode to that observed in the free ligand in the crystalline phase. Complexes poly-[Cu(L4)(OH 2 )]·2DMF·0.5H 2 O (2) and poly-[Cd 2 (L4) 2 (OH 2 ) 2 ]·1.5DMF·3H 2 O (3) are related noninterpenetrated two-dimensional coordination polymers defined by one-dimensional metal-carboxylate chains, forming layers that interdigitate with adjacent networks through naphthalimide π-π interactions. Both materials undergo structural rearrangements on solvent exchange with acetonitrile; in the case of 3, this transformation can be followed by single-crystal X-ray diffraction, revealing the structure of the acetonitrile solvate poly-[Cd 2 (OH 2 ) 2 (L4) 2 ]·2MeCN (4), which shows a significant compression of the primary channels to accommodate the solvent guest molecules. Both materials display modest CO 2 adsorption after complete evacuation, and the original expanded phases can be regenerated by reimmersion in DMF. The photophysical properties of each ligand and complex were also explored, which revealed variations in emission wavelength, based on solid-state interactions, including a notable shift in the fluorescence emission band of 3 upon structural rearrangement to 4.

  18. A Novel Coordination Polymer Based on 4,4'-(Hexauoroisopropylidene)diphthalic Acid: Synthesis, Structure and Physical Properties

    International Nuclear Information System (INIS)

    Wang, Jun; Tao, Jianqing; Xu, Xiaojuan; Tan, Chunyun

    2012-01-01

    The design and synthesis of coordination polymers is an attractive area of research, not only owing to their diverse topology and intriguing structures but also due to their potential applications in many fields, such as ion-exchange, catalysis, luminescence, magnets, and gas storage. The mainstream method of constructing such coordination polymers is to utilize organic ligands with aromatic polycarboxylate groups, because of their excellent coordination capability and flexible coordination patterns. Among them, aromatic polycarboxylic derivatives, such as 1,2,4,5-benzenetetracarboxylic acid, 4,4'-oxydiphthalic acid, 4,4'-(hexauoroisopropylidene) diphthalic acid (H 4 FA), and so on, have been extensively used to prepare coordination polymers. Meanwhile, the flexible 1,4-bis(1,2,4-triazol-1-ylmethyl)-benzene (BTX) as an excellent derivative of triazole not only possesses the merits of triazole, but also can adopt different conformations compared with the corresponding 1,2,4-triazole ligand on the basis of the relative orientations of its CH 2 groups.10 Taking these into consideration, we explored the self-assembly of Cd(II) ion, H 4 FA, and BTX under hydrothermal conditions, and obtained a novel 3D coordination polymer: [Cd 3 (BTX) 2 (HFA) 2 · 2 H 2 O] n . Herein, we report the synthesis, crystal structure, and physical properties

  19. A novel self-assembly with zinc porphyrin coordination polymer for enhanced photocurrent conversion in supramolecular solar cells

    International Nuclear Information System (INIS)

    Cao, Jing; Liu, Jia-Cheng; Deng, Wen-Ting; Li, Ren-Zhi; Jin, Neng-Zhi

    2013-01-01

    Graphical abstract: An innovative type of self-assembly based on acetohydrazide zinc porphyrin coordination polymer has been prepared in supramolecular solar cells. - Highlights: • A novel assembly with acetohydrazide porphyrin coordination polymer. • The assembly based on porphyrin is prepared as parallel sample. • Coordination polymer-based assembly shows enhanced photoelectronic behavior. • A series of different organic acid ligands as anchoring groups are prepared. - Abstract: In this work, a novel acetohydrazide zinc porphyrin-based coordination polymer (CP)-isonicotinic acid self-assembly by metal-ligand axial coordination to modify the nano-structured TiO 2 electrode surface has been investigated in photoelectrochemical device. Compared to the assembly based on corresponding zinc porphyrin combined with isonicotinic acid by metal-ligand axial coordination, CP-isonicotinic acid assembly exhibits a significantly enhanced photoelectronic behavior. In addition, a series of different organic acid ligands were prepared to probe the impact of their structures on the photoelectronic performances of their corresponding assemblies-sensitized cells. This study affords a novel type of self-assembly to functionalize the nanostructured TiO 2 electrode surface in supramolecular solar cells

  20. Three-Dimensional Cadmium(II Cyanide Coordination Polymers with Ethoxy-, Butoxy- and Hexyloxy-ethanol

    Directory of Open Access Journals (Sweden)

    Takeshi Kawasaki

    2016-08-01

    Full Text Available The three novel cadmium(II cyanide coordination polymers with alkoxyethanols, [Cd(CN2(C2H5OCH2CH2OH]n (I, [{Cd(CN2(C4H9OCH2CH2OH}3{Cd(CN2}]n (II and [{Cd(CN2(H2O2}{Cd(CN2}3·2(C6H13OCH2CH2OH]n (III, were synthesized and charcterized by structural determination. Three complexes have three-dimensional Cd(CN2 frameworks; I has distorted tridymite-like structure, and, II and III have zeolite-like structures. The cavities of Cd(CN2 frameworks of the complexes are occupied by the alkoxyethanol molecules. In I and II, hydroxyl oxygen atoms of alkoxyethanol molecules coordinate to the Cd(II ions, and the Cd(II ions exhibit slightly distort trigonal-bipyramidal coordination geometry. In II, there is also tetrahedral Cd(II ion which is coordinated by only the four cyanides. The hydroxyl oxygen atoms of alkoxyethanol connects etheric oxygen atoms of the neighboring alkoxyethanol by hydrogen bond in I and II. In III, hexyloxyethanol molecules do not coordinate to the Cd(II ions, and two water molecules coordnate to the octahedral Cd(II ions. The framework in III contains octahedral Cd(II and tetrahedral Cd(II in a 1:3 ratio. The Cd(CN2 framework structures depended on the difference of alkyl chain for alkoxyethanol molecules.

  1. Homochiral nickel coordination polymers based on salen(Ni) metalloligands: synthesis, structure, and catalytic alkene epoxidation.

    Science.gov (United States)

    Huang, Yuanbiao; Liu, Tianfu; Lin, Jingxiang; Lü, Jian; Lin, Zujin; Cao, Rong

    2011-03-21

    One-dimensional (1D) homochiral nickel coordination polymers [Ni(3)(bpdc)(RR-L)(2)·(DMF)](n) (2R, RR-L = (R,R)-(-)-1,2-cyclohexanediamino-N,N'-bis(3-tert-butyl-5-(4-pyridyl)salicylidene), bpdc = 4,4'-biphenyldicarboxylic acid) and [Ni(3)(bpdc)(SS-L)(2)·(DMF)](n) (2S, SS-L = (S,S)-(-)-1,2-cyclohexanediamino-N,N'-bis(3-tert-butyl-5-(4-pyridyl)salicylidene) based on enantiopure pyridyl-functionalized salen(Ni) metalloligand units NiL ((1,2-cyclohexanediamino-N,N'-bis(3-tert-butyl-5-(4-pyridyl)salicylidene))Ni(II)) have been synthesized and characterized by microanalysis, IR spectroscopy, solid-state UV-vis spectroscopy, thermogravimetric analysis (TGA), circular dichroism (CD) spectroscopy, cyclic voltammetric measurement, and powder and single crystal X-ray diffraction. Each NiL as unbridging pendant metalloligand uses one terminal pyridyl group to coordinate achiral unit (nickel and bpdc(2-)) building a helical chain, while the other pyridyl group remains uncoordinated. Both 2R and 2S contain left- and right-handed helical chains made of the achiral building blocks, while the NiL as remote external chiral source is perpendicular to the backbone of the helices. The nickel coordination polymers 2R and 2S containing unsaturated active nickel center in metalloligand NiL can be used as self-supported heterogeneous catalysts. They show catalytic activity comparable with their homogeneous counterpart in alkene epoxidation and exhibit great potential as recyclable catalysts.

  2. Alkaline earth-based coordination polymers derived from a cyclotriphosphazene-functionalized hexacarboxylate

    Science.gov (United States)

    Ling, Yajing; Bai, Dongjie; Feng, Yunlong; He, Yabing

    2016-10-01

    Combination of hexakis(4-carboxylatephenoxy)cyclotriphosphazene with alkaline earth ions of increasing ionic radii (Mg2+, Ca2+ and Ba2+) under different solvothermal conditions yielded three new coordination polymers, and their crystal structures were determined by single-crystal X-ray diffraction analysis. The magnesium compound displays a three dimensional (3D) network structure constructed from the deprotonated ligand and the secondary building block Mg(COO)4, which can be rationalized as a (4,6)-connected topological net with the Schläfli symbol of (44·62)3(49·66)2. The calcium compound consists of 1D infinite "Ca-O" inorganic chains connected by the deprotonated ligands to from a 3D framework. The barium compound exhibits a 3D framework in which 1D "Ba-O" inorganic chains are connected together by the deprotonated organic linkers. Due to the semi-rigid nature, the ligand adopts distinctly different conformations in the three compounds. The metal ions' influence exerted on the final structure of the resulting coordination polymers is also discussed. When the radii of alkaline earth ions increases descending down the group from Mg(II) to Ba(II), the coordination number becomes larger and more versatile: from 6 in the magnesium compound, to 6,7 and 10 in the calcium compound, and to 8 and 9 in the barium compound, thus substantially influencing the resulting final framework structures. Also, the photophysical properties were investigated systematically, revealing that the three compounds are photoluminscent in the solid state at room temperature. This work demonstrates that although the multiplicity of conformation in the hexacarboxylate ligand based on the inorganic scaffold cyclotriphosphazene makes it difficult to predict how this ligand will form extended network, but provides unique opportunities for the formation of diverse inorganic-organic hybrids exhibiting rich structural topologies.

  3. A Molecularly Imprinted Polymer with Incorporated Graphene Oxide for Electrochemical Determination of Quercetin

    Directory of Open Access Journals (Sweden)

    Xiwen He

    2013-04-01

    Full Text Available The molecularly imprinted polymer based on polypyrrole film with incorporated graphene oxide was fabricated and used for electrochemical determination of quercetin. The electrochemical behavior of quercetin on the modified electrode was studied in detail using differential pulse voltammetry. The oxidation peak current of quercetin in B-R buffer solution (pH = 3.5 at the modified electrode was regressed with the concentration in the range from 6.0 × 10−7 to 1.5 × 10−5 mol/L (r2 = 0.997 with a detection limit of 4.8 × 10−8 mol/L (S/N = 3. This electrode showed good stability and reproducibility. In the above mentioned range, rutin or morin which has similar structures and at the same concentration as quercetin did not interfere with the determination of quercetin. The applicability of the method for complex matrix analysis was also evaluated.

  4. Ion induced transformation of polymer films into diamond-like carbon incorporating silver nano particles

    International Nuclear Information System (INIS)

    Schwarz, Florian P.

    2010-01-01

    Silver containing diamond-like carbon (DLC) is an interesting material for medical engineering from several points of view. On the one hand DLC provides high mechanical robustness. It can be used as biocompatible and wear resistant coating for joint replacing implants. On the other hand silver has antimicrobial properties, which could reduce post-operative inflammations. However conventional production of Ag-DLC by co-deposition of silver and carbon in a plasma process is problematic since it does not allow for a separate control of nano particle morphology and matrix properties. In this work an alternative production method has been developed to circumvent this problem. In metall-DLC-production by ion implantation into a nano composite, silver nano particles are initially formed in solution and then incorporated within a polymer matrix. Finally the polymer is transformed into DLC by ion implantation. The aspects and single steps of this method were investigated with regard to the resulting material's properties. The goal was to design an economically relevant deposition method. Based on experimental results a model of the transformation process has been established, which has also been implemented in a computer simulation. Finally the antibacterial properties of the material have been checked in a biomedical test. Here a bacterial killing rate of 90% could be achieved. (orig.)

  5. Photosensitive semiconducting polymer-incorporated nanofibers for promoting the regeneration of skin wound

    International Nuclear Information System (INIS)

    Jin, Guorui; Li, Jun; Li, Kai

    2017-01-01

    Photosensitive semiconducting polymer (SP) combined with light stimulation has shown the capability in promoting the proliferation of human dermal fibroblasts (HDFs). However, the high cytotoxicity of the used SP hindered its further application in bioactive scaffolds. In this contribution, we designed and synthesized a SP, poly (N,N-bis(2-octyldodecyl)-3,6-di(thiophen-2-yl)-2,5-dihydropyrrolo[3,4-c] pyrrole-1,4-dione-alt-thieno[3,2-b]thiophene) (PDBTT) with low cytotoxicity and strong absorbance in red and near-infrared region (600–1200 nm). The photosensitive SP was then applied in electrospun poly(ε-caprolactone) (PCL) nanofibrous scaffold and evaluated its proliferative effect on HDFs under the illumination from red light-emitting diode (LED) with high tissue penetration. After 9 days of continuous stimulation, the hybrid electrospun PCL/PDBTT nanofibers with low cytotoxicity showed excellent support for HDFs adhesion, proliferation and collagen secretion than neat PCL nanofibers and HDFs on the stimulated PCL/PDBTT nanofibers gained typical spindle morphology, indicating the well cell spreading on the stimulated PCL/PDBTT nanofibers. The incorporation of functional materials within synthetic biomaterials could be a novel way in improving the performance of engineered tissue constructs by providing multiple cues (e.g. electrical stimulation) to the attached cells. - Highlights: • A photosensitive semiconducting polymer (SP) was applied in electrospun nanofibrous scaffold. • The SP-incorporated scaffold could promote cell proliferation upon light stimulation. • The designed photosensitive SP could be applied as functional material with low cost and high durability in skin tissue engineering.

  6. In-syringe extraction using dissolvable layered double hydroxide-polymer sponges templated from hierarchically porous coordination polymers.

    Science.gov (United States)

    Ghani, Milad; Frizzarin, Rejane M; Maya, Fernando; Cerdà, Víctor

    2016-07-01

    Herein we report the use of cobalt porous coordination polymers (PCP) as intermediates to prepare advanced extraction media based on layered double hydroxides (LDH) supported on melamine polymer foam. The obtained dissolvable Ni-Co LDH composite sponges can be molded and used as sorbent for the in-syringe solid-phase extraction (SPE) of phenolic acids from fruit juices. The proposed sorbent is obtained due to the surfactant-assisted self-assembly of Co(II)/imidazolate PCPs on commercially available melamine foam, followed by the in situ conversion of the PCP into the final dissolvable LDH coating. Advantageous features for SPE are obtained by using PCPs with hierarchical porosity (HPCPs). The LDH-sponge prepared using intermediate HPCPs (HLDH-sponge) is placed in the headspace of a glass syringe, enabling flow-through extraction followed by analyte elution by the dissolution of the LDH coating in acidic conditions. Three phenolic acids (gallic acid, p-hydroxybenzoic acid and caffeic acid) were extracted and quantified using high performance liquid chromatography. Using a 5mL sample volume, the obtained detection limits were 0.15-0.35μgL(-1). The proposed method for the preparation of HLDH-sponges showed a good reproducibility as observed from the intra- and inter-day RSD's, which were <10% for all analytes. The batch-to-batch reproducibility for three different batches of HLDH-sponges was 10.6-11.2%. Enrichment factors of 15-21 were obtained. The HLDH-sponges were applied satisfactorily to the determination of phenolic acids in natural and commercial fruit juices, obtaining relative recoveries among 89.7-95.3%. Copyright © 2016 Elsevier B.V. All rights reserved.

  7. Surface grafting of a dense and rigid coordination polymer based on tri-para-carboxy-polychlorotriphenylmethyl radical and copper acetate

    KAUST Repository

    Mugnaini, Verónica

    2013-01-01

    The step-by-step method is here presented as suitable to anchor on appropriately functionalized gold surfaces a metal-organic coordination polymer based on a non-planar trigonal tri-para-carboxy-polychlorotriphenylmethyl radical derivative and copper acetate. The structural characteristics of the grafted coordination polymer are derived during the step-wise growth from the real time changes in refractive index and oscillation frequency. The film thickness, as measured by scanning force microscopy, combined with the mass uptake value from the quartz crystal microbalance, are used to estimate an average density of the grafted metal-organic coordination polymer that suggests the formation of a dense and rather rigid thin film. This journal is © 2013 The Royal Society of Chemistry.

  8. New 3-D coordination polymers based on semi-rigid V-shape tetracarboxylates

    International Nuclear Information System (INIS)

    Huang, Jing-Jing; Xu, Wei; Wang, Yan-Ning; Yu, Jie-Hui; Zhang, Ping; Xu, Ji-Qing

    2015-01-01

    Under the hydrothermal conditions, the reactions of transition-metal salts, tetracarboxylic acids and N,N′-donor ligands yielded three new coordination polymers as [Cu 4 (fph) 2 (bpe) 3 (H 2 O) 2 ]·2H 2 O (fph=4,4′-(hexafluoroisopropylidene)diphthalate, bpe=1,2-bis(pyridyl)ethylene) 1, [Co 2 (fph)(bpa) 2 (H 2 O) 2 ]·3H 2 O (bpa=1,2-bis(pyridyl)ethylane) 2, and [Ni(H 2 O)(H 2 oph)(bpa)] (oph=4,4′-oxydiphthalate) 3. X-ray single-crystal diffraction analysis revealed that the title three compounds all possess the three-dimensional (3-D) network structures. For compound 1, the fph molecules first link the Cu 2+ ions into a two-dimensional (2-D) wave-like layer with a (4,4) topology. The bpe molecules act as the second linkers, extending the 2-D layers into a 3-D network. For compound 2, the fph molecules still serve as the first connectors, linking the Co 2+ ions into a one-dimensional (1-D) tube-like chain. Then the bpa molecules propagate the chains into a 3-D (4,4,4)-connected network. In the formation of the 3-D network of compound 3, the oph molecule does not play a role. The bpa molecules as well as the water molecules act as a mixed bridge. Only a kind of 4-connected metal node is observed in compound 3. The magnetic properties of compounds 1–3 were investigated and all exhibit the predominant antiferromegnetic magnetic behaviors. - Graphical abstract: Structures of three semi-rigid V-shape tetracarboxylate-based coordination polymers were reported, and their magnetic properties were investigated. - Highlights: • Structures of three tetracarboxylate-based coordination polymers were reported. • Role of organic bases in metal–tetracarboxylate compounds was discussed. • Characters of V-shape and semi-rigidity for tetracarboxylate play a key role in crystal growth. • Their magnetic properties were investigated

  9. New 3-D coordination polymers based on semi-rigid V-shape tetracarboxylates

    Energy Technology Data Exchange (ETDEWEB)

    Huang, Jing-Jing; Xu, Wei; Wang, Yan-Ning [College of Chemistry, Jilin University, Jiefang Road 2519, Changchun 130023, Jilin (China); State Key Laboratory of Inorganic Synthesis and Preparative Chemistry, Jilin University, Qianjin Road 2699, Changchun 130012, Jilin (China); Yu, Jie-Hui, E-mail: jhyu@jlu.edu.cn [College of Chemistry, Jilin University, Jiefang Road 2519, Changchun 130023, Jilin (China); State Key Laboratory of Inorganic Synthesis and Preparative Chemistry, Jilin University, Qianjin Road 2699, Changchun 130012, Jilin (China); Zhang, Ping, E-mail: zhangping@jlu.edu.cn [College of Chemistry, Jilin University, Jiefang Road 2519, Changchun 130023, Jilin (China); Xu, Ji-Qing [College of Chemistry, Jilin University, Jiefang Road 2519, Changchun 130023, Jilin (China); State Key Laboratory of Inorganic Synthesis and Preparative Chemistry, Jilin University, Qianjin Road 2699, Changchun 130012, Jilin (China)

    2015-03-15

    Under the hydrothermal conditions, the reactions of transition-metal salts, tetracarboxylic acids and N,N′-donor ligands yielded three new coordination polymers as [Cu{sub 4}(fph){sub 2}(bpe){sub 3}(H{sub 2}O){sub 2}]·2H{sub 2}O (fph=4,4′-(hexafluoroisopropylidene)diphthalate, bpe=1,2-bis(pyridyl)ethylene) 1, [Co{sub 2}(fph)(bpa){sub 2}(H{sub 2}O){sub 2}]·3H{sub 2}O (bpa=1,2-bis(pyridyl)ethylane) 2, and [Ni(H{sub 2}O)(H{sub 2}oph)(bpa)] (oph=4,4′-oxydiphthalate) 3. X-ray single-crystal diffraction analysis revealed that the title three compounds all possess the three-dimensional (3-D) network structures. For compound 1, the fph molecules first link the Cu{sup 2+} ions into a two-dimensional (2-D) wave-like layer with a (4,4) topology. The bpe molecules act as the second linkers, extending the 2-D layers into a 3-D network. For compound 2, the fph molecules still serve as the first connectors, linking the Co{sup 2+} ions into a one-dimensional (1-D) tube-like chain. Then the bpa molecules propagate the chains into a 3-D (4,4,4)-connected network. In the formation of the 3-D network of compound 3, the oph molecule does not play a role. The bpa molecules as well as the water molecules act as a mixed bridge. Only a kind of 4-connected metal node is observed in compound 3. The magnetic properties of compounds 1–3 were investigated and all exhibit the predominant antiferromegnetic magnetic behaviors. - Graphical abstract: Structures of three semi-rigid V-shape tetracarboxylate-based coordination polymers were reported, and their magnetic properties were investigated. - Highlights: • Structures of three tetracarboxylate-based coordination polymers were reported. • Role of organic bases in metal–tetracarboxylate compounds was discussed. • Characters of V-shape and semi-rigidity for tetracarboxylate play a key role in crystal growth. • Their magnetic properties were investigated.

  10. Coordination Polymer Modified Separator for Mitigating Polysulfide Shuttle Effect in Lithium-Sulfur Batteries

    KAUST Repository

    Wan, Yi

    2017-11-19

    The development of the new cathode and anode materials of Lithium-Ion Batteries (LIBs) with high energy density and outstanding electrochemical performance is of substantial technological importance due to the ever-increasing demand for economic and efficient energy storage system. Because of the abundance of element sulfur and high theoretical energy density, Lithium-Sulfur (Li-S) batteries have become one of the most promising candidates for the next-generation energy storage system. However, the shuttling effect of electrolyte-soluble polysulfides severely impedes the cell performance and commercialization of Li-S batteries, and significant progress have been made to mitigate this shuttle effect in the past two decades. Coordination polymers (CPs) or Metal-organic Frameworks (MOFs) have been attracted much attention by virtue of their controllable porosity, nanometer cavity sizes and high surface areas, which supposed to be an available material in suppressing polysulfide migration. In this thesis, we investigate different mechanisms of mitigating polysulfide diffusion by applying a layer of MOFs (including Y-FTZB, ZIF-7, ZIF-8, and HKUST-1) on a separator. We also fabricate a new free-standing 2D coordination polymer Zn2(Benzimidazolate)2(OH)2 with rich hydroxyl (OH-) groups by using a simple, scalable and low cost method at air/water surface. Our results suggest that the chemical stability, the cluster morphology and the surface function groups of MOFs shows a greater impact on minimizing the shuttling effect in Li-S batteries, other than the internal cavity size in MOFs. Meanwhile, the new design of 2D coordination polymer efficiently mitigate the shuttling effect in Li-S battery resulting in a largely promotion of the battery capacity to 1407 mAh g-1 at 0.1 C and excellent cycling performance (capacity retention of 98% after 200 cycles at 0.25C). Such excellent cell performance is mainly owing to the fancying physical and chemical structure controllability

  11. Dye-incorporated Polynaphthalenediimide Acceptor for Additive-free High-performance All-polymer Solar Cells.

    Science.gov (United States)

    Chen, Dong; Yao, Jia; Yin, Jingping; Lv, Ruizhi; Huang, Bin; Liu, Siqi; Yang, Chunhe; Zhang, Zhiguo; Chen, Lie; Chen, Yiwang; Li, Yongfang

    2018-02-22

    All-polymer solar cells (all-PSCs) can offer unique advantages for applications in flexible devices, and naphthalene diimide (NDI)-based polymer acceptors are the widely used polymer acceptors. However, their power conversion efficiency (PCE) still lags behind that of state-of-the-art polymer solar cells, due to low light absorption, suboptimal energy levels and the strong aggregation of the NDI-based polymer acceptor. In this work, by means of simple random copolymerization, a rhodanine-based dye molecule was introduced into the NDI-based polymer acceptor and showed an improved light absorption coefficient, an up-shifted lowest unoccupied molecular orbital level and reduced crystallization. Consequently, additive-free all-PSCs demonstrated a high PCE of 8.13%, which is one of the highest performance characteristics reported for all-PSCs to date. These results indicate that incorporating dye into the n-type polymer yields insights into the precise design of high-performance polymer acceptors for all-PSCs. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  12. A 1D coordination polymer of UF{sub 5} with HCN as a ligand

    Energy Technology Data Exchange (ETDEWEB)

    Scheibe, Benjamin; Rudel, Stefan S.; Buchner, Magnus R.; Kraus, Florian [Fachbereich Chemie, Philipps-Universitaet Marburg (Germany); Karttunen, Antti J. [Department of Chemistry, Aalto University (Finland)

    2017-01-05

    β-Uranium(V) fluoride was reacted with liquid anhydrous hydrogen cyanide to obtain a 1D coordination polymer with the composition {sup 1}{sub ∞}[UF{sub 5}(HCN){sub 2}], {sup 1}{sub ∞}[UF{sub 4/1}F{sub 2/2}-(HCN){sub 2/1}], revealed by single-crystal X-ray structure determination. The reaction system was furthermore studied by means of vibrational and NMR spectroscopy, as well as by quantum chemical calculations. The compound presents the first described polymeric HCN Lewis adduct and the first HCN adduct of a uranium fluoride. (copyright 2017 Wiley-VCH Verlag GmbH and Co. KGaA, Weinheim)

  13. Two new coordination polymers based on a flexible bib ligand: Structures and magnetic properties

    Science.gov (United States)

    Liu, Yong-Liang; Liu, Ping; Li, Ke-Bin; Zhou, Chun-Sheng; Yue, Ke-Fen

    2017-11-01

    Two new coordination polymers, {[Co(bib)0.5(bdc-Br2)]·CH3OH}n (1) and {[Co(bib)(1,4-ndc)]·0.5H2O}n (2) have been synthesized. The results of X-ray crystallographic analysis show that compound 1 exhibits a 6-connected three-dimensional (3D) 2-fold interpenetrated architectures with the point symbol of 412.63, 2 displays a 4-connected 3D 4-fold [2 + 2] interpenetrated structures with the point symbol of 66. The formulas of 1 and 2 were determined by X-ray crystallography, elemental analysis, and thermogravimetric analysis (TGA). In addition, the compounds 1 and 2 reveal antiferromagnetic interactions.

  14. Pressure Sensor via Optical Detection Based on a 1D Spin Transition Coordination Polymer

    Directory of Open Access Journals (Sweden)

    Cătălin M. Jureschi

    2015-01-01

    Full Text Available We have investigated the suitability of using the 1D spin crossover coordination polymer [Fe(4-(2’-hydroxyethyl-1,2,4-triazole3]I2∙H2O, known to crossover around room temperature, as a pressure sensor via optical detection using various contact pressures up to 250 MPa. A dramatic persistent colour change is observed. The experimental data, obtained by calorimetric and Mössbauer measurements, have been used for a theoretical analysis, in the framework of the Ising-like model, of the thermal and pressure induced spin state switching. The pressure (P-temperature (T phase diagram calculated for this compound has been used to obtain the P-T bistability region.

  15. Flexible Two-Dimensional Square-Grid Coordination Polymers: Structures and Functions

    Directory of Open Access Journals (Sweden)

    Hiroshi Kajiro

    2010-09-01

    Full Text Available Coordination polymers (CPs or metal-organic frameworks (MOFs have attracted considerable attention because of the tunable diversity of structures and functions. A 4,4'-bipyridine molecule, which is a simple, linear, exobidentate, and rigid ligand molecule, can construct two-dimensional (2D square grid type CPs. Only the 2D-CPs with appropriate metal cations and counter anions exhibit flexibility and adsorb gas with a gate mechanism and these 2D-CPs are called elastic layer-structured metal-organic frameworks (ELMs. Such a unique property can make it possible to overcome the dilemma of strong adsorption and easy desorption, which is one of the ideal properties for practical adsorbents.

  16. Coordination Nature of 4-Mercaptoaniline to Sn(II Ion: Formation of a One Dimensional Coordination Polymer and Its Decomposition to a Mono Nuclear Sn(IV Complex

    Directory of Open Access Journals (Sweden)

    Eon S. Burkett

    2014-12-01

    Full Text Available The coordination of the bifunctional ligand 4-mercaptoaniline with aqueo us tin(II metal ion was studied. A coordination polymer was synthesized when an aqueous solution of SnCl2 was treated with 4-MA. The crystalline material is stable under atmospheric conditions retaining its oxidation state. However, when submerged in a solution saturated with oxygen, the compound oxidizes to a mononuclear tin(IV complex. Both the compounds were characterized by single crystal X-ray diffraction studies. Although the structure of the tin(IV complex was previously reported, crystal structure of this compound was redetermined.

  17. Syntheses, structures and luminescence properties of lanthanide coordination polymers with helical character

    International Nuclear Information System (INIS)

    Zhou Ruisha; Cui Xiaobing; Song Jiangfeng; Xu Xiaoyu; Xu Jiqing; Wang Tiegang

    2008-01-01

    A series of lanthanide coordination polymers, (Him) n [Ln(ip) 2 (H 2 O)] n [Ln=La(1), Pr(2), Nd(3) and Dy(4), H 2 ip=isophthalic acid, im=imidazole] and [Y 2 (ip) 3 (H 2 O) 2 ] n .nH 2 O (5), have been synthesized and characterized by elemental analyses, infrared (IR), ultraviolet-visible-near infrared (UV-Vis-NIR) and single-crystal X-ray diffraction analyses. The isostructural compounds 1-4 possess 3-D structures with three different kinds of channels. Compound 5 features a 2-D network making of two different kinds of quadruple-helical chains. Compounds 2 and 3 present the characteristic emissions of Pr(III) and Nd(III) ions in NIR region, respectively. Compound 4 shows sensitized luminescence of Dy(III) ions in visible region. - Graphical abstract: A series of lanthanide coodination polymers, (Him) n [Ln(ip) 2 (H 2 O)] n [Ln=La(1), Pr(2), Nd(3) and Dy(4)] and [Y 2 (ip) 3 (H 2 O) 2 ] n .nH 2 O (5), have been reported. The isostructural compounds 1-4 possess 3-D structures with three different kinds of channels. Compound 5 displays a 2-D network making of two kinds of quadruple-helical chains. Display Omitted

  18. One Dimensional Coordination Polymer of Zn(II) for Developing Multifunctional Nanoparticles.

    Science.gov (United States)

    Agarwal, Rashmi A

    2017-10-16

    A variety of nanoparticles (NPs) including Ag, Au, Pd, Cr and mixed Cu/Fe have been synthesized in a non-activated (without solvent removal) one dimensional coordination polymer (CP) of Zn(II) via two different mechanisms, acid formation and redox activity of the framework. Main driving force to grow these NPs within the cavities of CP is the presence of free oxygens of one of the monodentate carboxylate groups of BDC ligand. These free oxygens act as anchoring sites for the metal ions of the metal precursors. Chemical and physical characteristics of the NPs within the framework have been evaluated by the high resolution transmission electron microscopic (HRTEM) images. Excluding Ag(0) and Pd(0) other NPs are present as combinations of their elemental as well as oxide forms (Au/Au 2 O 3 , Cr/Cr 2 O 3 /CrO 2 and Cu/Cu 2 O, Fe/FeO). Synthesized Ag NPs within the framework show remarkable antibacterial efficacy at extremely low concentrations. Ag, Au and Cu/Fe NPs show ferromagnetic properties within the framework at room temperature. This polymer has potential to sequester highly toxic Cr(VI) to non toxic Cr(0), Cr(III) and Cr(IV) species.

  19. Developing multifunctional nanoparticles in a 1-D coordination polymer of Cd(II)

    Science.gov (United States)

    Agarwal, Rashmi A.; Gupta, Neeraj K.

    2017-11-01

    A simple synthesis for the integration of different nanoparticles (NPs) including Ag, Au, Pd, Cr and mixed (Cu/Fe), has been demonstrated within the nanopores of a non-activated one dimensional porous coordination polymer (PCP) of Cd(II) due to its high flexible structure. There are two different mechanisms (acid formation (HCl/HNO3) and redox activity of the framework) elucidated by electron paramagnetic resonance (EPR). Presence of -NO2 groups of the ligand act as anchoring sites for metal ions of metal precursors leading to NPs growth within the PCP explained by FTIR. High resolution transmission electron microscopy (HRTEM) images provided insight of the chemical and physical characteristics of the NPs within the framework. Ag/AgO NPs exhibit excellent antibacterial properties at extremely low concentrations. The polymer shows potential for sequestration and reduction of hexavalent Cr (highly toxic) to elemental, trivalent and tetravalent Cr (non toxic). This framework is also an excellent template for fabrication and dry storage of nanoparticles synthesized by mixed metal precursors. Ferromagnetic properties have been shown by Ag and Au NPs integrated frameworks while Cu/Fe@Cd-PCP behaves as a paramagnet material at room temperature.

  20. Toward Activity Origin of Electrocatalytic Hydrogen Evolution Reaction on Carbon-Rich Crystalline Coordination Polymers.

    Science.gov (United States)

    Wang, Lihuan; Tranca, Diana C; Zhang, Jian; Qi, Yanpeng; Sfaelou, Stavroula; Zhang, Tao; Dong, Renhao; Zhuang, Xiaodong; Zheng, Zhikun; Seifert, Gotthard

    2017-10-01

    The fundamental understanding of electrocatalytic active sites for hydrogen evolution reaction (HER) is significantly important for the development of metal complex involved carbon electrocatalysts with low kinetic barrier. Here, the MS x N y (M = Fe, Co, and Ni, x/y are 2/2, 0/4, and 4/0, respectively) active centers are immobilized into ladder-type, highly crystalline coordination polymers as model carbon-rich electrocatalysts for H 2 generation in acid solution. The electrocatalytic HER tests reveal that the coordination of metal, sulfur, and nitrogen synergistically facilitates the hydrogen ad-/desorption on MS x N y catalysts, leading to enhanced HER kinetics. Toward the activity origin of MS 2 N 2 , the experimental and theoretical results disclose that the metal atoms are preferentially protonated and then the production of H 2 is favored on the MN active sites after a heterocoupling step involving a N-bound proton and a metal-bound hydride. Moreover, the tuning of the metal centers in MS 2 N 2 leads to the HER performance in the order of FeS 2 N 2 > CoS 2 N 2 > NiS 2 N 2 . Thus, the understanding of the catalytic active sites provides strategies for the enhancement of the electrocatalytic activity by tailoring the ligands and metal centers to the desired function. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  1. One-dimensional coordination polymers of whole row rare earth tris-pivalates

    Science.gov (United States)

    Tsymbarenko, Dmitry; Martynova, Irina; Grebenyuk, Dimitry; Shegolev, Vsevolod; Kuzmina, Natalia

    2018-02-01

    Fourteen 1D coordination polymers of rare earth pivalates [Ln(Piv)3]∞ (Ln = Y, La, Pr, Nd, Sm-Lu) were synthesized and characterized by powder X-ray diffraction, IR spectroscopy, TGA, and conventional elemental analysis. Crystal structures of [La(Piv)3]∞, [Yb(Piv)3]∞, [Lu(Piv)3]∞ were determined by means of single crystal X-ray analysis at 120 K, those of [Y(Piv)3]∞ and [Ho(Piv)3]∞ - from powder XRD data at 293 K. Transformation of [Ln(Piv)3]∞ structure and Piv- anions coordination mode along the whole row has been derived from powder XRD and IR spectroscopy results, and shown to crucially affect the relative location of 1D chains in the crystal structure, as well as the Ln···Ln distance within the single chain. Negative thermal expansion along 1D [Ln(Piv)3]∞ chain was revealed for Ln = Tm, Yb, Lu. Enforcement of 1D polymeric structure with the decrease of Ln ionic radius has been established from solid-state DFT calculations.

  2. Two coordination polymers based on semicarbazone Schiff base and azide: synthesis, crystal structure, electrochemistry, magnetic properties and biological activity

    Czech Academy of Sciences Publication Activity Database

    Shaabani, B.; Khandar, A.A.; Dušek, Michal; Pojarová, Michaela; Mahmoudi, F.; Feher, A.; Kajňaková, M.

    2013-01-01

    Roč. 66, č. 5 (2013), s. 748-762 ISSN 0095-8972 Grant - others:AV ČR(CZ) AP0701 Program:Akademická prémie - Praemium Academiae Institutional support: RVO:68378271 Keywords : Schiff bases * semicarbazone * coordination polymer * structure analyses Subject RIV: CB - Analytical Chemistry, Separation Impact factor: 2.224, year: 2013

  3. Stereoselectivity in metallocene-catalyzed coordination polymerization of renewable methylene butyrolactones: From stereo-random to stereo-perfect polymers

    KAUST Repository

    Chen, Xia

    2012-05-02

    Coordination polymerization of renewable α-methylene-γ-(methyl) butyrolactones by chiral C 2-symmetric zirconocene catalysts produces stereo-random, highly stereo-regular, or perfectly stereo-regular polymers, depending on the monomer and catalyst structures. Computational studies yield a fundamental understanding of the stereocontrol mechanism governing these new polymerization reactions mediated by chiral metallocenium catalysts. © 2012 American Chemical Society.

  4. Copper-based coordination polymers from thiophene and furan dicarboxylates with high isosteric heats of hydrogen adsorption

    NARCIS (Netherlands)

    Yang, Jie; Lutz, Martin; Grzech, Anna; Mulder, Fokko M.; Dingemans, Theo J.

    2014-01-01

    Self-assembled Cu-based coordination polymers derived from thiophene-2,5-dicarboxylic acid (Cu-TDC) and furan-2,5-dicarboxylic acid (Cu-FDC) were synthesized via a solvothermal method and their H2 adsorption behaviour was investigated and contrasted with isophthalic acid (Cu-m-BDC) and terephthalic

  5. Recovery of metals from simulant spent lithium-ion battery as organophosphonate coordination polymers in aqueous media

    Energy Technology Data Exchange (ETDEWEB)

    Perez, Emilie; Andre, Marie-Laure; Navarro Amador, Ricardo [ICSM, Institut de Chimie Séparative de Marcoule, UMR 5257, CEA/CNRS/ENSCM/UM, Bât 426, BP 17171, 30207 Bagnols-sur-Cèze cedex (France); Hyvrard, François; Borrini, Julien [SARPI VEOLIA, Direction Technique et Innovations, Zone portuaire de Limay-Porcheville, 427 route du Hazay, 78520 Limay (France); Carboni, Michaël, E-mail: michael.carboni@cea.fr [ICSM, Institut de Chimie Séparative de Marcoule, UMR 5257, CEA/CNRS/ENSCM/UM, Bât 426, BP 17171, 30207 Bagnols-sur-Cèze cedex (France); Meyer, Daniel [ICSM, Institut de Chimie Séparative de Marcoule, UMR 5257, CEA/CNRS/ENSCM/UM, Bât 426, BP 17171, 30207 Bagnols-sur-Cèze cedex (France)

    2016-11-05

    Highlights: • Original waste disposal strategies for battery. • Precipitation of metals as coordination polymers. • Organo-phosphonate coordination polymers. • Selective extraction of manganese or co-precipitation of manganese/cobalt. • The recycling process give a promising application on any waste solution. - Abstract: An innovative approach is proposed for the recycling of metals from a simulant lithium-ion battery (LIBs) waste aqueous solution. Phosphonate organic linkers are introduced as precipitating agents to selectively react with the metals to form coordination polymers from an aqueous solution containing Ni, Mn and Co in a hydrothermal process. The supernatant is analyzed by ICP-AES to quantify the efficiency and the selectivity of the precipitation and the materials are characterized by Scanning Electron Microscopy (SEM), Powder X-Ray Diffraction (PXRD), Thermogravimetric Analyses (TGA) and nitrogen gas sorption (BET). Conditions have been achieved to selectively precipitate Manganese or Manganese/Cobalt from this solution with a high efficiency. This work describes a novel method to obtain potentially valuable coordination polymers from a waste metal solution that can be generalized on any waste solution.

  6. Stereoselectivity in metallocene-catalyzed coordination polymerization of renewable methylene butyrolactones: from stereo-random to stereo-perfect polymers.

    Science.gov (United States)

    Chen, Xia; Caporaso, Lucia; Cavallo, Luigi; Chen, Eugene Y-X

    2012-05-02

    Coordination polymerization of renewable α-methylene-γ-(methyl)butyrolactones by chiral C(2)-symmetric zirconocene catalysts produces stereo-random, highly stereo-regular, or perfectly stereo-regular polymers, depending on the monomer and catalyst structures. Computational studies yield a fundamental understanding of the stereocontrol mechanism governing these new polymerization reactions mediated by chiral metallocenium catalysts. © 2012 American Chemical Society

  7. Hexafluoridophosphate partial hydrolysis leading to the one-dimensional coordination polymer [{Cu(xantphos)(µ-PO2F2)}n

    OpenAIRE

    Keller, S.; Brunner, F.; Prescimone, A.; Constable, E. C.; Housecroft, C. E.

    2015-01-01

    The one-dimensional coordination polymer [{Cu(xantphos)(μ-PO2F2)}n] (xantphos = 4,5-bis(diphenylphosphino)-9,9-dimethylxanthene) is reported, the first extended structure in which copper(I) centres are linked by μ-PO2F2 units.

  8. Two-dimensional copper(I) coordination polymer materials as photocatalysts for the degradation of organic dyes.

    Science.gov (United States)

    Wen, Tian; Zhang, De-Xiang; Zhang, Jian

    2013-01-07

    Two isomeric two-dimensional copper(I) coordination polymer materials based on an in situ generated 5-(3-pyridyl)tetrazole ligand show similar layer structures but distinct photoluminescent and photocatalytic properties, which present an interesting comparative study on the structure-property correlation between isomeric materials.

  9. Hydrothermal reactions: From the synthesis of ligand to new lanthanide 3D-coordination polymers

    Energy Technology Data Exchange (ETDEWEB)

    Silva, Fausthon Fred da; Fernandes de Oliveira, Carlos Alberto; Lago Falcão, Eduardo Henrique [Laboratório de Terras Raras, Departamento de Química Fundamental, Universidade Federal de Pernambuco (DQF-UFPE), 50590-470 Recife, PE (Brazil); Gatto, Claudia Cristina [Laboratório de Síntese Inorgânica e Cristalografia, Instituto de Química, Universidade de Brasília (IQ-UnB), 70904-970 Brasilia, DF (Brazil); Bezerra da Costa, Nivan; Oliveira Freire, Ricardo [Pople Computational Chemistry Laboratory, Departamento de Química, Universidade Federal de Sergipe, São Cristóvão-SE 49100-000 (Brazil); Chojnacki, Jarosław [Department of Inorganic Chemistry, Gdansk University of Technology, 80-233 Gdansk (Poland); Alves Júnior, Severino, E-mail: salvesjr@ufpe.br [Laboratório de Terras Raras, Departamento de Química Fundamental, Universidade Federal de Pernambuco (DQF-UFPE), 50590-470 Recife, PE (Brazil)

    2013-11-15

    The organic ligand 2,5-piperazinedione-1,4-diacetic acid (H{sub 2}PDA) was synthesized under hydrothermal conditions starting from the iminodiacetic acid and catalyzed by oxalic acid. The X-ray powder diffraction data indicates that the compound crystallizes in the P2{sub 1}/c monoclinic system as reported in the literature. The ligand was also characterized by elemental analysis, magnetic nuclear resonance, infrared spectroscopy and thermogravimetric analysis. Two new coordination networks based on lanthanide ions were obtained with this ligand using hydrothermal reaction. In addition to single-crystal X-ray diffraction, the compounds were characterized by infrared spectroscopy, thermogravimetric analysis, scanning electron microscopy and elemental analysis. Single-crystal XRD showed that the compounds are isostructural, crystallizing in P2{sub 1}/n monoclinic system with chemical formula [Ln(PDA){sub 1.5}(H{sub 2}O)](H{sub 2}O){sub 3} (Ln=Gd{sup 3+}(1) and Eu{sup 3+}(2)).The luminescence properties of both compounds were studied. In the compound (1), a broad emission band was observed at 479 nm, redshifted by 70 nm in comparison of the free ligand. In (2), the typical f–f transition was observed with a maximum peak at 618 nm, related with the red emission of the europium ions. Computational methods were performed to simulate the crystal structure of (2). The theoretical calculations of the intensity parameters are in good agreement with the experimental values. - Graphical abstract: Scheme of obtaining the ligand 2,5-piperazinedione-1,4-diacetic acid (H{sub 2}PDA) and two new isostructural 3D-coordination polymers [Ln(PDA){sub 1.5}(H{sub 2}O)](H{sub 2}O){sub 3} (Ln=Gd{sup 3+} and Eu{sup 3+}) by hydrothermal synthesis. Display Omitted - Highlights: • The ligand 2,5-piperazinedione-1,4-diacetic acid was synthetized using the hydrothermic method and characterized. • Two new 3D-coordination polymers with this ligand containing Gd{sup 3+} and Eu{sup 3+} ions

  10. [Synthesis and structure of silver(I) coordination polymers with bis(pyridyl) ligands linked by an aromatic sulfonamide].

    Science.gov (United States)

    Katagiri, Kosuke

    2014-01-01

    Aromatic sulfonamides exist in a synclinal conformation with the twisted structure arising from rotation around the S-N bond in both the solid state and in solution. Simple bidentate ligands containing the sulfonamide moiety can be extended to form elongated ligands, and optically active components can be added to form a versatile building block for the construction of coordination polymers with many structures. Mixing the simple ligands 1 and 2 and the elongated ligands 3 and 4 with different Ag(I) salts yielded the corresponding complexes [Ag(1)OTf]n (1a), [Ag(2)]n•nOTf(2a), [Ag(3)OTf]n (3a), [Ag(3)]n•nBF₄ (3b), [Ag(4)CH₃CN]n•nBF₄•nCHCl₃ (4b), and [Ag(4)]n•nSbF₆•nCH₄O (4c). Straight chains and racemic helical polymers were observed in the crystal structure of complexes 1a and 2a, respectively. In the crystal structures of complexes 3a and 4b, infinite 1D straight chains containing a T-shaped coordination geometry about the Ag(I) centers were formed by the reaction of ligands 3 or 4 with Ag(I) salts in CH₃CN/CHCl₃. A continuous 1D coordination polymer containing a racemic mixture of left- and right-handed helices formed in the crystal structure of complex 3b. Furthermore, a layered coordination polymer consisting of a racemic mixture of left- and right-handed polymers was observed from the crystal structure of complex 4c. The construction of optically pure left- or right-handed 1D helical polymers via the introduction of chiral functional groups on the nitrogen atom of the sulfonamide ligand is currently under investigation in our laboratory.

  11. Solvent-vapour-assisted pathways and the role of pre-organization in solid-state transformations of coordination polymers

    Directory of Open Access Journals (Sweden)

    James S. Wright

    2015-03-01

    Full Text Available A family of one-dimensional coordination polymers, [Ag4(O2C(CF22CF34(phenazine2(arenen]·m(arene, 1 (arene = toluene or xylene, have been synthesized and crystallographically characterized. Arene guest loss invokes structural transformations to yield a pair of polymorphic coordination polymers [Ag4(O2C(CF22CF34(phenazine2], 2a and/or 2b, with one- and two-dimensional architectures, respectively. The role of pre-organization of the polymer chains of 1 in the selectivity for formation of either polymorph is explored, and the templating effect of toluene and p-xylene over o-xylene or m-xylene in the formation of arene-containing architecture 1 is also demonstrated. The formation of arene-free phase 2b, not accessible in a phase-pure form through other means, is shown to be the sole product of loss of toluene from 1-tol·tol [Ag4(O2C(CF22CF34(phenazine2(toluene]·2(toluene, a phase containing toluene coordinated to Ag(I in an unusual μ:η1,η1 manner. Solvent-vapour-assisted conversion between the polymorphic coordination polymers and solvent-vapour influence on the conversion of coordination polymers 1 to 2a and 2b is also explored. The transformations have been examined and confirmed by X-ray diffraction, NMR spectroscopy and thermal analyses, including in situ diffraction studies of some transformations.

  12. Electrical and optical properties of hybrid polymer solar cells incorporating Au and CuO nanoparticles

    Directory of Open Access Journals (Sweden)

    Aruna P. Wanninayake

    2015-12-01

    Full Text Available In this study, to enhance the power conversion efficiency (PCE of the polymer solar cells (PSCs, Gold (Au and Copper oxide nanoparticles (CuO-NPs are incorporated into the PEDOT:PSS and P3HT/PCBM active layers respectively. PSCs with a constant CuO-NP content were fabricated with varying amounts of Au NPs. Addition of Au NPs increased the power conversion efficiency by up to 18% compared to a reference cell without Au-NPs. The short circuit current(Jsc of the cells containing 0.06 mg of Au NPs was measured at 7.491 mA/cm2 compared to 6.484 mA/cm2 in the reference cells with 0.6 mg of CuO nanoparticles; meanwhile, the external quantum efficiency(EQE increased from 53% to 61%, showing an enhancement of 15.1%. Au-NPs improved the charge collection at the anode, which results in higher short circuit current and fill factor. However, the strong near field surrounding Au-NPs due to localized surface plasmonic resonance (LSPR effect is not distributed into the active layer. Instead, it is spread horizontally through the PEDOT:PSS layer, thus minimizing the light absorption in the active layer.

  13. Hazardous Waste Cleanup: El Paso Energy Corporation Polymers Incorporated in Flemington, New Jersey

    Science.gov (United States)

    The El Paso Energy Corporation Polymers, Inc. (EPEC Polymers, Inc.), formerly known as Tenneco Polymers, Inc., is located at 45 River Road, at the juncture of the South Branch of the Raritan River and Bushkill Brook in Flemington/Raritan Townships,

  14. The influence of different coordination environments on one-dimensional Cu(ii) coordination polymers for the photo-degradation of organic dyes.

    Science.gov (United States)

    Hussain, Navid; Bhardwaj, Vimal K

    2016-05-04

    Three new Cu(ii) coordination polymers, namely, {[Cu3(L(1))(NO3)2(DMF)(H2O)]·3(DMF)}n (), [Cu3(L(1))(Cl)2(DMF)2]n () and [Cu3(L(2))(NO3)4(H2O)4]n (), were synthesized from pyridine-2,6-dicarbohydrazide based imine linked tritopic ligands. All the complexes were characterized using elemental analysis, IR, UV-vis spectroscopy and ESI-MS. The solid state structures of complexes were determined using single crystal X-ray crystallography. The complexes contain trinuclear copper units connected through different anions that lead to the formation of one dimensional (ID) chain structures. Depending upon the anion of the copper salt and donor atoms of the ligands used in complexation, a small variation in the structures was observed. In complex , the trinuclear copper units are connected by phenoxo-bridging (μ2-O(-)) along with one coordinated water molecule, whereas complex is connected through chloride bridging (μ2-Cl) and complex is connected through nitrate ions (μ-[O-N-O]) along with four water molecules. Photo-catalytic activities of the synthesized complexes () were investigated. All the complexes were found to be photo-catalytically active; however, the distinct coordination environment of the metal ions (i.e. difference in the coordinated water molecules and donor sites of ligands) played a significant role in the catalytic activities. Therefore, this study presents comparative photo-catalytic studies of different coordination environments of metal ions in one-dimensional Cu(ii) coordination polymers. The results provide a potential pathway for the rational design of more efficient photo-catalysts.

  15. A Molecular Antenna Coordination Polymer from Cadmium(II and 4,4’-Bipyridine Featuring Three Distinct Polymer Strands in the Crystal

    Directory of Open Access Journals (Sweden)

    Iris M. Oppel

    2011-09-01

    Full Text Available Reaction of cadmium perchlorate and the prototypical linear bridging ligand 4,4’-bipyridine (4,4’-bipy in an ethanol/water mixture affords the one-dimensional coordination polymer, [{Cd(m-4,4’-bipy(4,4’-bipy2(H2O2}(ClO42 × 2 4,4’-bipy × 4.5 H2O]n (1. The Cd2+ ions adopt an octahedral coordination sphere and are joined into linear chains by 4,4’-bipy via two trans coordination sites. The remaining two trans sites in the equatorial plane carry terminally monodentate-bound 4,4’-bipy ligands, resulting in a molecular antenna arrangement. The two axial sites of each Cd2+ ion are occupied by aqua ligands. Compound 1 crystallizes in the non-centrosymmetric, monoclinic space group C2 with three similar, crystallographically independent, cationic coordination polymer strands in the unit cell, which essentially differ only in the conformations of the 4,4’-bipyridyl ligands. Consistent with the similarity of the local coordination environments of the three independent Cd atoms in the structure, 113Cd MAS NMR spectroscopy reveals a single resonance line at 89 ppm.

  16. Radiation luminescence of polymers - emission behaviour of aromatic compounds incorporated in synthetic rubbers

    International Nuclear Information System (INIS)

    Kawanishi, Shunichi; Hagiwara, Miyuki

    1986-01-01

    For a deep understanding of a radiation protection mechanism of some aromatic compounds on synthetic polymers, their optical emission behavior under electron irradiation was studied. The fluorescence light was led out of an irradiation room through a wave guide and detected by a photomultiplier so that less noisy spectrum was obtained. Acenaphthene or acenaphthylene was added to the synthetic rubbers such as ethylene propylene diene terpolymer, styrene butadiene rubber and cis-1,4-polybutadiene. The intensities of optical emission induced by electron beams changed from polymer to polymer, while those by ultraviolet lights were independent of the kind of polymers. The dependence of emission intensity on polymers under electron irradiation was estimated to show the fact that the radiation excited energy transfers occur from the polymer matrix to the additives and that an efficiency of the energy transfer is dependent on kinds of polymers. (author)

  17. An initial demonstration of hierarchically porous niobium alkylphosphonates coordination polymers as potent radioanalytical separation materials.

    Science.gov (United States)

    Lv, Kai; Yang, Chu-Ting; Han, Jun; Hu, Sheng; Wang, Xiao-Lin

    2017-06-30

    Combining the merits of soft-templating and perchlorate oxidation methods, the first-case investigation of niobium alkylphosphonates has uncovered their unique morphology, backbone composition, thermal behavior and huge potentiality as radioanalytical separation materials. These hierarchically porous solids are random aggregates of densely stacked nanolayers perforated with worm-like holes or vesicular voids, manifesting the massif-, tower-like "polymer brush" elevated up to ∼150nm driven by the minimal surface free energy principle. These coordination polymers consist of distorted niobium (V) ions strongly linked with tetrahedral alkylphosphonate building units, exposing uncoordinated phosphonate moieties and defective metal sites. Despite the amorphous features, they demonstrate multimodal porosity covering continuous micropores, segregated mesopores and fractional macropores, beneficial for the sequestration by active Lewis acid-base center. Evidenced by the maximum distribution coefficients of thorium, lanthanides reaching 9.0×10 4 , 9.5×10 4 mLg -1 and large separation factor at pH≤1 20-element cocktail, this category of niobium alkylphosphonates are capable of harvesting thorium, lanthanides directly from the radionuclide surrogate, comparable to or even surpass the performance of the metal (IV) arylphosphonates counterparts. They also display appreciable SF Eu/Sm ∼20 in 1molL -1 HNO 3 , shedding light on dual approaches to achieve the isolation of americium from curium. A combinatorial radioanalytical separation protocol has been proposed to enrich thorium and europium, revealing facile utilization of these highly stable, phosphonated hybrids in sustainable development of radioanalytical separation. Copyright © 2017 Elsevier B.V. All rights reserved.

  18. Experimental characterization and computational modeling of unimorph shape memory polymer actuators incorporating transverse curvature in the substrate

    Science.gov (United States)

    Cantrell, Jason T.

    This document outlines in detail the research performed by applying shape memory polymers in a generic unimorph actuator configuration. A set of experiments designed to investigate the influence of transverse curvature, the relative widths of shape memory polymer and composite substrates, and shape memory polymer thickness on actuator recoverability after multiple thermo-mechanical cycles is presented in detail. A theoretical model of the moment required to maintain shape fixity with minimal shape retention loss was developed and experimentally validated for unimorph composite actuators of varying cross-sectional areas. Theoretical models were also developed and evaluated to determine the relationship between the materials neutral axes and thermal stability during a thermo-mechanical cycle. Research was conducted on the incorporation of shape memory polymers on micro air vehicle wings to maximize shape fixity and shape recoverability while minimizing the volume of shape memory polymer on the wing surface. Applications based research also included experimentally evaluating the feasibility of shape memory polymers on deployable satellite antenna ribs both with and without resistance heaters which could be utilized to assist in antenna deployment.

  19. Crystal structures and luminescent properties of lanthanide nitrate coordination polymers with structurally related amide type bridging podands

    Science.gov (United States)

    Wang, Qing; Yan, Xuhuan; Zhang, Hongrui; Liu, Weisheng; Tang, Yu; Tan, Minyu

    2011-01-01

    A one-dimensional linear chain coordination polymer [ErL I(NO 3) 3(CH 3CO 2Et)] n (L I=1,2-bis{[(2'-furfurylaminoformyl)phenoxyl]methyl}benzene) and a one-dimensional zig-zag coordination polymer {[TbL II(NO 3) 3(H 2O)]·(H 2O)} n (L II=1,2-bis{[2'-(2-pyridylmethylaminoformyl)phenoxyl]methyl}benzene) were assembled by two structurally related bridging podands L I and L II which have uniform skeleton and different terminal groups. In {[TbL II(NO 3) 3(H 2O)]·(H 2O)} n, the neutral chains were linked by the hydrogen bonding interactions between the free and coordinated water molecules from two different directions to interpenetrate into a 3D supramolecular structure. At the same time, the luminescent properties of the solid Tb(III) nitrate complexes of these podands were investigated at room temperature. The lowest triplet state energy levels T 1 of the podands L I and L II indicate that the triplet state energy levels of the antennae are both above the lowest excited resonance level of 5D 4 of Tb 3+ ion. Thus the absorbed energy could be transferred from ligands to the central Tb 3+ ions. And the influence of the hydrogen bonding on the luminescence efficiencies of the coordination polymers was also discussed.

  20. Syntheses, crystal structures and thermal properties of six coordination polymers based on 2-(p-methylphenyl)-imidazole dicarboxylate.

    Science.gov (United States)

    Zhang, Yu; Yuan, Pengfei; Zhu, Yanyan; Li, Gang

    2013-10-01

    Through solvothermal reactions of 2-(p-methylphenyl)-1H-imidazole-4,5-dicarboxylic acid (p-MePhH3IDC) with transition-metal ions, six coordination polymers [Pb2(p-MePhHIDC)(p-MePhH2IDC)2(phen)2]n (phen = 1,10-phenanthroline) (), [Pb(p-MePhH2IDC)2]n (), [Cd3(p-MePhHIDC)2(p-MePhH2IDC)2(H2O)2]n (), {[Cd(p-MePhHIDC)(H2O)]4·H2O}n (), {[Cd2(p-MePhHIDC)2(4,4'-bipy)]·4H2O}n (4,4'-bipy = 4,4'-bipyridine) () and [Mn3(p-MePhHIDC)2(p-MePhH2IDC)2(4,4'-bipy)]n () have been synthesized successfully. X-ray single-crystal analyses show that polymers have rich structural chemistry ranging from one-dimensional (), two-dimensional () to three-dimensional polymers (, , and ). In these polymers, the p-MePhH3IDC ligand shows flexible coordination modes tuned by different synthetical conditions, including the addition of coligands, temperature, pH value and so on. Furthermore, the polymers have been investigated by solid-state ultraviolet spectra and thermogravimetric analyses.

  1. Amino acid-incorporated polymer network by thiol-ene polymerization

    Directory of Open Access Journals (Sweden)

    R. Yokose

    2015-08-01

    Full Text Available Triallyl L-alanine (A3A and triallyl L-phenylalanine (A3F were synthesized by reactions of L-alanine and L-phenylalanine with allyl bromide in the presence of sodium hydroxide, respectively. Thiol-ene thermal polymerization of A3A or A3F with pentaerythritol-based primary tetrathiol (pS4P or pentaerythritol-based secondary tetrathiol (S4P at allyl/SH 1/1 in the presence of 2,2'-azobis(isobutyronitrile produced an amino acid-incorporated polymer network (A3ApS4P, A3A-S4P or A3F-S4P. Although the thermally cured resins were homogeneous and flat films, the corresponding thiol-ene photopolymerization did not give a successful result. Degree of swelling for each thermally cured film in N,Ndimethylformamide was much higher than that in water. The glass transition and 5% weight loss temperatures (Tg and T5 of A3F-pS4P and A3F-S4P were higher than those of A3A-pS4P and A3A-S4P, respectively. Also, A3F-pS4P and A3F-S4P exhibited much higher tensile strengths and moduli than A3A-pS4P and A3A-S4P did, respectively. Consequently, A3FpS4P displayed the highest Tg (38.7°C, T5 (282.0°C, tensile strength (9.5 MPa and modulus (406 MPa among all the thermally cured resins.

  2. Incorporation of Polymers into Calcined Clays as Improved Thermal Insulating Materials for Construction

    OpenAIRE

    Ng, Serina; Jelle, Bjørn Petter

    2017-01-01

    Calcined clay is a Type Q supplementary cementing material according to EN197-1:2000. It possesses lower thermal conductivity than cement. To further improve its thermal insulation property, polymer-calcined clay complexes (PCCs) were produced in a one-pot synthesis. Two contrasting polymers, polystyrene (PS) and polyethylene glycol (PEG), were employed. The hydrophilicity of the polymers influenced the thermal conductivity of PCC. Hydrophilic PEG entrapped more water molecules on clay layers...

  3. Efficient tetracycline adsorption and photocatalytic degradation of rhodamine B by uranyl coordination polymer

    Science.gov (United States)

    Ren, Ya-Nan; Xu, Wei; Zhou, Lin-Xia; Zheng, Yue-Qing

    2017-07-01

    Two mixed uranyl-cadmium malonate coordination polymers [(UO2)2Cd(H-bipy)2(mal)4(H2O)2]·4H2O 1 and [(UO2)Cd(bipy)(mal)2]·H2O 2 (H2mal = malonic acid, bipy =4,4‧-bipyridine) have been synthesized in room temperature. Compound 1 represents a one-dimensional (1D) chain assembly of Cd(II) ions, uranyl centers and malonate ligands. Compound 2 exhibits a two-dimensional (2D) 2D +2D → 3D polycatenated framework based on inclined interlocked 2D 44 sql grids. The two compounds have been characterized by elemental analysis, IR and UV-vis spectroscopy, thermal analysis, powder X-ray diffraction and photoluminescence spectroscopy. And the ferroelectric property of 2 also has been studied. Moreover, compound 2 exhibits good photocatalytic activity for dye degradation under UV light and is excellent adsorbent for removing tetracycline antibiotics in the aqueous solution.

  4. Synthesis and characterization of the mixed ligand coordination polymer CPO-5

    International Nuclear Information System (INIS)

    Kongshaug, K.O.; FjellvAg, Helmer

    2003-01-01

    The synthesis and crystal structures of a novel coordination polymer and its high-temperature variant are described. The as-synthesized material (CPO-5-as), of composition Zn(4,4'-bipyridine)(4,4'-biphenyldicarboxylate)·3H 2 O, crystallizes in the triclinic space group P-1 (No. 2) with a=11.0197(2), b=14.2975(3), c=7.6586(1) A, α=95.9760(9) deg. , β=108.026(1) deg. , γ=91.373(1) deg. and V=1139.16(4) A 3 . CPO-5-as is composed of tetrahedral zinc centers that are connected by the organic linkers to give five independent, interpenetrating diamond networks. In the structure, there is additional space for channels that are filled with three water molecules. These water molecules can be removed, leading to an anhydrous variant at 130 o C. CPO-5-130, of composition Zn(4,4'-bipyridine)(4,4'-biphenyldicarboxylate), crystallizes in the triclinic space group P-1 (No. 2) with a=11.1844(6), b=14.0497(7), c=7.7198(3) A, α=96.917(2) deg. , β=109.527(2) deg. , γ=89.115(3) deg. and V=1134.6(1) A 3 . The structure of the five interpenetrating networks is virtually unchanged after the dehydration resulting in CPO-5-130 being a porous structure with an estimated free volume of 19.8%

  5. A new zinc coordination polymer in (10, 3)-d framework with unusual redox property

    Science.gov (United States)

    Huo, Jianqiang; Yan, Shuai; Arulsamy, Navamoney

    2017-11-01

    A new coordination polymer, [Zn(H1dimb)(Cl)]n (1) (H1dimb = 2,5-di (1H-imidazol-1-yl)benzoate), is obtained by hydrothermal synthesis and characterized by single crystal X-ray diffraction data and elemental analysis. Compound 1 crystallizes in the orthorhombic space group Pccn, and its structure exhibits a rarely observed ultimate racemic 3D network with 2-fold interpenetrating (10, 3)-d (or utp) topology due to the presence of alternating arrays of left- and right-handed helices. Thermo-gravimetric analysis (TGA) data for 1 reveals that the metal-organic framework (MOF) is thermally stable up to 350 °C under a N2 atmosphere. Compound 1 also possesses interesting photoluminescent properties as expected for Zn2+ complexes of aromatic ligands. Photoemission spectra measured in the solid state reveal a very strong emission band centered at 417 nm. Cyclic voltammetric data reveal that the compound exhibits quasi reversible two-electron redox process in acidic aqueous solution and the surprising electrochemical behavior is attributed to the Zn/Zn2+ process.

  6. Hydrothermal syntheses, crystal structures, and photophysical properties of two coordination polymers with mixed ligands

    Science.gov (United States)

    Yan, Li; Liu, Chun-Ling

    2017-10-01

    Two novel metal-organic coordination polymers [Cd(ipdt)(m-BDC)·3H2O]n (1) and [Pb(mip)2(NTC) ·2H2O]n (2) [ipdt = 2,6-Dimethoxy-4-(1H-1,3,7,8-tetraaza-cyclopenta[l]phenanthren-2-yl)-phenol, mip = 2-(3-methoxyphenyl)-1H-imidazo[4,5-f][1,10]phenanthroline, m-BDC = isophthalic acid, NTC = nicotinic acid] have been synthesized by hydrothermal reactions and characterized by elemental analysis, thermogravimetric (TG) analysis, infrared spectrum (IR) and single-crystal X-ray diffraction. Single-crystal X-ray diffraction reveals that 1 exhibits two-dimensional (2D) layer architecture, and 2 shows 1D chain architecture. TG analysis shows clear courses of weight loss, which corresponds to the decomposition of different ligands. The luminescent properties for the ligand ipdt, mip and complexes 1-2 are also discussed in detail, which should be acted as potential luminescent material.

  7. Preparation and characterization of organotin-oxomolybdate coordination polymers and their use in sulfoxidation catalysis.

    Science.gov (United States)

    Abrantes, Marta; Valente, Anabela A; Pillinger, Martyn; Gonçalves, Isabel S; Rocha, João; Romão, Carlos C

    2003-06-16

    The organotin-oxomolybdates [(R(3)Sn)(2)MoO(4)].n H(2)O (R=methyl, n-butyl, cyclohexyl, phenyl, benzyl) have been prepared and tested as catalysts for the oxidation of benzothiophene with aqueous hydrogen peroxide, at 35 degrees C and atmospheric pressure. In all cases, the 1,1-dioxide was the only observed product. The kinetic profiles depend on the nature of the tin-bound R group and also on the addition of a co-solvent. For the tribenzyltin derivative, the apparent activation energies for sulfoxidation as a function of the co-solvent are in the order 1,2-dichloroethane (5 kcal mol(-1))ethanolpolymers also have different structures, as evidenced by Xray powder diffraction. Mo K-edge and Sn K-edge EXAFS spectroscopy confirmed that the structures arise from the self-assembly of tetrahedral [MoO(4)](2-) subunits and [R(3)Sn](+) spacers. The Mo...Sn separation in the trimethyltin derivative is a uniform 3.84 A. By contrast, the EXAFS results revealed the coexistence of short (3.67-3.79 A) and long (3.93-4.07 A) Mo.Sn separations in the other coordination polymers. The catalyst precursors were also characterized in the solid state by thermogravimetric analysis, FTIR, and Raman spectroscopy, and MAS NMR ((13)C, (119)Sn) spectroscopy.

  8. New 4-carboxylphthalhydrazidate-bridged Mn2+/In3+ coordination polymers

    Science.gov (United States)

    Jin, Juan; Yan, Wen-Fu; Yu, Xiao-Yang; Yang, Qing-Feng; Liu, Bing; Xu, Ji-Qing; Gao, Shan-Min; Li, Chuan-Zhao; Lin, Chen

    2017-04-01

    Based on the hydrothermal in situ acylation reaction of benzene-1,2,4-tricarboxylic acid (btca) with N2H4·H2O, two containing-4-carboxylphthalhydrazidate Mn2+/In3+ coordination polymers, [Mn(cpth)(phen)] 1 and [In(cpth)(ox)0.5(phen)]·H2O 2 (cpth = 4-carboxylphthalhydrazidate, phen = 1,10-phenanthroline, ox = oxalate), were obtained and characterized by elemental analysis, IR spectroscopy, X-ray powder diffraction (XRD), thermogravimetric analysis (TGA), and single-crystal X-ray diffraction. In compound 1, the cpth ligands exhibit a μ4-bridging mode, which link Mn(II) centers into a 2-D layer structure with ancillary phen molecules. In compound 2, the cpth ligands exhibit a μ2-bridging mode, which link In(III) centers into a binuclear unit. Ox ligands act as the second linkers, extending binuclear unit into a 1-D chain with ancillary phen molecules. Via Nsbnd H⋯O interactions, compound 2 self-assembles into a 2-D supramolecular layer. The magnetic analysis indicates that there exists antiferromagnetic interactions between magnetic centers in compound 1. The photoluminescence properties of compounds 1 and 2 were also investigated in an aqueous solution.

  9. One-dimensional homochiral cyano-bridged heterometallic chain coordination polymers with metamagnetic or ferroelectric properties.

    Science.gov (United States)

    Wen, He-Rui; Tang, Yun-Zhi; Liu, Cai-Ming; Chen, Jing-Lin; Yu, Chang-Lin

    2009-11-02

    Two couples of enantiomerically pure chiral cyano-bridged heterobimetallic chain coordination polymers, [Mn((R,R)-Salcy)Fe(Tp)(CN)(3) x H(2)O x 1/2 CH(3)CN](n) (1), [Mn((S,S)-Salcy)Fe(Tp)(CN)(3) x H(2)O x 1/2 CH(3)CN](n) (2), [Mn((R,R)-Salcy)Fe(bpca)(CN)(3) x H(2)O](n) (3), and [Mn((S,S)-Salcy)Fe(bpca)(CN)(3) x H(2)O](n) (4) [(R,R)-Salcy or (S,S)-Salcy = (R,R)- or (S,S)-N,N'-(1,2-cyclohexanediylethylene)bis(salicylideneiminato) dianion, Tp = tris(pyrazolyl)hydroborate, bpca = bis(2-pyridylcarbonyl)amidate anion], were synthesized using the modified cyanometalate building blocks [Fe(L)(CN)(3)](-) (L = Tp, bpca) and the chiral polydentate Schiff base manganese(III) complex fragments. The circular dichroism measurements showed Cotton effects of the opposite sign at the same wavelength for each pair of enantiomers. Magnetic property studies indicated that complexes 1 and 2 show not only intrachain but also interchain field-induced metamagnetic transitions from an antiferromagnetic to a ferromagnetic state and exhibit an antiferromagnetic long-range ordering with a T(N) of 3.2 K, while enantiomers 3 and 4 are typical antiferromagnetic coupling compounds. Furthermore, complex 3 exhibits a ferroelectric behavior that relates to the polar point group C(2), in which it crystallizes.

  10. Synthesis, crystal structure and adsorption properties of a novel Mn(II) coordination polymer

    Science.gov (United States)

    Cui, Lian-Sheng; Gan, Yong-Le; Li, Yuan-Cheng; Meng, Jun-Rong

    2017-11-01

    A novel Mn(II) coordination polymer based on a "V"-shaped 1,3-di(4‧-carboxyl-phenyl)benzene acid (H2dpb, dpb = 1,3-di(4‧-carboxyl-phenyl)benzene), namely {[Mn(dpb)(4,4‧-bibp)]·H2O}n (4,4‧-bibp = 4,4‧-bis(imidazol-1-yl)biphenyl) has been hydrothermally synthesized and characterized by single-crystal X-ray diffraction and further characterized by elemental analysis, IR spectra, and thermogravimetric analysis (TGA). Furthermore, CO2 and SO2 adsorption properties of the complex were tested by high-pressure adsorption instrument under different pressure. The results show that the adsorption performance of CO2 is far superior to SO2 on the same conditions. The adsorption capacity increases with temperature rising. Very interestingly, the saturated adsorption amount (5.5 mmol/g) at 100 °C is less than the one at 80 °C (7.20 mmol/g). This phenomenon is caused by the escape of water vapor.

  11. Reversible and Topotactic Solvent Removal in a Magnetic Ni(NCS)2 Coordination Polymer.

    Science.gov (United States)

    Suckert, Stefan; Rams, Michał; Rams, Marek M; Näther, Christian

    2017-07-17

    Reaction of Ni(NCS) 2 with 4-(Boc-amino)pyridine in acetonitrile leads to the formation of a new coordination polymer with the composition Ni(NCS) 2 (4-(Boc-amino)pyridine) 2 ·MeCN (1-MeCN). In the crystal structure the Ni(II) cations are linked by the anionic ligands into chains that are further connected into layers by intermolecular N-H···O hydrogen bonding. These layers are stacked and channels are formed, in which acetonitrile molecules are located. Solvent removal leads to the ansolvate 1, which shows microporosity as proven by sorption measurements. Single crystal X-ray investigations reveal that the solvent removal leads to a change in symmetry from primitive to C-centered, which is reversible and which proceeds via a topotactic reaction leaving the network intact. The magnetic properties of 1-MeCN and 1 are governed by the ferromagnetic exchange between spins of Ni(II) forming chains. The susceptibility and specific heat for such a quantum Heisenberg chain of S = 1 spins with zero-field splitting are calculated using the DMRG method and compared with the experimental results.

  12. Weak cooperativity in selected iron(II) 1D coordination polymers

    Energy Technology Data Exchange (ETDEWEB)

    Dirtu, Marinela M.; Gillard, Damien; Naik, Anil D. [Universite Catholique de Louvain, Institute of Condensed Matter and Nanosciences, MOST - Inorganic Chemistry (Belgium); Rotaru, Aurelian [' Stefan cel Mare' University, Department of Electrical Engineering and Computer Science (Romania); Garcia, Yann, E-mail: ann.garcia@uclouvain.be [Universite Catholique de Louvain, Institute of Condensed Matter and Nanosciences, MOST - Inorganic Chemistry (Belgium)

    2012-03-15

    The spin crossover behaviour of a new class of Fe{sup II} coordination polymers [Fe(phtptrz){sub 3}]I{sub 2} (1), [Fe(phtptrz){sub 3}](ReO{sub 4}){sub 2} Bullet CH{sub 3}OH (2) and [Fe(phtptrz){sub 3}]TaF{sub 7} Bullet 6H{sub 2}O (3) based on a novel ligand 4-(3{sup Prime} -N-phtalimido-propyl)-1,2,4-triazole (phtptrz), were investigated by temperature dependent {sup 57}Fe Moessbauer spectroscopy and magnetic susceptibility measurements. The adverse effect of bulky substituent on 1,2,4-triazole, favorable supramolecular interactions and influence of increasing anion size on spin crossover profile is discussed. 1 and 2 show thermally induced spin conversions of gradual and incomplete nature with associated thermochromism, and transition temperatures T{sub 1/2} {approx} 163 K and 137 K, respectively. A spin state crossover is also identified for 3.

  13. Incorporation of ester groups into low band-gap diketopyrrolopyrrole containing polymers for solar cell applications

    DEFF Research Database (Denmark)

    Hu, Xiaolian; Zuo, Lijian; Fu, Weifei

    2012-01-01

    To increase the open circuit voltage (VOC) of polymer solar cells based on diketopyrrolopyrrole (DPP) containing polymers, the weakly electron-withdrawing thiophene-3,4-dicarboxylate unit was introduced into the polymer backbone. Two ester group functionalized DPP containing polymers, PCTDPP...... with a random structure and PDCTDPP with a regular structure, were designed and synthesized by the Stille coupling reaction. The resulting copolymers exhibit broad and strong absorption bands from 350 to 1000 nm with low optical band gaps below 1.40 eV. Through cyclic voltammetry measurements, it is found...

  14. Incorporation of Furan into Low Band-Gap Polymers for Efficient Solar Cells

    KAUST Repository

    Woo, Claire H.

    2010-11-10

    The design, synthesis, and characterization of the first examples of furan-containing low band-gap polymers, PDPP2FT and PDPP3F, with substantial power conversion efficiencies in organic solar cells are reported. Inserting furan moieties in the backbone of the conjugated polymers enables the use of relatively small solubilizing side chains because of the significant contribution of the furan rings to overall polymer solubility in common organic solvents. Bulk heterojunction solar cells fabricated from furan-containing polymers and PC71BM as the acceptor showed power conversion efficiencies reaching 5.0%. © 2010 American Chemical Society.

  15. Synthesis, Crystal Structure and Thermal Stability of 1D Linear Silver(I Coordination Polymers with 1,1,2,2-Tetra(pyrazol-1-ylethane

    Directory of Open Access Journals (Sweden)

    Evgeny Semitut

    2016-10-01

    Full Text Available Two new linear silver(I nitrate coordination polymers with bitopic ligand 1,1,2,2-tetra(pyrazol-1-ylethane were synthesized. Synthesized compounds were characterized by IR spectroscopy, elemental analysis, powder X-ray diffraction and thermal analysis. Silver coordination polymers demonstrated a yellow emission near 500 nm upon excitation at 360 nm. Crystal structures of coordination polymers were determined and structural peculiarities are discussed. In both of the structures, silver ions are connected via bridging ligand molecules to form polymeric chains with a five-atomic environment. The coordination environment of the central atom corresponds to a distorted trigonal bipyramid with two N atoms of different ligands in apical positions. The Ag–N bond distances vary in a wide range of 2.31–2.62 Å, giving strongly distorted metallacycles. Thermolysis of coordination polymers in reductive atmosphere (H2/He leads to the formation of silver nanoparticles with a narrow size distribution.

  16. Syntheses, structures and properties of four Cd(II) coordination polymers induced by the pH regulator

    Science.gov (United States)

    Xu, Yun; Ding, Fang; Liu, Dong; Yang, Pei-Pei; Zhu, Li-Li

    2018-03-01

    Four new coordination polymers [Cd2(CHDC)2(APYZ)(H2O)2](H2O) (1), [Cd(HCHDC)2(APYZ) (H2O)] (2), [Cd2(CHDC)2(PYZ)(H2O)2](H2O) (3), and [Cd(HCHDC)2(PYZ)(H2O)] (4) (H2CHDC = 1,4-cyclohexanedicarboxylic acid, APYZ = 2-aminopyrazine, PYZ = pyrazine) have been synthesized under the hydrothermal conditions by changing the pH regulator and the N-containing ligands. The pH regulator impacted on the degree of deprotonation of the 1,4-cyclohexanedicarboxylic acid ligand and resulted in the formation of the two pairs of different networks. Polymers 1 and 3 crystallize in monoclinic, space group P21/c, exhibit two dimensional 63 net, which further formed three-dimensional supramolecular structure by the Csbnd H⋯O hydrogen bond interactions. While polymers 2 and 4 possess one dimensional chain structures and further link into two dimensional layered supramolecular structures by intermolecular hydrogen bonding interactions. From all three conformers of H2CHDC, e,a-cis is consistently present in the Cd coordination polymers. Furthermore, photoluminescence properties of four polymers are also investigated, the luminescent intensity of polymer 1 (or 2) with amino group in pyrazine is dramatically stronger than that of the similar structure of polymer 3 (or 4) without amino group in pyrazine, the results shown that the presence of the amino group from 2-aminopyrazine play a key role in increasing the luminescence properties.

  17. Ionochromic effects and structures of metalated poly(p-phenylenevinylene) polymers incorporating 2,2'-bipyridines

    International Nuclear Information System (INIS)

    Chen, L.X.; Jager, W.J.H.; Gosztola, D.J.; Niemczyk, M.P.; Wasielewski, M.R.

    2000-01-01

    The effects of metal ion chelation to the 2,2'-bipyridine (bpy) groups on the photophysics and exciton dynamics of two conjugated polymers 1 and 2 in solution are investigated. The structures of polymers 1 and 2 have 2,2'-bipyridyl-5-vinylene units that alternate with one and three 2,5-bis(n-decyloxy)-1,4-phenylenevinylene monomer units, respectively. The photophysics and exciton dynamics of metalated polymers 1 and 2 are compared to those of the metal-free polymers (Chen et al. J. Phys. Chem. A 1999, 103, 4341-4351). The origins of ionochromic effects due the metal ion chelation were studied using both steady-state and transient optical spectroscopy, and the results indicate that both conformational flattening and participation of Jr electrons from the metal in the π-conjugation of the polymer backbone play important roles in metal ion binding induced red shifts in absorption and photoluminescence spectra. The photoluminescence properties of the metalated polymers are determined by the metal ion electronic structures, where the closed shell Zn 2+ -bound polymer 2 has an increased photoluminescence quantum yield and the corresponding open shell Ni 2+ - or Fe 3+ -bound polymers have quenched photoluminescence due to spin-orbit coupling. The dual character of metalated polymer 2 as a conjugated polymer and as a metal-bpy complex is discussed. In addition, the structures of metal ion binding sites are studied via X-ray absorption fine structure (XAFS) and are related to the photophysical properties of the metalated polymers

  18. Coordination polymers of La(III) acetate with terephthalaldehyde bis isonicotinic acid hydrazone (Paper No. AL-12)

    International Nuclear Information System (INIS)

    Dwivedi, D.K.; Shukla, B.K.; Shukla, R.K.

    1990-02-01

    Polymerization reactions involving the formation of schiff base metal complexes by condensation have been described. Metal complexes of schiff bases of hyrazides with aldehydes and ketones have been of special interest in recent years, particularly in the context of therapeutic value of hydrazide and hydrazone. The coordination occurs both in keto as well as in enolic form of ligands with metal ions. Coordination polymers of 3-d series have been extensively studied but less attention has been paid on rare earths polymeric complexes. The synthesis and characterization of lanthanide (La, Pr, Nd, Sr and Gd) acetate complexes with a schiff base derived from terephthalaldehyde and isonicotinic acidhydrazide are reported. (author)

  19. Design of superhydrophobic porous coordination polymers through the introduction of external surface corrugation by the use of an aromatic hydrocarbon building unit.

    Science.gov (United States)

    Rao, Koya Prabhakara; Higuchi, Masakazu; Sumida, Kenji; Furukawa, Shuhei; Duan, Jingui; Kitagawa, Susumu

    2014-07-28

    We demonstrate a new approach to superhydrophobic porous coordination polymers by incorporating an anisotropic crystal morphology featuring a predominant surface that is highly corrugated and terminated by aromatic hydrocarbon moieties. The resulting low-energy surface provides particularly promising hydrophobic properties without the need for postsynthetic modifications or surface processing that would block the porosity of the framework. Consequently, hydrophobic organic molecules and water vapor are able to penetrate the surface and be densely accommodated within the pores, whereas bulk water is repelled as a result of the exterior surface corrugation derived from the aromatic surface groups. This study provides a new strategy for the design and development of superhydrophobic porous materials. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  20. Synthesis of porphyrin-incorporated polymers and their application for simultaneous detection of multimetal components by using spectrophotometry

    Science.gov (United States)

    Asano, Takaharu; Wang, Pi-Chao; Iwasaki, Akio

    2010-01-01

    For the purpose of detection of multimetal components in environment, alteration of the spectrophotometrical metal sensitivity of porphyrin was attempted. Two porphyrin-incorporated polymers were newly synthesized by the free radical copolymerization of protoporphyrin IX disodium salt and vinyl monomers, and their metal sensitivities were examined by measuring the difference absorption spectra. These porphyrin-incorporated polymers showed different metal sensitivities and their sensitivities were altered by change of pH. Three measuring reagents, which were different in the combination of the porphyrin-incorporated polymers and pH, were used for the simultaneous detection of multimetal components in metal ion mixtures. The difference spectra of these reagents showed the separate peaks corresponding to six metal ions, Bi(III), Co(II), Cu(II), Mn(II), Pb(II), and Zn(II). The spectra were acquired reproducibly by using standard normal variate (SNV) transformation. Furthermore, this method was applied to detect multimetal components in water samples such as tap water and industrial effluent.

  1. Crystal Structure and Band-Gap Engineering of a Semiconducting Coordination Polymer Consisting of Copper(I) Bromide and a Bridging Acceptor Ligand.

    Science.gov (United States)

    Okubo, Takashi; Himoto, Kento; Tanishima, Koki; Fukuda, Sanshiro; Noda, Yusuke; Nakayama, Masanobu; Sugimoto, Kunihisa; Maekawa, Masahiko; Kuroda-Sowa, Takayoshi

    2018-03-05

    A new semiconducting 3D coordination polymer, [Cu 2 Br 2 (ttz)] n (1), with an acceptor bridging ligand, 1,2,4,5-tetrazine (ttz), was synthesized. The complex shows large absorption bands extending to the near-IR region, indicating a small band gap in the coordination polymer. This complex shows higher conductivity than those of [CuBr(pyz)] n (2), including pyrazine (pyz) with a higher lowest unoccupied molecular orbital level. We performed density functional theory band calculations using the VASP program to understand the electronic states and conducting paths of the coordination polymer.

  2. Incorporation of Mean Stress Effects into the Micromechanical Analysis of the High Strain Rate Response of Polymer Matrix Composites

    Science.gov (United States)

    Goldberg, Robert K.; Roberts, Gary D.; Gilat, Amos

    2002-01-01

    The results presented here are part of an ongoing research program, to develop strain rate dependent deformation and failure models for the analysis of polymer matrix composites subject to high strain rate impact loads. A micromechanics approach is employed in this work, in which state variable constitutive equations originally developed for metals have been modified to model the deformation of the polymer matrix, and a strength of materials based micromechanics method is used to predict the effective response of the composite. In the analysis of the inelastic deformation of the polymer matrix, the definitions of the effective stress and effective inelastic strain have been modified in order to account for the effect of hydrostatic stresses, which are significant in polymers. Two representative polymers, a toughened epoxy and a brittle epoxy, are characterized through the use of data from tensile and shear tests across a variety of strain rates. Results computed by using the developed constitutive equations correlate well with data generated via experiments. The procedure used to incorporate the constitutive equations within a micromechanics method is presented, and sample calculations of the deformation response of a composite for various fiber orientations and strain rates are discussed.

  3. A new bismuth-based coordination polymer as an efficient visible light responding photocatalyst under white LED irradiation

    Energy Technology Data Exchange (ETDEWEB)

    Huang, Ya-Jing; Zheng, Yue-Qing, E-mail: zhengyueqing@nbu.edu.cn; Wang, Jin-Jian; Zhou, Lin-Xia

    2017-02-15

    A new bismuth-based polymer, [Hbpe][Bi(Hpydc){sub 2}(pydc)]·H{sub 2}O (H{sub 2}pydc=pyridine-2,5-dicarboxylic acid, bpe=trans-bis(4-pyridyl) ethylene) has been hydrothermally synthesized. Transient photocurrent response and electrochemical impedance spectroscopy studies indicate that the synthesized polymer with efficient charge separation and transportation can be used as a potential photocatalyst. So we use it for the degradation of rhodamine B (RhB) dye wastewater under visible light. The comparative study on commercial Bi{sub 2}O{sub 3} shows [Hbpe][Bi(Hpydc){sub 2}(pydc)]·H{sub 2}O has the higher photocatalytic performance, with the degradation rate of 97% and 2% within 100 min for [Hbpe][Bi(Hpydc){sub 2}(pydc)]·H{sub 2}O and commercial Bi{sub 2}O{sub 3} respectively. Additionally, the five cycle reproducibility results of [Hbpe][Bi(Hpydc){sub 2}(pydc)]·H{sub 2}O implies that it can be used as a stable photocatalyst. - Graphical abstract: We report a new 1D coordination polymer [Hbpe][Bi(Hpydc){sub 2}(pydc)]·H{sub 2}O by a facile hydrothermal method. The Bi-CP shows good photoelectric property and photocatalytic activity for RhB degradation under visible white LED lamp irradiation. And the stability of the visible-light-responsive bismuth-based coordination polymer has also been examined. - Highlights: • A new Bi(III) coordination polymer is hydrothermally synthesized. • The Bi-CP shows good photoelectric and photocatalytic properties. • Bi-CP shows higher activity than the commercial Bi{sub 2}O{sub 3} for RhB degradation.

  4. Reversible Guest Binding in a Non-Porous FeII Coordination Polymer Host Toggles Spin Crossover

    DEFF Research Database (Denmark)

    Lennartson, Anders; Southon, Peter; Sciortino, Natasha F.

    2015-01-01

    Formation of either a dimetallic compound or a 1 D coordination polymer of adiponitrile adducts of [Fe(bpte)]2+ (bpte=[1,2-bis(pyridin-2-ylmethyl)thio]ethane) can be controlled by the choice of counteranion. The iron(II) atoms of the bis(adiponitrile)-bridged dimeric complex [Fe2(bpte)2(μ2-(NC(CH2...

  5. A coordination polymer based magnetic adsorbent material for hemoglobin isolation from human whole blood, highly selective and recoverable

    Science.gov (United States)

    Zhang, Xiaoxing; Tan, Jipeng; Xu, Xinxin; Shi, Fanian; Li, Guanglu; Yang, Yiqiao

    2017-09-01

    A composite material has been obtained successfully through the loading of nanoscale coordination polymer on magnetic Fe3O4@SiO2 core-shell particle. In this composite material, coordination polymer nanoparticles distribute uniformly on Fe3O4@SiO2 and these two components are "tied" together firmly with chemical bonds. Adsorption experiments suggest this composite material exhibits very excellent selectivity to hemoglobin. But under the same condition, its adsorption to bovine serum albumin can almost be ignored. This selectivity can be attributed to the existence of hydrophobic interactions between coordination polymer nanoparticle and hemoglobin. For composite material, the hemoglobin adsorption process follows Langmuir model perfectly with high speed. The adsorbed hemoglobin can be eluted easily by sodium dodecyl sulfate stripping reagent with structure and biological activity of hemoglobin keeps well. The composite material was also employed to separate hemoglobin from human whole blood, which receives a very satisfactory result. Furthermore, magnetic measurement reveals ferromagnetic character of this composite material with magnetization saturation 3.56 emu g-1 and this guarantees its excellent magnetic separation performance from the treated solution.

  6. Self-Compacting Concrete Incorporating Micro-SiO2 and Acrylic Polymer

    Directory of Open Access Journals (Sweden)

    Ali Heidari

    2014-01-01

    Full Text Available This study examined the effects of using acrylic polymer and micro-SiO2 in self-compacting concrete (SCC. Using these materials in SCC improves the characteristics of the concrete. Self-compacting samples with 1-2% of a polymer and 10% micro-SiO2 were made. In all cases, compressive strength, water absorption, and self-compacting tests were done. The results show that adding acrylic polymer and micro-SiO2 does not have a significant negative effect on the mechanical properties of self-compacting concrete. In addition using these materials leads to improving them.

  7. Zirconium(IV)-Benzene Phosphonate Coordination Polymers: Lanthanide and Actinide Extraction and Thermal Properties.

    Science.gov (United States)

    Luca, Vittorio; Tejada, Juan J; Vega, Daniel; Arrachart, Guilhem; Rey, Cyrielle

    2016-08-15

    Coordination polymers with different P/(Zr + P) molar ratios were prepared by combining aqueous solutions of Zr(IV) and benzenephosphonate derivatives. 1,3,5-Benzenetrisphosphonic acid (BTP) as well as phosphonocarboxylate derivatives in which carboxylate substitutes one or two of the phosphonate groups were chosen as the building blocks. The precipitates obtained on combining the two solutions were not X-ray amorphous but rather were indicative of poorly ordered materials. Hydrothermal treatment did not alter the structure of the materials produced but did result in improved crystalline order. The use of HF as a mineralizing agent during hydrothermal synthesis resulted in the crystallization of at least three relatively crystalline phases whose structure could not be determined owing to the complexity of the diffraction patterns. Gauging from the similarity of the diffraction patterns of all the phases, the poorly ordered precipitates and crystalline materials appeared to have similar underlying structures. The BTP-based zirconium phosphonates all showed a higher selectivity for lanthanides and thorium compared with cations such as Cs(+), Sr(2+), and Co(2+). Substitution of phosphonate groups by carboxylate groups did little to alter the pattern of selectivity implying that selectivity in the system was entirely determined by the -POH group with little influence from the -COOH groups. Samples with the highest phosphorus content showed the highest extraction efficiencies for lanthanide elements, especially the heavy lanthanides such as Dy(3+) and Ho(3+) with separation factors of around four with respect to La(3+). In highly acid solutions (4 M HNO3) there was a pronounced variation in extraction efficiency across the lanthanide series. In situ, nonambient diffraction was performed on ZrBTP-0.8 loaded with Th, Ce, and a complex mixture of lanthanides. In all cases the crystalline Zr2P2O7 pyrophosphate phase was formed at ∼800 °C demonstrating the versatility of

  8. Recycled Glass Fiber Reinforced Polymer Composites Incorporated in Mortar for Improved Mechanical Performance

    Science.gov (United States)

    2017-12-11

    Glass fiber reinforced polymer (GFRP) recycled from retired wind turbines was implemented in mortar as a volumetric replacement of sand during the two phases of this study. In Phase I, the mechanically refined GFRP particle sizes were sieved for four...

  9. SYNTHESIS, CHARACTERIZATION AND ANTITUMOR ACTIVITY OF A Ca (II COORDINATION POLYMER BASED ON 3-AMINO-2-PYRAZINECARBOXYLIC ACID

    Directory of Open Access Journals (Sweden)

    XI-SHI TAI

    2015-10-01

    Full Text Available A new Ca(II coordination polymer has been obtained by reaction of Ca(ClO42·H2O with 3-amino-2-pyrazinecarboxylic acid in CH3CH2OH/H2O. It was characterized by IR, 1HNMR, thermal analysis and X-ray single crystal diffraction analysis. X-ray analysis reveals that each Ca(II center is seven-coordination with a N2O5 distorted pentagonal bipyramidal coordination environment. The Ca(II ions are linked through the O atoms of 3-amino-2-pyrazinecarboxylic acid ligands to form 1D chain structure. And then a 3D network structure is constructed by hydrogen bonds and π-π stacking. The antitumor activity of 3-amino-2-pyrazinecarboxylic acid ligand and its Ca(II coordination polymer against human intestinal adenocarcinoma HCT-8 cells, lung adenocarcinoma HCT-116 cells and human lung adenocarcinoma A549 cells line have been investigated.

  10. The role of IAEA in coordinating research and transferring technology in radiation chemistry and processing of polymers

    International Nuclear Information System (INIS)

    Haji-Saeid, M.; Sampa, M.H.; Ramamoorthy, N.; Gueven, O.; Chmielewski, A.G.

    2007-01-01

    The IAEA has been playing a significant role in fostering developments in radiation technology in general and radiation processing of polymers in particular, among its Member States (MS) and facilitate know-how/technology transfer to developing MS. The former is usually achieved through coordinated research projects (CRP) and thematic technical meetings, while the latter is mainly accomplished through technical cooperation (TC) projects. Coordinated research projects encourage research on, and development and practical application of, radiation technology to foster exchange of scientific and technical information. The technical cooperation (TC) programme helps Member States to realize their development priorities through the application of appropriate radiation technology. The IAEA has implemented several coordinated research projects (CRP) recently, including one on-going project, in the field of radiation processing of polymeric materials. The CRPs facilitated the acquisition and dissemination of know-how and technology for controlling of degradation effects in radiation processing of polymers, radiation synthesis of stimuli-responsive membranes, hydrogels and absorbents for separation purposes and the use of radiation processing to prepare biomaterials for applications in medicine. The IAEA extends cooperation to well-known international conferences dealing with radiation technology to facilitate participation of talented scientists from developing MS and building collaborations. The IAEA published technical documents, covering the findings of thematic technical meetings (TM) and coordinated research projects have been an important source of valuable practical information

  11. Modification de kaolinites submicroniques en vue de leur incorporation dans des matrices polymères

    OpenAIRE

    Batistella, Marcos

    2013-01-01

    Kaolinite is one of the most used mineral fillers since ancient times. Indeed, because of their properties, this clay is used as filler in many industrial applications, particularly in the industry of paper, cement, ceramics, glass etc... This use is related to their good optical, mineralogical and chemical properties. However the addition of kaolinite in polymer matrices leads to some difficulties especially related to their incompatibility with most polymers. In this context, this work prop...

  12. Supramolecular coordination polymers using a close to 'V-shaped' fluorescent 4-amino-1,8-naphthalimide Tröger's base scaffold.

    Science.gov (United States)

    Shanmugaraju, Sankarasekaran; Hawes, Chris S; Savyasachi, Aramballi J; Blasco, Salvador; Kitchen, Jonathan A; Gunnlaugsson, Thorfinnur

    2017-11-21

    A V-shaped 4-amino-1,8-naphthalimide derived dipyridyl ligand comprising the Tröger's base structural motif has been synthesised and subsequently used in the formation of two new supramolecular coordination polymers.

  13. Synthesis, Crystal Structure, and Antimicrobial Properties of a Novel 1-D Cobalt Coordination Polymer with Dicyanamide and 2-Aminopyridine

    Directory of Open Access Journals (Sweden)

    Amah Colette Benedicta Yuoh

    2015-01-01

    Full Text Available A novel one-dimensional coordination polymer bis(2-aminopyridine-μ-bis(dicyanamido cobaltate(II has been synthesized and characterized by elemental analyses and infrared and ultraviolet visible spectroscopies and the structure has been determined by single crystal X-ray diffraction. Co(II ion in the complex is coordinated to two axial 2-aminopyridine ligands through the pyridine N-atom and four equatorial dicyanamide ligands to give a CoN6 slightly distorted octahedral coordination environment around the metal ion. The amino N-atom forms intrachain hydrogen bonds. Antimicrobial screening of the complex against eight pathogenic microorganisms (four bacteria and four fungi isolated from humans, indicates that the complex is moderately active.

  14. Structural diversity of a series of terpyridyl carboxylate coordination polymers: Luminescent sensor and magnetic properties

    Science.gov (United States)

    Yuan, Fei; Yuan, Chun-Mei; Hu, Huai-Ming; Wang, Ting-Ting; Zhou, Chun-Sheng

    2018-02-01

    Eleven new coordination polymers, [Zn2(ctpy)2(HCOO)2]n·3nH2O (1), [Zn2(ctpy)2(HCOO)2(H2O)2]n·nH2O (2), [Zn2(ctpy)2(H2O)4]n·2n(CH3COO)·nH2O (3), [Zn2(ctpy)2(CH3COO)2]n·nH2O (4), [Zn(ctpy)2]n·nH2O (5), [Zn2(ctpy)2(Hidc)(H2O)2]n(6), [Cd2(ctpy)4]n(7), [Cd2(ctpy)2(Hidc)]n(8), [Co2(ctpy)2(HCOO)2(H2O)2]n·nH2O (9), [Co(ctpy)(DMF)(ox)0.5]n(10), [Co(ctpy)(ox)0.5]n(11) and the closely related compound [Zn(ctpy)(ox)0.5]n·0.5nH2O (12) (Hctpy = 4‧-carboxy-4,2‧:6‧,4‧‧-terpyridine, H2ox = oxalic acid and H3idc = imidazole-4,5-dicarboxylic acid) have been synthesized by hydro(solvo)thermal reaction of 4‧-carboxy-4,2‧:6‧,4‧‧-terpyridine with divalent metal salts and characterized by elemental analysis, IR spectra, single crystal X-ray diffraction. Compounds 1 and 4 have similar structure which demonstrate a two-fold interpenetrating 3D framework with a 3-connected utp topological net, which contains the same number of left and right-handed 21 helical chains. Compounds 2 and 9 are isostructural 2D layer with a 3-connected hcb topological net. Similar to 2, compound 3 also displays a 3-connected 2D hcb topological net. Compounds 5 and 10 are a 2D layer with a 4-connected sql topological net. Compound 6 shows a chiral 2D layer based on a 1D left- or right-handed helical chains, which are further extended into an achiral 2D + 2D→3D supramolecular network by hydrogen bonds with alternately arrangement. Compound 7 features an unusual 2-fold interpenetrating 3D coordination network which exhibits a new intriguing (3,5)-connected binodal topological net with the Schläfli symbol of (52·6)(53·63·73·8). Compound 8 shows a 2D→3D supramolecular structure based on (3,4)-connected 2D bilayers with the Schläfli symbol of (44·62). Compound 11 displays an unusual three-dimensional coordination network which exhibits an intriguing (3,8)-connected binodal new topological net with Schläfli symbol (42·62)2(42·623·83). Compound 12 features a two

  15. A strategy to synthesize graphene-incorporated lignin polymer composite materials with uniform graphene dispersion and covalently bonded interface engineering

    Science.gov (United States)

    Wang, Mei; Duong, Le Dai; Ma, Yifei; Sun, Yan; Hong, Sung Yong; Kim, Ye Chan; Suhr, Jonghwan; Nam, Jae-Do

    2017-08-01

    Graphene-incorporated polymer composites have been demonstrated to have excellent mechanical and electrical properties. In the field of graphene-incorporated composite material synthesis, there are two main obstacles: Non-uniform dispersion of graphene filler in the matrix and weak interface bonding between the graphene filler and polymer matrix. To overcome these problems, we develop an in-situ polymerization strategy to synthesize uniformly dispersed and covalently bonded graphene/lignin composites. Graphene oxide (GO) was chemically modified by 4,4'-methylene diphenyl diisocyanate (MDI) to introduce isocyanate groups and form the urethane bonds with lignin macromonomers. Subsequential polycondensation reactions of lignin groups with caprolactone and sebacoyl chloride bring about a covalent network of modified GO and lignin-based polymers. The flexible and robust lignin polycaprolactone polycondensate/modified GO (Lig-GOm) composite membranes are achieved after vacuum filtration, which have tunable hydrophilicity and electrical resistance according to the contents of GOm. This research transforms lignin from an abundant biomass into film-state composite materials, paving a new way for the utilization of biomass wastes.

  16. Control of water molecule aggregations in copper 1,4-cyclohexanedicarboxylate coordination polymers containing pyridyl-piperazine type ligands

    Science.gov (United States)

    Qiblawi, Sultan H.; LaDuca, Robert L.

    2014-01-01

    A series of layered divalent copper coordination polymers containing 1,4-cyclohexanedicarboxylate and long-spanning pyridyl-piperazine type ligands exhibits greatly different co-crystallized water molecule aggregations depending on the specific ligands used. Both [Cu(t-14cdc)(4-bpmp)]n (1, t-14cdc = trans-1,4-cyclohexanedicarboxylate, 4-bpmp = bis(4-pyridylmethyl)piperazine) and {[Cu(t-14cdc)(4-bpfp)(H2O)2]·6H2O}n (2, 4-bpfp = bis(4-pyridylformyl)piperazine) possess 2D (4,4) coordination polymer grids. However 1 lacks any co-crystallized water and has pinched grid apertures, while 2 manifests infinite water tapes with T6(2)4(2) classification and rectangular grid apertures. {[Cu2(c-14cdc)2(4-bpmp)]·2H2O}n (3, c-14cdc = cis-1,4-cyclohexanedicarboxylate) has [Cu2(c-14cdc)]2 ribbons with paddlewheel dimeric units linked into 2D slabs by 4-bpmp tethers, along with isolated water molecule pairs. In contrast, {[Cu2(c-14cdc)2(4-bpfp)]·10H2O}n (4) shows a very similar underlying coordination polymer topology but entrains unique decameric water molecule clusters. The minor product {[Cu2(c-14cdcH)2(t-1,4-cdc)(4-bpfp)2(H2O)2]·2H2O}n (5) was isolated along with 4; this compound underwent some in situ cis to trans cyclohexane-dicarboxylate ligand isomerization and exhibits a ladder polymer motif.

  17. Incorporation of Polymers into Calcined Clays as Improved Thermal Insulating Materials for Construction

    Directory of Open Access Journals (Sweden)

    Serina Ng

    2017-01-01

    Full Text Available Calcined clay is a Type Q supplementary cementing material according to EN197-1:2000. It possesses lower thermal conductivity than cement. To further improve its thermal insulation property, polymer-calcined clay complexes (PCCs were produced in a one-pot synthesis. Two contrasting polymers, polystyrene (PS and polyethylene glycol (PEG, were employed. The hydrophilicity of the polymers influenced the thermal conductivity of PCC. Hydrophilic PEG entrapped more water molecules on clay layers than the hydrophobic PS, making PEG-PCC more thermally conducting than PS-PCC. Contaminants in calcined clays played a role in affecting the overall thermal conductivity. PCC can improve thermal insulation properties for future construction applications.

  18. Selective high capacity adsorption of Congo red, luminescence and antibacterial assessment of two new cadmium(II) coordination polymers

    Science.gov (United States)

    Beheshti, Azizolla; Nozarian, Kimia; Ghamari, Narges; Mayer, Peter; Motamedi, Hossein

    2018-02-01

    Coordination polymers [CdCl(NCS)L]n (1) and {[Cd2I4(L)2]·H2O·DMF}n (2) (where L = 1, 1-(1,4-butanediyl)bis(1,3-dihydro-3-methyl-1H-imidazole- 2-thione)) were synthesized and structurally characterized. Compounds 1 and 2 both possess a tetrahedral arrangement with CdS2NCl and CdS2I2 cores, respectively. In these structures, the flexible thione ligands adopt a μ- bridging coordination mode to form 1D chains along the b-axis. The 1D chains are join together by C-H--Cl hydrogen bonds (in 1) and water molecules (in 2) to create a 2D supramolecular framework with an ABAB…packing mode. Remarkably, compounds 1 and 2 in particular polymer 1 exhibit excellent capacity to adsorb Congo red (CR) with high selectivity. The experimental data demonstrate that the mechanism of sorption process can be described by the Elovich and pseudo second order kinetic models for 1 and 2, respectively. Furthermore, the possible mechanism of CR absorption was investigated by UV-Vis and solid state fluorescence spectra for the title polymers. In addition, the antibacterial assessment of these compounds have also been studied.

  19. Design and construction of diverse structures of coordination polymers: Photocatalytic properties

    Energy Technology Data Exchange (ETDEWEB)

    Wu, Yu, E-mail: wuyuhlj@163.com [College of Chemistry and Environmental Engineering, Sichuan University of Science & Engineering, Zigong 643000 (China); Institute of Functional Materials, Sichuan University of Science & Engineering, Zigong 643000 (China); Lu, Lu [College of Chemistry and Environmental Engineering, Sichuan University of Science & Engineering, Zigong 643000 (China); Institute of Functional Materials, Sichuan University of Science & Engineering, Zigong 643000 (China); Feng, Jianshen [Institute of Functional Materials, Sichuan University of Science & Engineering, Zigong 643000 (China); Li, Yulong; Sun, Yanchun [College of Chemistry and Environmental Engineering, Sichuan University of Science & Engineering, Zigong 643000 (China); Institute of Functional Materials, Sichuan University of Science & Engineering, Zigong 643000 (China); Ma, Aiqing, E-mail: maqandght@126.com [School of Pharmacy, Guangdong Medical University, Dongguan 523808 (China)

    2017-01-15

    The reaction of Cu(NO{sub 3}){sub 2}·3H{sub 2}O/Ni(NO{sub 3}){sub 2}·6H{sub 2}O with 4′-(4-(3,5-dicarboxylphenoxy)phenyl)-4,2′:6′,4′′-terpyridine (H{sub 2}dbp) gave [Cu{sub 0.5}(Hdbp)]{sub n} (1) and [Ni(dbp)(H{sub 2}O)]{sub n} (2), while the reactions of Co(NO{sub 3}){sub 2}·6H{sub 2}O with H{sub 2}dbp in the presence of 4,4′-bipy and 2,2′-bpy generated [Co(dbp)(4,4′-bipy)]{sub n} (3) and ([Co(dbp)(2,2′-bipy)]{sub n}·H{sub 2}O) (4), respectively (4,4′-bipy=4.4′-pyridine and 2,2′-bipy=2,2′-bipyridine). X-Ray single-crystal analyses reveal that 1 contains a 1D double chain. 2 possesses a 3D architecture with (4.6{sup 2}0.8{sup 3}){sub 2} topology that is interpenetrated with each other to form a 2-fold network. In 3, the 2D [Co(dbp)]n sheets are pillared by 4,4′-bpy to form a 3D framework with 1D open channel. Compound 4 consists of a 1D ladder-like chain. The results showed that the structural diversity of the coordination polymers resulted from the different geometries of metal ions and effect of assistant ligands. Furthermore, the photocatalytic properties of 1–4 for degradation of the methyl violet (MV) have been examined. - Graphical abstract: The photocatalytic activity and selectivity of complexes 1–4 prove that they may be good and stable photocatalysts for degradation of organic dyes.

  20. Vapochromic Behaviour of M[Au(CN2]2-Based Coordination Polymers (M = Co, Ni

    Directory of Open Access Journals (Sweden)

    Daniel B. Leznoff

    2012-03-01

    Full Text Available A series of M[Au(CN2]2(analytex coordination polymers (M = Co, Ni; analyte = dimethylsulfoxide (DMSO, N,N-dimethylformamide (DMF, pyridine; x = 2 or 4 was prepared and characterized. Addition of analyte vapours to solid M(μ-OH2[Au(CN2]2 yielded visible vapochromic responses for M = Co but not M = Ni; the IR νCN spectral region changed in every case. A single crystal structure of Zn[Au(CN2]2(DMSO2 revealed a corrugated 2-D layer structure with cis-DMSO units. Reacting a Ni(II salt and K[Au(CN2] in DMSO yielded the isostructural Ni[Au(CN2]2(DMSO2 product. Co[Au(CN2]2(DMSO2 and M[Au(CN2]2(DMF2 (M = Co, Ni complexes have flat 2-D square-grid layer structures with trans-bound DMSO or DMF units; they are formed via vapour absorption by solid M(μ-OH2[Au(CN2]2 and from DMSO or DMF solution synthesis. Co[Au(CN2]2(pyridine4 is generated via vapour absorption by Co(μ-OH2[Au(CN2]2; the analogous Ni complex is synthesized by immersion of Ni(μ-OH2[Au(CN2]2 in 4% aqueous pyridine. Similar immersion of Co(μ-OH2[Au(CN2]2 yielded Co[Au(CN2]2(pyridine2, which has a flat 2-D square-grid structure with trans-pyridine units. Absorption of pyridine vapour by solid Ni(μ-OH2[Au(CN2]2 was incomplete, generating a mixture of pyridine-bound complexes. Analyte-free Co[Au(CN2]2 was prepared by dehydration of Co(μ-OH2[Au(CN2]2 at 145 °C; it has a 3-D diamondoid-type structure and absorbs DMSO, DMF and pyridine to give the same materials as by vapour absorption from the hydrate.

  1. Crystal structures and thermodynamics/kinetics of Zn(II) coordination polymers with helical chains

    International Nuclear Information System (INIS)

    He, Tian; Yue, Ke-Fen; Zhao, Yi-xing; Chen, San-Ping; Zhou, Chun-sheng; Yan, Ni

    2016-01-01

    Solvothermal reactions of Zn(II) acetates and four V-shaped carboxylates ligands in the presence of 1,4-Bis(2-methyl-imidazol-1-yl)butane afforded four interesting Zn(II) coordination polymers with helical chains, namely, {[Zn(bib)(atibdc)]·2H 2 O} n (1), {[Zn(bib)(atbip)]·H 2 O} n (2), [Zn(bib)(2,2′-tda)]} n (3) and {[Zn(bib)(5-tbipa)]·EtOH} n (4), (H 2 atibdc=5-amino-2,4,6-triiodoisophthalic acid, H 2 atbip=5-amino-2,4,6-tribromoisophthalic acid, 2,2′-H 2 tad=2,2′-thiodiacetic acid, 5-H 2 tbipa=5-tert-butyl-isophthalic acid). 1 reveals a 3D chiral framework with three kinds of helical chains along a, b and c axis. 2 shows a 2D step-type chiral framework with right-handed helical chains. 3 displays a wavelike 2D layer network possessing alternate left- and right-handed helical chains. 4 presents a four-connected 3D framework with zigzag and meso-helical chains. The different spacers and substituent group of carboxylic acid ligands may lead to the diverse network structures of 1–4. The fluorescent properties of complexes 1−4 were studied. In addition, the thermal decompositions properties of 1–4 were investigated by simultaneous TG/DTG–DSC technique. The apparent activation energy E and the pre-exponential factor (A) of skeleton collapse for the complexes 1–4 are calculated by the integral Kissinger's method and Ozawa–Doyle's method. The activation energy E (E 1 =209.658 kJ·mol −1 , E 2 =250.037 kJ mol −1 , E 3 =225.300 kJ mol −1 , E 4 =186.529 kJ·mol −1 ) demonstrates that the reaction rate of the melting decomposition is slow. The thermodynamic parameters (ΔH ‡ , ΔG ‡ and ΔS ‡ ) at the peak temperatures of the DTG curves were also calculated. ΔG ‡ >0 indicates that the skeleton collapse is not spontaneous. ΔH d >0 suggests that the skeleton collapse is endothermic, corresponding to the intense endothermic peak of the DSC curve. The structural stability could be illustrated from the point of thermodynamics and

  2. Base-induced self-assembly for one-dimensional coordination polymers via chiral pendant-armed Schiff base mononuclear Pb(II) macrocycles.

    Science.gov (United States)

    Zhang, Kun; Jin, Chao; Sun, Yuchen; Chang, Feifan; Huang, Wei

    2014-08-04

    A pair of 18-membered [1 + 1] chiral pendant-armed Schiff base macrocyclic mononuclear Pb(II) complexes with an unusual N1O2 coordination mode, synthesized from two chiral isomeric dialdehyde components, can be further self-assembled to one-dimensional ribbon coordination polymers by adding NaOH as a base to remove two phenolic protons.

  3. Mössbauer Spectroscopic Study on Hofmann-like Coordination Polymer Fe(4-Clpy2[Ni(CN4

    Directory of Open Access Journals (Sweden)

    Takafumi Kitazawa

    2016-06-01

    Full Text Available 57Fe Mössbauer spectroscopic results on the 2D Hofmann-like coordination polymer Fe(4-Clpy2Ni(CN4 (sample 1 indicate that iron(II ions are in a high spin state both at R.T. and T = 80 K, showing that the compound exhibits no spin crossover (SCO behavior. Mössbauer spectra at R.T. and T = 80 K show one major doublet which corresponds to the HS1 is due to high spin iron(II sites coordinated by four N atoms of cyano groups and two N atoms of 4-Clpy ligand in the sample 1. Two minor doublets coexisted in sample 1. One minor doublet with a large quadrupole splitting can be explained by the presence of defects in the coordination polymer frameworks. Another minor doublet is with a small quadrupole splitting, indicating the presence of iron(III high spin species or iron(II low spin species. This work is licensed under a Creative Commons Attribution 4.0 International License.

  4. Electrical conductivity studies on Ammonium bromide incorporated with Zwitterionic polymer blend electrolyte for battery application

    Science.gov (United States)

    Parameswaran, V.; Nallamuthu, N.; Devendran, P.; Nagarajan, E. R.; Manikandan, A.

    2017-06-01

    Solid polymer blend electrolytes are widely studied due to their extensive applications particularly in electrochemical devices. Blending polymer makes the thermal stability, higher mechanical strength and inorganic salt provide ionic charge carrier to enhance the conductivity. In these studies, 50% polyvinyl alcohol (PVA), 50% poly (N-vinyl pyrrolidone) (PVP) and 2.5% L-Asparagine mixed with different ratio of the Ammonium bromide (NH4Br), have been synthesized using solution casting technique. The prepared PVA/PVP/L-Asparagine/doped-NH4Br polymer blend electrolyte films have been characterized by various analytical methods such as FT-IR, XRD, impedance spectroscopy, TG-DSC and scanning electron microscopy. FT-IR, XRD and TG/DSC analysis revealed the structural and thermal behavior of the complex formation between PVA/PVP/L-Asparagine/doped-NH4Br. The ionic conductivity and the dielectric properties of PVA/PVP/L-Asparagine/doped-NH4Br polymer blend electrolyte films were examined using impedance analysis. The highest ionic conductivity was found to be 2.34×10-4 S cm-1 for the m.wt. composition of 50%PVA:50%PVP:2.5%L-Asparagine:doped 0.15 g NH4Br at ambient temperature. Solid state proton battery is fabricated and the observed open circuit voltage is 1.1 V and its performance has been studied.

  5. Incorporation of Znq2 complexes into mesoporous silica and their transparent polymer luminescent nanocomposites

    International Nuclear Information System (INIS)

    Du Yaying; Fu Yuqin; Shi Yongli; Lue Xiaodan; Lue Changli; Su Zhongmin

    2009-01-01

    Znq 2 -functionalized colloidal mesoporous silicas (Znq 2 -CMS)/polymer transparent nanocomposites were prepared by in situ bulk polymerization. CMS nanoparticles or nanorods with hydroxyl-, mercapto- and sulfonic-functionalized interiors were obtained by different synthetic routes in the nanosize dimensions between 50 and 500 nm. The luminescent Znq 2 complex was successfully introduced in the pores of different mesoporous silicas by chemical adsorption as the driving force. The different internal circumstances of mesoporous silicas had an obvious effect on the luminescence and lifetime of Znq 2 complex. The transparent fluorescent nanocomposites were fabricated from different Znq 2 -CMS and suitable monomers. The Znq 2 -CMS were uniformly dispersed in the polymer matrix without evident aggregation. The photoluminescence properties of Znq 2 -CMS in the transparent matrix exhibited a dependence on the inner surrounding of CMS due to the interaction between Znq 2 -CMS and polymers. The maximum emission peak of the nanocomposites had a red-shift of 28 nm as compared to pure Znq 2 -CMS. - Graphical abstract: Znq 2 -functionalized colloidal mesoporous silicas (Znq 2 -CMS)/polymer transparent fluorescent nanocomposites were prepared by in situ bulk polymerization. The figure shows the synthetic scheme for the Znq 2 -CMS and their transparent bulk nanocomposites.

  6. Structural diversification and photocatalytic properties of three Cd(II) coordination polymers decorated with different auxiliary ligands

    Energy Technology Data Exchange (ETDEWEB)

    Yin, Wen-Yu; Zhuang, Guo-Yong; Huang, Zuo-Long; Cheng, Hong-Jian; Zhou, Li; Ma, Man-Hong; Wang, Hao; Tang, Xiao-Yan, E-mail: xytang@cslg.edu.cn; Ma, Yun-Sheng; Yuan, Rong-Xin, E-mail: yuanrx@cslg.edu.cn

    2016-03-15

    Three cadmium coordination polymers, [Cd(bismip)]{sub n} (1), {[Cd(bismip)(phen)]·H_2O}{sub n} (2) and {[Cd_2(bismip)_2(4,4′-bipy)]·2H_2O}{sub n} (3) (H{sub 2}bismip=5-(1H-benzoimidazol-2-ylsulfanylmethyl)-isophthalic acid, phen=1,10-phenanthroline, 4,4′-bipy=4,4′-bipyridine) have been prepared under solvothermal conditions. In 1, the [Cd{sub 4}(bismip){sub 3}] units are jointed by bismip ligands to afford a three-dimensional (3D) architecture. Complex 2 exhibits a 3D supramolecular framework based on the interconnection of 1D chains through hydrogen bonding interactions and π-π packing interactions. 3 is a two-fold interpenetrating 3D architecture with a (4·8{sup 2})(4{sup 2}·8{sup 4}) Schläfli symbol in which 2D layers are interlinked by 4,4′-bipy ligands. The diverse structures of compounds 1–3 indicate that the auxiliary ligands have significant effects on the final structures. The photoluminescent properties and photocatalytic properties of these coordination polymers in the solid state were also investigated. Remarkably, 3 shows the wide gap semiconductor nature and exhibit excellent photocatalytic performance. - Graphical abstract: Three cadmium coordination polymers with different architectures based on 5-(1H-benzoimidazol-2-ylsulfanylmethyl)-isophthalic acid have been prepared. Their photoluminescent properties were also investigated. - Highlights: • Three new Cd(II) Cps were synthesized based on H{sub 2}bismip. • Compounds 1 and 3 show 3D networks and 2 exhibits a 1D chain. • Compoud 3 exhibits good catalytic activity of methylene blue photodegradation.

  7. [Bimetallic coordination polymers [[ML][FeIIFeIII(ox)3].1.5H2O] infinity with layer structure syntheses, spectra characterization].

    Science.gov (United States)

    Chen, You-cun; Liu, Guang-xiang; Zhou, Hong; Ren, Xiao-ming

    2002-10-01

    Two new schiff base complexes, NiL(ClO4).3H2O (1) and CuL(ClO4).4H2O (2) [L was condensed from equation molar salicylaldehyde and diethylenetriamine] have been synthesized and characterized. Further, two new bimetallic coordination polymers, [[ML][FeIIFeIII(ox)3].1.5H2O] infinity were synthesized and characterized, where ox2- = oxalate, M = Ni2+ (3) or Cu2+ (4). The tested results of elementary analysis of coordination polymers (3) and (4) were according with the theoretical value, and the results of the IR indicated that the coordination of oxalate were bridgetype in compound (3) and (4). 2-D layer coordination polymers were synthesized by oxalate and Fe3+, Fe2+. The result of Mössbauer spectra of (3) and (4) in room temperature revealed that two different postural ferric ions were found in coordination polymer (3) and (4), and anions layer was formed by [FeIIFeIII(ox)3]- unit. The compounds of (3) and (4) were bimetallic coordination polymers.

  8. Dynamic porous coordination polymer based on 2D stacked layers exhibiting high sorption selectivity for CO2.

    Science.gov (United States)

    Liu, Bo; Hou, Lei; Wang, Yao-Yu; Miao, Hui; Bao, Li; Shi, Qi-Zhen

    2012-03-21

    A new dynamic porous coordination polymer (PCP) [Ni(dcpy)(bipy)(0.5)(H(2)O)]·1.5H(2)O (1) was synthesized by assembly of 3-(2',5'-dicarboxylphenyl)pyridine (dcpy), 4,4'-bipyridine (bipy) and NiSO(4)via solvothermal, hydrothermal and microwave methods, displaying a wavelike 2D stacked layer framework. Gas adsorption studies for 1 shows a high selective adsorption of CO(2) over other gases (N(2), CH(4) and CO). The adsorption capacity for N(2) can be moderately altered by different activation temperatures demonstrating the framework flexibility of 1.

  9. The Role of IAEA in Coordinating Research and Transferring Technology in Radiation Chemistry and Processing of Polymers

    International Nuclear Information System (INIS)

    Haji Saeid, M.

    2006-01-01

    The IAEA has been playing a significant role in fostering developments in radiation technology in general and radiation processing of polymers in particular, among its Member States (MS) and facilitate know-how/technology transfer to developing MS. The former is usually achieved through coordinated research projects (CRP) and thematic technical meetings, while the latter is mainly accomplished through Technical Cooperation (TC) projects. Coordinated research projects encourage research on, and development and practical application of, radiation technology to foster exchange of scientific and technical information. The CRP brings together typically 10 - 15 groups of participants to share and complement core competencies and work on specific areas of development needed to benefit from an emerging radiation technique and its applications. The technical cooperation (TC) programme helps Member States realize their development priorities through the application of appropriate radiation technology. TC builds national capacities through training, expert advice and delivery of equipment. The impact of the IAEA's efforts is visible by the progress noticeable in adoption of radiation technology and/or growth in the range of activities in several MS in different regions. The IAEA has implemented several coordinated research projects (CRP) recently, including one on-going project, in the field of radiation processing of polymeric materials. The CRPs facilitated the acquisition and dissemination of know-how and technology for controlling of degradation effects in radiation processing of polymers, radiation synthesis of stimuli-responsive membranes, hydrogels and absorbents for separation purposes and the use of radiation processing to prepare biomaterials for applications in medicine. A number of technical cooperation projects have been implemented in this field to strengthen the capability of developing Member States and to create awareness in the industries about the technical

  10. Self-Assembled ROS-Sensitive Polymer-Peptide Therapeutics Incorporating Built-in Reporters for Evaluation of Treatment Efficacy.

    Science.gov (United States)

    Qiao, Zeng-Ying; Zhao, Wen-Jing; Cong, Yong; Zhang, Di; Hu, Zhiyuan; Duan, Zhong-Yu; Wang, Hao

    2016-05-09

    One of the major challenges in current cancer therapy is to maximize therapeutic effect and evaluate tumor progression under the scheduled treatment protocol. To address these challenges, we synthesized the cytotoxic peptide (KLAKLAK)2 (named KLAK) conjugated amphiphilic poly(β-thioester)s copolymers (H-P-K) composed of reactive oxygen species (ROS) sensitive backbones and hydrophilic polyethylene glycol (PEG) side chains. H-P-K could self-assemble into micelle-like nanoparticles by hydrophobic interaction with copolymer backbones as cores and PEG and KLAK as shells. The assembled polymer-peptide nanoparticles remarkably improved cellular internalization and accumulation of therapeutic KLAK in cells. Compared to free KLAK peptide, the antitumor activity of H-P-K was significantly enhanced up to ∼400 times, suggesting the effectiveness of the nanoscaled polymer-peptide conjugation as biopharmaceuticals. The higher antitumor activity of nanoparticles was attributed to the efficient disruption of mitochondrial membranes and subsequent excessive ROS production in cells. To realize the ROS monitoring and treatment evaluation, we encapsulated squaraine (SQ) dyes as built-in reporters in ROS-sensitive H-P-K micelles. The overgenerated ROS around mitochondria stimulated the swelling of nanoparticles and subsequent release of SQ, which formed H-aggregates and significantly increased the photoacoustic (PA) signal. We believed that this self-assembled polymer-peptide nanotherapeutics incorporating built-in reporters has great potential for high antitumor performance and in situ treatment evaluation.

  11. Synthesis, structure, and luminescence property of a series of Ag–Ln coordination polymers with the N-heterocyclic carboxylato ligand

    International Nuclear Information System (INIS)

    Jin, Jing; Chen, Chong; Gao, Yan; Zhao, Ran; Wang, Xiuyan; Lü, Chunxin; Chi, Yuxian; Niu, Shuyun

    2016-01-01

    Six Ln–Ag coordination polymers {[LnAg 2 (IN) 4 (H 2 O) 5 ]·NO 3 ·2H 2 O} n (Ln=Ho (1) and Tb (2), HIN=isonicotinic acid), {[PrAg 2 (IN) 4 (H 2 O) 2 ]·NO 3 ·H 2 O} n (3), [LnAg(pdc) 2 ] n (Ln=Eu(4) and Pr (5), H 2 pdc=3,4-pyridine-dicarboxylic acid) and [NdAg(bidc) 2 (H 2 O) 4 ] n (6) (H 2 bidc=benzimidazole-5,6-dicarboxylic acid) have been hydrothermally synthesized and characterized by single crystal X-ray diffraction, elemental analysis, IR, UV–vis-NIR absorption spectra, fluorescence spectra and thermogravimetric analysis. Structural analyses reveal that the six polymers exhibit 0D (polymer (1)), 1D (polymer (2)), 2D (polymers (3) and (5)) and 3D (polymers (4) and (6)) infinite structures, respectively. Polymers (1)–(6) exhibit the Ln(III) characteristic emission in the near-infrared (NIR) region or in the visible region. Especially, the NIR emission bands of polymers 1, 5 and 6 evidently present shift or splitting due to formation of the Ln–Ag coordination polymers. This can be attributed to the tune of inner levels in Ln–Ag system caused by the interact and influence between the 4d orbital of the Ag(I) ion and the 4f orbital of the Ln(III) ion, which can be confirmed by the UV–vis-NIR absorption spectra of the polymers. In addition, the distortion of coordination geometry as well as difference of the coordination number around the Ag(I) ion affect the structure framework. - Graphical abstract: Six Ag–Ln coordination polymers have been hydrothermally synthesized and characterized. The photoluminescence properties were studied. The distortion of coordination geometry of Ag(I) ion affect structure framework. Introduction of Ag(I) cause wonderful changes to the NIR emission of Ln(III) ions. - Highlights: • Six Ln–Ag polymers have been synthesized and characterized. • The distortion of coordination geometry of Ag(I) ion affect structure framework. • Introduction of Ag(I) cause wonderful changes to the NIR emission of Ln(III) ions.

  12. A kinematic wave model in Lagrangian coordinates incorporating capacity drop: Application to homogeneous road stretches and discontinuities

    Science.gov (United States)

    Yuan, Kai; Knoop, Victor L.; Hoogendoorn, Serge P.

    2017-01-01

    On freeways, congestion always leads to capacity drop. This means the queue discharge rate is lower than the pre-queue capacity. Our recent research findings indicate that the queue discharge rate increases with the speed in congestion, that is the capacity drop is strongly correlated with the congestion state. Incorporating this varying capacity drop into a kinematic wave model is essential for assessing consequences of control strategies. However, to the best of authors' knowledge, no such a model exists. This paper fills the research gap by presenting a Lagrangian kinematic wave model. "Lagrangian" denotes that the new model is solved in Lagrangian coordinates. The new model can give capacity drops accompanying both of stop-and-go waves (on homogeneous freeway section) and standing queues (at nodes) in a network. The new model can be applied in a network operation. In this Lagrangian kinematic wave model, the queue discharge rate (or the capacity drop) is a function of vehicular speed in traffic jams. Four case studies on links as well as at lane-drop and on-ramp nodes show that the Lagrangian kinematic wave model can give capacity drops well, consistent with empirical observations.

  13. Syntheses, structures and magnetic properties of four coordination polymers based on nitrobenzene dicarboxylate and various N-donor coligands

    International Nuclear Information System (INIS)

    Li, Gui-Lian; Yin, Wei-Dong; Liu, Guang-Zhen; Ma, Lu-Fang; Wang, Li-Ya

    2014-01-01

    Four new coordination polymers ([Ni(4-Nbdc)(bpa)(H 2 O)]) n (1), ([Co(4-Nbdc)(bpp) (H 2 O)]) n (2), ([Ni(4-Nbdc)(bpp)(H 2 O)]·H 2 O) n (3), and ([Mn 2 (3-Nbdc) 2 (bib) 3 ]·2H 2 O) n (4) (4-Nbdc=4-nitrobenzene-1,2-dicarboxylate, 3-Nbdc=3-nitrobenzene-1,2-dicarboxylate, bpa=1,2-bi(4-pyridyl)ethane, bpp=1,3-bis(4-pyridyl)propane, and bib=1,4-bis(1-imidazoly)benzene), were synthesized by hydrothermal reactions, and characterized by single-crystal X-ray diffractions, elemental analysis, FT-IR, PXRD, TGA and magnetic analysis. Complexes 1 and 2 display quasi-trapezoidal chain and brick-wall layer, and both of them contain metal–carboxylate binuclear units. Complexes 3 and 4 exhibit three-dimensional frameworks with the (6 6 ) dia topology and (4 4 .6 10 .8)(4 4 .6 2 ) fsc topology, and both of them contain metal–carboxylate chains. The carboxyl groups with syn-anti coordination mode mediate effectively the weak ferromagnetic coupling interaction within Ni(II)–carboxylate binuclear in 1 (J=1.27 cm −1 ) and Ni(II)–carboxylate chain in 3 (J=1.44 cm −1 ), respectively, and the carboxyl groups with anti-anti coordination mode leads to the classic antiferromagnetic coupling interaction within Mn(II)–carboxylate chain in 4 (J=−0.77 cm −1 ). - Highlights: • Four novel coordination polymers were hydrothermally synthesized. • 1 is 1D quasi-trapezoidal chain and 2 is brick-wall layer both with dinuclear units. • 3 and 4 show 3D frameworks both with 1D metal–carboxylate chains. • 1 and 3 exhibit ferromagnetic coupling, while 4 shows antiferromagnetic coupling

  14. Rare configuration of tautomeric benzimidazolecarboxylate ligands in cadmium(II) and copper(II) coordination polymers

    International Nuclear Information System (INIS)

    Wu, Jing-Yun; Yang, Ciao-Wei; Chen, Hui-Fang; Jao, Yu-Chen; Huang, Sheng-Ming; Tsai, Chiitang; Tseng, Tien-Wen; Lee, Gene-Hsiang; Peng, Shie-Ming; Lu, Kuang-Lieh

    2011-01-01

    Two Cd(HBimc)-based isomers, [Cd(HBimc N )(HBimc T )(H 2 O)].3.5H 2 O.EtOH (1a.3.5H 2 O.EtOH, H 2 Bimc=1H-benzimidazole-5-carboxylic acid) and [Cd(HBimc N )(HBimc T )(H 2 O)] (1b), and two Cu(HMBimc)-based coordination polymers, [Cu(HMBimc N ) 2 (H 2 O)].1/2H 2 O (2.1/2H 2 O, H 2 MBimc=2-methyl-1H-benzimidazole-5-carboxylic acid) and [Cu(HMBimc T ) 2 ].2THF.H 2 O (3.2THF.H 2 O), were self-assembled from Cd(ClO 4 ) 2 .6H 2 O/H 2 Bimc and Cu(ClO 4 ) 2 .6H 2 O/H 2 MBimc systems, respectively. Compound 1a adopts a ladder-like chain structure, comprised of a hydrogen-bond-stabilized Cd 2 (HBimc N ) 2 -metallocyclic stair and a 1D straight -(Cd-HBimc T ) n - edge, whereas compound 1b exhibits a 2D (4,4)-rhombus layered structure, intercrossed by 1D -(Cd-HBimc N ) n - chains and -(Cd-HBimc T ) n - chains. Compound 2 shows a 1D double-stranded wave-like chain from two single-stranded wave-like -(Cu-HMBimc N ) n - chains and compound 3 adopts a 2D (4,4)-topological layer structure, intercrossed by subunits of 1D -(Cu-HMBimc T ) n - chains. Interestingly, a pair of tautomeric HBimc building blocks-normal (N or HBimc N ) and tautomer (T or HBimc T )-is simultaneously included in the structures of 1a and 1b, whilst the N- and T-configured HMBimc building blocks are present as separate entities in Cu species, 2 and 3, respectively. The existence of only a tautomer (T) mode of the benzimidazolecarboxylate-based ligand in a Cu(II) network is observed for the first time. - Graphical abstract: A pair of tautomeric HBimc building blocks (normal (N) and tautomer (T)) is found simultaneously in two Cd(II) networks, whereas, the normal and tautomer modes of HMBimc are present as separate entities in two Cu(II) frameworks. The isolation of a Cu(II) network with only a tautomer (T) mode of the benzimidazolecarboxylate-based ligand is achieved for the first time. Highlights: →Benzimidazolecarboxylates could exhibit normal (N) and tautomer (T) configurations. → A pair of N- and T

  15. A novel oxalate-based three-dimensional coordination polymer showing magnetic ordering and high proton conductivity.

    Science.gov (United States)

    Mon, Marta; Vallejo, Julia; Pasán, Jorge; Fabelo, Oscar; Train, Cyrille; Verdaguer, Michel; Ohkoshi, Shin-Ichi; Tokoro, Hiroko; Nakagawa, Kosuke; Pardo, Emilio

    2017-11-07

    A novel three-dimensional (3D) coordination polymer with the formula (C 3 N 2 H 5 ) 4 [MnCr 2 (ox) 6 ]·5H 2 O (2), where ox = oxalate and C 3 N 2 H 5 = imidazolium cation, is reported. Single crystal X-ray diffraction reveals that this porous coordination polymer adopts a chiral three-dimensional quartz-like architecture, with the guest imidazolium cations and water molecules being hosted in its pores. This novel multifunctional material exhibits both a ferromagnetic ordering at T C = 3.0 K, related to the host MnCr 2 network, and high proton conductivity [1.86 × 10 -3 S cm -1 at 295 K and 88% relative humidity (RH)] due to the presence of the acidic imidazolium cations and free water molecules. The similarity of the structure of compound 2 to that of the previously reported analogous compound (NH 4 ) 4 [MnCr 2 (ox) 6 ]·4H 2 O, (1), also allows us to analyse, to a certain extent, the effect of the acidity of the proton donating guest molecules on proton conduction properties. 2 hosts, in one-dimensional (1D) channels, imidazolium cations, which are more acidic than the ammonium ones in 1 and, as a consequence, 2 shows higher proton conduction than 1, highlighting the effect of the pK a of the proton donating guest molecules on proton conductivity.

  16. Syntheses, structures, and photoluminescence of three-dimensional lanthanide coordination polymers with 2,5-pyridinedicarboxylic acid

    International Nuclear Information System (INIS)

    Huang Yan; Song Yishan; Yan, Bing; Shao Min

    2008-01-01

    Four new open-framework coordination polymers of lanthanide 2,5-pyridinedicarboxylates, with the formulas Pr2(pydc) 3 (H 2 O) 2 (1), Ln(pydc)(Hpydc) (Ln=Tb (2), Er (3), Eu (5)), and Gd(pydc)(nic)(H 2 O) (4) (H 2 pydc=2,5-pyridinedicarboxylic acid, Hnic=nicotinic acid), have been hydrothermally synthesized and four of them (except Eu (5)) have been structurally characterized. Complex 1 consists of two types of ligand-binding modes contributing to link the PrO 7 N(H 2 O) polyhedral chains to three-dimensional (3D) open-framework architecture. Complexes 2 and 3 are isostructural and feature unique 3D cage-like supramolecular frameworks remarkably different from that of 1, owing to the different ligand-bridging pattern. Complex 4, however, has the distinct 3D open-framework architecture due to the presence of unexpected nicotinate ligands, which may be derived from pydc ligands via in-situ decarboxylation under the hydrothermal condition. - Graphical abstract: Four new lanthanide coordination polymers have been hydrothermally synthesized by the reaction of 2,5-pyridinedicarboxylic acid with the corresponding lanthanide nitrates, and they show three types of 3D open-framework architecture. Complexes 2 and 5 show strong characteristic green (or red) luminescence and long lifetimes

  17. A luminescent lanthanide coordination polymer based on energy transfer from metal to metal for hydrogen peroxide detection.

    Science.gov (United States)

    Zeng, Hui-Hui; Zhang, Li; Rong, Lian-Qing; Liang, Ru-Ping; Qiu, Jian-Ding

    2017-03-15

    A bimetal lanthanide coordination polymer nanoparticle (ATP-Ce/Tb-Tris CPNs) with good biocompatibility was synthesized in Tris-HCl buffer using adenosine triphosphate (ATP) molecules as the bridge ligands. The large absorption cross section and suitable emission energy of Ce 3+ matching to the adsorption energy of Tb 3+ ( 4 f n ) results in the efficient energy transfer from Ce 3+ to Tb 3+ , thus the synthesized ATP-Ce/Tb-Tris CPNs exhibit the characteristic green emission of Tb 3+ . Such energy transfer from metal to metal in fluorescent lanthanide coordination polymer nanoparticles (Ln-CPNs) has been demonstrated. It is found that the oxidation of Ce 3+ in ATP-Ce/Tb-Tris CNPs to Ce 4+ would interrupt the energy transfer from Ce 3+ to Tb 3+ , leading to fluorescence quenching of Tb 3+ . On the basis of this quenching mechanism, ATP-Ce/Tb-Tris CPNs has been successfully used to detect reactive oxygen H 2 O 2 with detection limit as low as 2nM. If glucose oxidase is present in the system, glucose can be determined using the ATP-Ce/Tb-Tris CNPs nanosensor. Copyright © 2016 Elsevier B.V. All rights reserved.

  18. Impact of ligand spacer and counter-anion in selected 1D iron(II) spin crossover coordination polymers

    Energy Technology Data Exchange (ETDEWEB)

    Dirtu, Marinela M.; Schmit, France; Naik, Anil D. [Universite Catholique de Louvain, Institute of Condensed Matter and Nanosciences (Belgium); Rotaru, Aurelian [' Stefan cel Mare' University, Department of Electrical Engineering and Computer Science (Romania); Marchand-Brynaert, Jacqueline; Garcia, Yann, E-mail: yann.garcia@uclouvain.be [Universite Catholique de Louvain, Institute of Condensed Matter and Nanosciences (Belgium)

    2012-03-15

    A new 1D coordination polymer [Fe({beta}Alatrz){sub 3}](ClO{sub 4}){sub 2} Bullet-Operator H{sub 2}O (1) with a neutral bidentate ligand, {beta}Alatrz = 4H-1,2,4-triazol-4-yl-propionate, was prepared and its magnetic behavior was investigated by temperature dependent magnetic susceptibility measurements and {sup 57}Fe Moessbauer spectroscopy. The temperature dependence of the high-spin molar fraction derived from {sup 57}Fe Moessbauer spectroscopy recorded on cooling below room temperature reveals a gradual single step transition with T{sub 1/2} = 173 K between high-spin and low-spin states in agreement with magnetic susceptibility measurements. 1 presents striking reversible thermochromism from white, at room temperature, to pink on quench cooling to liquid nitrogen. The phase transition is of first order as deduced from differential scanning calorimetry, with T{sub 1/2} matching the one determined by both SQUID and {sup 57}Fe Moessbauer spectroscopy. A brief assessment has been made among closely related 1D coordination polymers to perceive the effect of ligand spacer length and anion effect on the spin crossover behavior of these new materials.

  19. Aerogels of 1D Coordination Polymers: From a Non-Porous Metal-Organic Crystal Structure to a Highly Porous Material

    Directory of Open Access Journals (Sweden)

    Adrián Angulo-Ibáñez

    2016-01-01

    Full Text Available The processing of an originally non-porous 1D coordination polymer as monolithic gel, xerogel and aerogel is reported as an alternative method to obtain novel metal-organic porous materials, conceptually different to conventional crystalline porous coordination polymer (PCPs or metal-organic frameworks (MOFs. Although the work herein reported is focused upon a particular kind of coordination polymer ([M(μ-ox(4-apy2]n, M: Co(II, Ni(II, the results are of interest in the field of porous materials and of MOFs, as the employed synthetic approach implies that any coordination polymer could be processable as a mesoporous material. The polymerization conditions were fixed to obtain stiff gels at the synthesis stage. Gels were dried at ambient pressure and at supercritical conditions to render well shaped monolithic xerogels and aerogels, respectively. The monolithic shape of the synthesis product is another remarkable result, as it does not require a post-processing or the use of additives or binders. The aerogels of the 1D coordination polymers are featured by exhibiting high pore volumes and diameters ranging in the mesoporous/macroporous regions which endow to these materials the ability to deal with large-sized molecules. The aerogel monoliths present markedly low densities (0.082–0.311 g·cm−3, an aspect of interest for applications that persecute light materials.

  20. Stable material modication with polymers incorporation for broad application in microfabrication

    DEFF Research Database (Denmark)

    Mednova, Olga

    The aim of this thesis is to improve SU-8 fracture resistance in order to eliminate micro crack formation during fabrication of microelectromechanical system (MEMS). An amphiphilic block copolymer incorporation, as an efficient method of material toughening without changing its original propertie...

  1. Enhancing relative permittivity by incorporating PDMS-PEG multi block copolymers in binary polymer blends

    DEFF Research Database (Denmark)

    A Razak, Aliff Hisyam; Szabo, Peter; Skov, Anne Ladegaard

    Polydimethylsiloxanes (PDMS) are well-known to actuate with relatively large strains due to low modulus, but they possess lowpermittivity. Contrary, polyethyleneglycols (PEG) are not stretchable but possess high permittivity. Combination of the two polymers in a block copolymer depicts a possibil......Polydimethylsiloxanes (PDMS) are well-known to actuate with relatively large strains due to low modulus, but they possess lowpermittivity. Contrary, polyethyleneglycols (PEG) are not stretchable but possess high permittivity. Combination of the two polymers in a block copolymer depicts...... a possibility for substantial improvement of properties such as high permittivity, stretchability and non-conductivity – if carefully designed. The objective is to synthesize PDMS-PEG multiblock copolymer assembling into discontinuous morphologies in PEG based on variation of volume fractions of PDMS....... The utilized synthesis of PDMS-PEG multiblock copolymer is based on hydrosilylation reaction, which is amended from Klasner et al.1 and Jukarainen etal.2 Variation in the ratio between the two constituents introduces distinctive properties in terms of dielectric permittivity and rheological behaviour. PDMS...

  2. Assembly of three new POM-based Ag(I) coordination polymers with antibacterial and photocatalytic properties

    Energy Technology Data Exchange (ETDEWEB)

    Lu, Xin-Xin; Luo, Yu-Hui [Institute of Polyoxometalate Chemistry, Department of Chemistry, Northeast Normal University, Changchun, Jilin 130024, PR China (China); Lu, Chen [School of Pharmaceutical and Life Sciences,Changzhou University, Changzhou, Jiangsu 213164 (China); Chen, Xin, E-mail: xinchen@cczu.edu.cn [School of Pharmaceutical and Life Sciences,Changzhou University, Changzhou, Jiangsu 213164 (China); Zhang, Hong, E-mail: zhangh@nenu.edu.cn [Institute of Polyoxometalate Chemistry, Department of Chemistry, Northeast Normal University, Changchun, Jilin 130024, PR China (China)

    2015-12-15

    Three new silver coordination polymers, namely, {Ag_3(bpy)_6[PW_1_2O_4_0]} (1), {Ag_5(H_2biim)_2(Hbiim-NO_2)_2[PW_1_2O_4_0]} (2), {Ag_7(pytz)_4[PW_1_2O_4_0]} (3) (bpy=2,2′-bipyridine, H{sub 2}biim=2,2′-biimidazole, pytz=4-(1H-tetrazol-5-yl)pyridine), have been synthesized under hydrothermal condition. Compound 1 shows a 3D supramolecular framework based on 0D moieties. Compound 2 exhibits an attractive 2D biologic screw axis. Compound 3 displays a 3D structure, which consists of Ag(I)···π interactions, π···π stacking and weak Ag···Ag interactions. It is noteworthy that nitration happens to compound 2 during the hydrothermal condition, which is quite rare. Through contrasting the antibacterial activities of gram negative and gram positive bacteria, we find compounds 1–3 have better antibacterial property in gram negative bacteria than gram positive bacteria. In addition, compounds 1–3 also exhibit efficiency of photocatalytic decomposition of organic dyes. Those compounds may be used as potential multifunctional materials in wastewater treatment, because they not only can kill bacteria but also degrade organic pollutants. - Highlights: • Three new silver coordination polymers have been synthesized under hydrothermal condition. • Due to different coordination modes of rigid N-donor ligands, structures of the title compounds vary from 0D to 3D frameworks. • It is noteworthy that nitration happens to compound 2 during the hydrothermal condition, which is quite rare. • In addition, these compounds exhibit efficiency of photocatalytic decomposition of dyes and antibacterial activities.

  3. Functionalized 2D-MoS2-Incorporated Polymer Ternary Solar Cells: Role of Nanosheet-Induced Long-Range Ordering of Polymer Chains on Charge Transport.

    Science.gov (United States)

    Ahmad, Razi; Srivastava, Ritu; Yadav, Sushma; Chand, Suresh; Sapra, Sameer

    2017-10-04

    In this paper, we demonstrated the enhancement in power conversion efficiency (PCE) of solar cells based on poly(3-hexylthiophene-2,5-diyl) (P3HT)/[6,6]-phenyl C 71 butyric acid methyl ester (PC 71 BM) by incorporation of functionalized 2D-MoS 2 nanosheets (NSs) as an additional charge-transporting material. The enhancement in PCE of ternary solar cells arises due to the synergic enhancement in exciton dissociation and the improvement in mobility of both electrons and holes through the active layer of the solar cells. The improved hole mobility is attributed to the formation of the long-range ordered nanofibrillar structure of polymer phases and improved crystallinity in the presence of 2D-MoS 2 NSs. The improved electron mobility arises due to the highly conducting 2D network of MoS 2 NSs which provides additional electron transport channels within the active layer. The nanosheet-incorporated ternary blend solar cells exhibit 32% enhancement in PCE relative to the binary blend P3HT/PC 71 BM.

  4. Photopatternable Conducting Polymer Nanocomposite with Incorporated Gold Nanoparticles for Use in Organic Field Effect Transistors

    Energy Technology Data Exchange (ETDEWEB)

    Huh, Sung; Choi, Hyun Ho; Cho, Kil Won; Kim, Seung Bin [Pohang University of Science and Technology, Pohang (Korea, Republic of)

    2012-04-15

    We investigated a new method for patterning organic field-effect transistors (OFETs) using a photopatternable conducting polymer nanocomposite, consisting of poly(3-hexylthiophene) (P3HT)-coated gold nanoparticles (AuNPs) that had been modified with a photoreactive cinnamate group, to form P3HT-AuNP-CI. We found that the addition of the cinnamate group to the nanoparticle surface assisted the preparation of a solvent resistive semiconducting film and preserved the P3HT ordering, which was interrupted by Au-P3HT interactions, as well as provided UV-controllable electrical properties. The P3HT-AuNPs-CI films could be microscale-patterned via a UV crosslinking photoreaction, represented as a promising photopatternable semiconductor material for use in advanced applications, with tunable electrical properties for fabrication of sub-micron and microscale electronic devices

  5. Thiophene fused azacoronenes: regioselective synthesis, self organization, charge transport, and its incorporation in conjugated polymers

    Science.gov (United States)

    Liu, Yi; He, Bo

    2015-09-15

    A regioselective synthesis of an azacoronene fused with two peripheral thiophene groups has been realized through a concise synthetic route. The resulting thienoazacoronene (TAC) derivatives show high degree of self-organization in solution, in single crystals, in the bulk, and in spuncast thin films. Spuncast thin film field-effect transistors of the TACs exhibited mobilities up to 0.028 cm.sup.2V.sup.-1 S.sup.-1, which is among the top field effect mobilities for solution processed discotic materials. Organic photovoltaic devices using TAC-containing conjugated polymers as the donor material exhibited a high open-circuit voltage of 0.89 V, which was ascribable to TAC's low-lying highest occupied molecular orbital energy level.

  6. Photopatternable Conducting Polymer Nanocomposite with Incorporated Gold Nanoparticles for Use in Organic Field Effect Transistors

    International Nuclear Information System (INIS)

    Huh, Sung; Choi, Hyun Ho; Cho, Kil Won; Kim, Seung Bin

    2012-01-01

    We investigated a new method for patterning organic field-effect transistors (OFETs) using a photopatternable conducting polymer nanocomposite, consisting of poly(3-hexylthiophene) (P3HT)-coated gold nanoparticles (AuNPs) that had been modified with a photoreactive cinnamate group, to form P3HT-AuNP-CI. We found that the addition of the cinnamate group to the nanoparticle surface assisted the preparation of a solvent resistive semiconducting film and preserved the P3HT ordering, which was interrupted by Au-P3HT interactions, as well as provided UV-controllable electrical properties. The P3HT-AuNPs-CI films could be microscale-patterned via a UV crosslinking photoreaction, represented as a promising photopatternable semiconductor material for use in advanced applications, with tunable electrical properties for fabrication of sub-micron and microscale electronic devices

  7. Synthesis, characterization and NLO properties of a new 3D coordination polymer assembled from p-aminobenzoic acid

    Science.gov (United States)

    Li, Li; Sun, Daofeng; Wang, Zhengping; Song, Xinyu; Sun, Sixiu

    2009-05-01

    Reaction of Zn(NO 3) 2·6H 2O with p-aminobenzoic acid in a 1:2 molar ratio under ethanol medium at room temperature affords a new three dimensional (3D) coordination polymer [Zn(PABA) 2]·H 2O ( 1) (PABA = p-aminobenzoic acid). Single-crystal X-ray diffraction reveals that 1 crystallizes in the orthorhombic system, space group P2 12 12 1, a = 7.614(2), b = 11.133(3), c = 16.869(4). 1 adopts a 3D open framework with H 2O molecules in the cavities. PABA, acting as bridging ligand as well as coordinating ligand, adopts a different coordination mode to bridge Zn atoms and form the 3D supramolecular structure which is further stabilized by N-H⋯O, O-H⋯O hydrogen bonding and π-π stacking interactions. Powder second-harmonic generation (SHG) efficiency measurement with Nd:YAG laser (1064 nm) radiation shows that the SHG efficiency of 1 is equivalent to KDP crystal. The present work also demonstrates that the framework of 1 is retained after removal of the guest H 2O molecules, and the H 2O molecules can be reintroduced into the framework, indicating that this complex may also be used to generate porous materials.

  8. Synthesis, Crystal Structure, Luminescence and Magnetism of Three Novel Coordination Polymers Based on Flexible Multicarboxylate Zwitterionic Ligand

    Directory of Open Access Journals (Sweden)

    Yulu Ma

    2017-01-01

    Full Text Available Three novel zwitterionic coordination polymers, namely, {[Zn(HCbdcp2]·H2O} (1, {[Mn(Cbdcp]·3H2O} (2 and {[Cu2(Cbdcp(HCbdcpCl·H2O]·2H2O} (3, Cbdcp = 3,5-dicarboxy-1-(4-carboxybenzylpyridin-1-ium, have been prepared by a hydrothermal method and characterized by X-ray single crystal diffraction analysis, powder X-ray diffraction analysis, IR spectroscopy, and thermogravimetric analysis. With the changing of metal centers, these complexes show distinct structures: a mononuclear 2D 44-sql network for 1, a 3D 6,6-connected-type topology for 2 and a novel dinuclear 2D layer for 3. These diverse architectures prove that coordination geometry of metal ions, coordination modes of carboxylate groups and the rotationally flexible CH2 linker played significant roles in the construction of CPs; moreover, they also indicated that H3CbdcpCl is an ideal organic candidate for the building of novel structures. The solid-state luminescent properties of complexes 1–3 were investigated, respectively. In addition, the magnetic properties of 2 and 3 were studied and both of them exhibit antiferromagnetic behaviors.

  9. Tellurium rings as electron pair donors in cluster compounds and coordination polymers; Tellurringe als Elektronenpaardonoren in Clusterverbindungen und Koordinationspolymeren

    Energy Technology Data Exchange (ETDEWEB)

    Guenther, Anja

    2011-11-08

    In this dissertation novel and already known molecular tellurium rings are presented in cluster compounds and quasi-one-dimensional coordination polymers. The cyclic, homonuclear units are always stabilized by coordination to electron-rich transition metal atoms, with the coordinating tellurium atoms acting as two-electron donors. As a synthesis route, the solid-state reaction in quartz glass vials was used uniformly. In addition to structural determination, the focus was on the characterization of the resulting compounds. For this purpose, resistance measurements were carried out on selected compounds, the magnetic behavior and the thermal degradation reactions were investigated and accompanying quantum chemical calculations were carried out. [German] In dieser Dissertation werden neuartige sowie bereits bekannte molekulare Tellurringe in Clusterverbindungen und quasi-eindimensionalen Koordinationspolymeren vorgestellt. Die Stabilisierung der zyklischen, homonuklearen Einheiten erfolgt dabei stets durch die Koordination an elektronenreiche Uebergangsmetallatome, wobei die koordinierenden Telluratome gegenueber diesen als Zwei-Elektronendonoren fungieren. Als Syntheseroute wurde dabei einheitlich auf die Festkoerperreaktion in Quarzglasampullen zurueckgegriffen. Neben der Strukturaufklaerung stand die Charakterisierung der erhaltenden Verbindungen im Fokus der Arbeit. Dazu wurden an ausgewaehlten Verbindungen Widerstandsmessungen durchgefuehrt, das magnetische Verhalten sowie die thermischen Abbaureaktionen untersucht und begleitende quantenchemische Rechnungen durchgefuehrt.

  10. Synthesis of Biocompatible Nanoparticulate Coordination Polymers for Diagnostic and Therapeutic Applications

    Science.gov (United States)

    Kandanapitiye, Murthi S.

    The combination of nanotechnology with medicinal chemistry has developed into a burgeoning research area. Nanomaterials (NMs) could be seamlessly interfaced with various facets in biology, biochemistry, medicinal chemistry and environmental chemistry that may not be available to the same material in the bulk scale. This dissertation research has focused on the development of nanoparticulate coordination polymers for diagnostic and therapeutic applications. Modern imaging techniques include X-ray computed tomography (CT), magnetic resonance imaging (MRI), single photon emission computed tomography (SPECT) and positron emission tomography (PET). We have successfully developed several types of nanoparticulate diagnostics and therapeutics that have some potential usefulness in biomedicine. Synthesis and characterization of nanoparticulate based PET (Positron emission tomography)/SPECT (Single photon emission computed tomography) are discussed in chapter 3. In chapter 4, preparation and potential utility of non-gadolinium based MRI contrast agent are reported for T1-weighted application. As far as the solely effectiveness of relaxation is concerned, Gd-based T 1-weighted MRI contrast agents have excellent enhancement of image contrast but they have risks of biological toxicity. Consequently, the search for T 1-weighted CAs with high efficacy and low toxicity has gained attention toward the Mn(II) and Fe(III). Fe(III) is considered to be more toxic to cells because free ferric or ferrous ions can catalyze the production of reactive oxygen species via the Fenton reactions. Paramagnetic chelates of Mn(II) could be employed as T1-weighted CAs. However, it is challenging to design and synthesize highly stable Mn(II) complexes that could maintain the integrity when administered to living system. Chapter 4 describes the synthesis and utility of nanoparticulate Mn analogue of Prussian blue (K2Mn 3[FeII(CN)6]2) as an effective T1 MRI contrast agent for cellular imaging X

  11. Dimensional modulation and magnetic properties of triazole- and bis(triazole)-based copper(II) coordination polymers tuned by aromatic polycarboxylates

    International Nuclear Information System (INIS)

    Zhang, Ju-Wen; Zhao, Wei; Lu, Qi-Lin; Luan, Jian; Qu, Yun; Wang, Xiu-Li

    2014-01-01

    Five new metal–organic coordination polymers ([Cu 3 (μ 2 -OH) 2 (atrz) 2 (nph) 2 (H 2 O) 2 ]·2H 2 O) n (1), ([Cu 2 (μ 3 -OH)(atrz)(1,2,4-btc)]·2H 2 O) n (2), ([Cu 2 (μ 3 -OH)(atrz)(1,2,4-btc)(H 2 O)]·H 2 O) n (3), [Cu(dth) 0.5 (nph)(H 2 O)] n (4) and [Cu(dth)(Hnip) 2 ] n (5) [atrz=4-amino-1,2,4-triazole, dth=N,N'-di(4H-1,2,4-triazole)hexanamide, H 2 nph=3-nitrophthalic acid, 1,2,4-H 3 btc=1,2,4-benzenetricarboxylic acid and H 2 nip=5-nitroisophthalic acid] were hydrothermally synthesized and structurally characterized. Polymer 1 shows a one-dimensional (1D) chain. Polymers 2 and 3 exhibit similar tetranuclear Cu II 4 cluster-based three-dimensional (3D) frameworks with the same components. Polymer 4 possesses a 3D framework with a 4 12 ·6 3 -pcu topology. Polymer 5 displays a 3D framework with a 4 4 ·6 10 ·8-mab topology. The magnetic properties of 1–4 were investigated. - Graphical abstract: Five triazole-based copper(II) polymers modulated by polycarboxylates were synthesized. Bis-triazole-bis-amide ligand and polycarboxylates play important roles in tuning dimensionality of polymers. Magnetic properties of polymers were investigated. - Highlights: • Five triazole- and bis(triazole)-based copper(II) coordination polymers tuned by aromatic polycarboxylates were obtained. • The aromatic polycarboxylates have an important influence on the dimensionality of five polymers. • The magnetic properties of four polymers were investigated

  12. Zn(II) coordination polymers with flexible V-shaped dicarboxylate ligand: Syntheses, helical structures and properties

    Energy Technology Data Exchange (ETDEWEB)

    Li, Lin [School of Environment and Chemical Engineering, Nanchang Hangkong University, Nanchang 330063 (China); Liu, Chong-Bo, E-mail: cbliu@nchu.edu.cn [School of Environment and Chemical Engineering, Nanchang Hangkong University, Nanchang 330063 (China); Yang, Gao-Shan [School of Environment and Chemical Engineering, Nanchang Hangkong University, Nanchang 330063 (China); Xiong, Zhi-Qiang [Center for Analysis and Testing, Nanchang Hangkong University, Nanchang 330063 (China); Liu, Hong [School of Environment and Chemical Engineering, Nanchang Hangkong University, Nanchang 330063 (China); Wen, Hui-Liang [State Key Laboratory of Food Science and Technology, Nanchang University, Nanchang 330047 (China)

    2015-11-15

    Hydrothermal reactions of 2,2′-[hexafluoroisopropylidenebis(p-phenyleneoxy)]diacetic acid (H{sub 2}L) and zinc ions in the presence of N-donor ancillary ligands afford four novel coordination polymers, namely, [Zn{sub 2}(μ{sub 2}-OH)(μ{sub 4}-O){sub 0.5}(L)]·0.5H{sub 2}O (1), [Zn(L)(2,2′-bipy)(H{sub 2}O)] (2), [Zn{sub 3}(L){sub 3}(phen){sub 2}]·H{sub 2}O (3) and [Zn{sub 2}(L){sub 2}(4,4′-bipy)] (4) (2,2′-bipy=2,2′-bipyridine; 4,4′-bipy=4,4′-bipyridine; phen=1,10-phenanthroline). Their structures have been determined by single-crystal X-ray diffraction analyses, elemental analyses, IR spectra, powder X-ray diffraction (PXRD), and thermogravimetric (TG) analyses. Complex 1 shows a 3-D clover framework consisting of [Zn{sub 4}(µ{sub 4}-O)(µ{sub 2}-OH){sub 2}]{sup 4+} clusters, and exhibits a novel (3,8)-connected topological net with the Schläfli symbol of {3·4·5}{sub 2}{3"4·4"4·5"2·6"6·7"1"0·8"2}, and contains double-stranded and two kinds of meso-helices. 2 displays a helical chain structure, which is further extended via hydrogen bonds into a 3-D supramolecular structure with meso-helix chains. 3 displays a 2-D {4"4·6"2} parallelogram structure, which is further extended via hydrogen bonds into a 3-D supramolecular structure with single-stranded helical chains. 4 shows a 2-D {4"4·6"2} square structure with left- and right-handed helical chains. Moreover, the luminescent properties of 1–4 have been investigated. - Graphical abstract: Four new Zn(II) coordination polymers with helical structures based on flexible V-shaped dicarboxylate ligand have been synthesized and structurally characterized. Photoluminescent properties have been investigated. - Highlights: • Four novel Zn(II) coordination polymers with V-shaped ligand were characterized. • Complexes 1–4 show diverse intriguing helical characters. • Fluorescence properties of complexes 1–4 were investigated.

  13. Gas adsorption/separation properties of metal directed self-assembly of two coordination polymers with 5-nitroisophthalate

    Energy Technology Data Exchange (ETDEWEB)

    Arıcı, Mürsel [Department of Chemistry, Faculty of Arts and Sciences, Eskişehir Osmangazi University, 26480 Eskişehir (Turkey); Yeşilel, Okan Zafer, E-mail: yesilel@ogu.edu.tr [Department of Chemistry, Faculty of Arts and Sciences, Eskişehir Osmangazi University, 26480 Eskişehir (Turkey); Keskin, Seda [Department of Chemical and Biological Engineering, Koç University, İstanbul (Turkey); Şahin, Onur [Scientific and Technological Research Application and Research Center, Sinop University, 57010 Sinop (Turkey)

    2014-02-15

    Two new coordination polymers, namely, [Co(µ-nip)(µ-bpe)]{sub n} (1) and [Zn(µ-nip)(µ-bpe)]{sub n} (2) (nip: 5-nitroisophthalate, bpe: 1,2-bis(4-pyridyl)ethane) were hydrothermally synthesized and structurally characterized by single crystal X-ray diffraction, IR spectroscopy, elemental analysis and thermal analysis. Moreover, atomically detailed simulation studies of complex 2 for CO{sub 2}/CH{sub 4} adsorption and separation were performed. Complex 1 consists of two dimensional (2D) (4,4) grid networks with the point symbol of 4{sup 4}.6{sup 2}. Complex 2 exhibits a 3-fold interpenetrating 3D framework with 6{sup 5}.8-dmp topology. Thermal properties of the complexes showed that both complexes were stable over 320 °C. Simulation studies demonstrated that complex 2 can separate CO{sub 2} from CH{sub 4} at low pressures at 273 K. - Graphical abstract: In this study, two new coordination polymers, namely, [Co(µ-nip)(µ-bpe)]{sub n} (1) and [Zn(µ-nip)(µ-bpe)]{sub n} (2) (nip: 5-nitroisophthalate, bpe: 1,2-bis(4-pyridyl)ethane) were hydrothermally synthesized and structurally characterized by single crystal X-ray diffraction, IR spectroscopy, elemental analysis and thermal analysis. Moreover, atomically detailed simulation studies of complex 2 for CO{sub 2}/CH{sub 4} adsorption and separation were performed. Complex 1 consists of two dimensional (2D) (4,4) grid networks with the point symbol of 4{sup 4}.6{sup 2}. Complex 2 exhibits a 3-fold interpenetrating 3D framework with 6{sup 5}.8-dmp topology. Simulation studies demonstrated that complex 2 can separate CO{sub 2} from CH{sub 4} at low pressures at 273 K. Display Omitted - Highlights: • Two new coordination polymers with 5-nitroisophthalate and 1,2-bis(4-pyridyl)ethane. • Atomically detailed simulation studies of the complexes. • Complex 2 can be proposed as molecular sieve to separate CO{sub 2} from CH{sub 4} at low pressures.

  14. Polyacetylene-Type Networks Prepared by Coordination Polymerization of Diethynylarenes: New Type of Microporous Organic Polymers

    Czech Academy of Sciences Publication Activity Database

    Hanková, V.; Slováková, E.; Zednik, J.; Vohlídal, J.; Sivková, R.; Balcar, Hynek; Zukal, Arnošt; Brus, Jiří; Sedláček, J.

    2012-01-01

    Roč. 33, č. 2 (2012), s. 158-163 ISSN 1022-1336 R&D Projects: GA ČR(CZ) GAP108/11/1661; GA ČR GA203/08/0604; GA ČR GD203/08/H032 Institutional research plan: CEZ:AV0Z40400503; CEZ:AV0Z40500505 Keywords : adsorption * conjugated polymers * hydrogen storage Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 4.929, year: 2012

  15. Construction of copper-based coordination polymers with 1D chain ...

    Indian Academy of Sciences (India)

    bChina-Australia Joint Research Center for Functional Molecular Materials, School of Chemical and Material. Engineering, Jiangnan ..... grids and are packed in parallel fashion in the crystal lattice (figure 3d). Owing to the position of pyridyl-N and N-coordinated distance of 3,3'-bptz and 4,4'-bptz ligands, the 2D pattern and ...

  16. coordination polymers based on semi-rigid/flexible bis-pyridyl-bis ...

    Indian Academy of Sciences (India)

    pounds with intriguing structures and desired proper- ties have been successfully prepared by hydrothermal method.4–6 Although many factors can affect the ulti- mate structures of coordination compounds, the selec- tion of suitable organic ligands plays a crucial role.7–9. Among the diverse organic ligands, the analogs of.

  17. Solvent-free porous framework resulted from 3D entanglement of 1D zigzag coordination polymer

    KAUST Repository

    Kole, Goutam Kumar Umar

    2010-01-01

    A solvent-free porous metal organic framework is constructed by the 3D entanglement of 1D zigzag coordination polymeric chains. The role of solvents and the effect of reaction conditions on such unique entanglement are addressed. © 2010 The Royal Society of Chemistry and the Centre National de la Recherche Scientifique.

  18. A novel Mn(II) oxalato-bridged 2D coordination polymer: synthesis ...

    Indian Academy of Sciences (India)

    Hiba Sehimi

    2018-02-28

    Feb 28, 2018 ... o-phthalic acid5 and carboxylic acid,6 due to their excel- lent coordinating ability. And among this wide variety of ligands, the oxalate ion was proven to be ..... ganic Crystal Structure Database Acta Crystallogr., Sect. B 41 244. 30. Lethbridge Z A D, Congreve A F, Esslemont E, Slawin. A M Z and Lightfoot P ...

  19. Hand-Ground Nanoscale ZnII -Based Coordination Polymers Derived from NSAIDs: Cell Migration Inhibition of Human Breast Cancer Cells.

    Science.gov (United States)

    Paul, Mithun; Sarkar, Koushik; Deb, Jolly; Dastidar, Parthasarathi

    2017-04-27

    Increased levels of intracellular prostaglandin E 2 (PGE 2 ) have been linked with the unregulated cancer cell migration that often leads to metastasis. Non-steroidal anti-inflammatory drugs (NSAIDs) are known inhibitors of cyclooxygenase (COX) enzymes, which are responsible for the increased PGE 2 concentration in inflamed as well as cancer cells. Here, we demonstrate that NSAID-derived Zn II -based coordination polymers are able to inhibit cell migration of human breast cancer cells. Various NSAIDs were anchored to a series of 1D Zn II coordination polymers through carboxylate-Zn coordination, and these structures were fully characterized by single-crystal X-ray diffraction. Hand grinding in a pestle and mortar resulted in the first reported example of nanoscale coordination polymers that were suitable for biological studies. Two such hand-ground nanoscale coordination polymers NCP1 a and NCP2 a, which contained naproxen (a well-studied NSAID), were successfully internalized by the human breast cancer cells MDA-MB-231, as was evident from cellular imaging by using a fluorescence microscope. They were able to kill the cancer cells (MTT assay) more efficiently than the corresponding mother drug naproxen, and most importantly, they significantly inhibited cancer cell migration thereby displaying anticancer activity. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  20. Synthesis, Structural Characterization, and Antitumor Activity of a Ca(II Coordination Polymer Based on 1,6-Naphthalenedisulfonate and 4,4′-Bipyridyl

    Directory of Open Access Journals (Sweden)

    Xishi Tai

    2013-08-01

    Full Text Available A novel Ca(II coordination polymer, [CaL(4,4′-bipyridyl(H2O4]n (L = 1,6-naphthalenedisulfonate, was synthesized by reaction of calcium perchlorate with 1,6-naphthalenedisulfonic acid disodium salt and 4,4′-bipyridyl in CH3CH2OH/H2O. It was characterized by elemental analysis, IR, molar conductivity and thermogravimetric analysis. X-ray crystallography reveals that the Ca(II coordination polymer belongs to the orthorhombic system, with space group P212121. The geometry of the Ca(II ion is a distorted CaNO6 pengonal bipyramid, arising from its coordination by four water molecules, one nitrogen atom of 4,4′-bipyridyl molecule, and two oxygen atoms from two L ligands. The complex molecules form a helical chain by self-assembly. The antitumor activity of 1,6-naphthalenedisulfonic acid disodium salt and the Ca(II coordination polymer against human hepatoma smmc-7721 cell line and human lung adenocarcinoma A549 cell line reveals that the Ca(II coordination polymer inhibits cell growth of human lung adenocarcinoma A549 cell line with IC50 value of 27 μg/mL, and is more resistive to human lung adenocarcinoma A549 cell line as compared to 1,6-naphthalenedisulfonic acid disodium salt.

  1. Ionothermal Synthesis of a Novel 3D Cobalt Coordination Polymer with a Uniquely Reported Framework: [BMI]2[Co2(BTC2(H2O2

    Directory of Open Access Journals (Sweden)

    Il-Ju Ko

    2017-01-01

    Full Text Available The framework of [RMI]2[Co2(BTC2(H2O2] (RMI = 1-alkyl-3-methylimidazolium, alkyl; ethyl (EMI; propyl (PMI; butyl (BMI, which has uniquely occurred in ionothermal reactions of metal salts and H3BTC (1,3,5-benzenetricarboxylic acid, an organic ligand, reappeared in this work. Ionothermal reaction of cobalt acetate and H3BTC with [BMI]Br ionic liquid as the reaction medium yielded the novel coordination polymer [BMI]2[Co2(BTC2(H2O2] (compound B2. Similar ionothermal reactions with different [EMI]Br and [PMI]Br as the reaction media have been previously reported to produce [EMI]2[Co3(BTC2(OAc2] (compound A1 and [PMI]2[Co2(BTC2(H2O2] (compound B1, respectively. In contrast with the trinuclear secondary building unit of A1, the framework structure of B1 and B2 consists of dinuclear secondary building units in common, but with subtle distinction posed by the different size of the incorporated cations. These structural differences amidst the frameworks showed interesting aspects, including guest and void volume, and were used to explain the chemical trend observed in the system. Moreover, the physicochemical properties of the newly synthesized compound have been briefly discussed.

  2. Tunable white-light emission PMMA-supported film materials containing lanthanide coordination polymers: preparation, characterization, and properties.

    Science.gov (United States)

    Chen, Wei; Fan, Ruiqing; Zhang, Huijie; Dong, Yuwei; Wang, Ping; Yang, Yulin

    2017-03-27

    A series of lanthanide coordination polymers(LnCPs) containing both light and heavy rare-earth elements, namely {[Eu 2 (pydc) 3 (H 2 O)]·2H 2 O} n (1-Eu, H 2 pydc = pyridine-2,3-dicarboxylic acid), [Ln(pyc) 2 (Hpyc)(NO 3 )] n (Ln = Nd (2-Nd), Sm (3-Sm), Eu (4-Eu), Gd (5-Gd), Tb (6-Tb), Ho (7-Ho), and Er (8-Er), Hpyc = pyridine-3-carboxylic acid), has been synthesized under hydro(solvo)thermal conditions and fully characterized. The crystal structure analysis indicates that in situ decarboxylation of H 2 pydc occurred in the synthesis process of 2-Nd-8-Er. Coordination polymer 1-Eu displays a 3-D pcu network with central-symmetric quad-core structural units [Eu 4 (COO) 6 ] linked by 1-D chains. 2-Nd-8-Er are of triple helical chain enantiomeric pair 6 1 /6 5 axis, and can be further linked through two separate kinds of Hbonding interaction to form a mirror symmetrical 3-D framework; the final topological symbol of the jointly connected network is rare {4 7 ·6 8 }. Solid-state luminescence studies show that the emission spectra of these LnCPs cover both the visible and near-infrared luminescence region. 2-Nd exhibits characteristic 4 F 3/2 → 4 I J/2 (J = 9, 11, 13) transition NIR emission. 1-Eu and 4-Eu provide characteristic 5 D 0 → 7 F J intense and bright red luminescence, while 4-Eu exhibits better luminescence performance because of the presence of the O-H oscillators within 1-Eu. 6-Tb exhibits characteristic 5 D 4 → 7 F J intense and bright green luminescence. Furthermore, through doping with PMMA polymer, the luminescence properties of 4-Eu and 6-Tb are all improved. The results show the best doping concentration is 4%. The thermal stabilities of 4-Eu-PMMA and 6-Tb-PMMA increased from 270 to 315 °C when compared with single coordination polymers 4-Eu and 6-Tb. The co-doping of 4-Eu, 5-Gd, and 6-Tb (0.92/0.04/0.04) with PMMA at a total concentration of 4% resulted in a tunable luminescence material W ( 4-Eu , 5-Gd , 6-Tb ) -PMMA film. When excited at

  3. Effects of different factors on the formation of nanorods and nanosheets of silver(I) coordination polymer

    Science.gov (United States)

    Shahangi Shirazi, Fatemeh; Akhbari, Kamran; Kawata, Satoshi; Ishikawa, Ryuta

    2016-11-01

    In order to evaluation the effects of solvent, concentration of initial reagents and ultrasonic irradiations on formation different morphologies of [Ag2(pta)(H2O)]n (1), [H2pta = phthalic acid], nanostructures, we design some experiments and synthesized six sample of 1 under different conditions. nanorods and nanosheets of a silver(I) coordination polymer, were synthesized under these conditions. These nanostructures were characterized by scanning electron microscopy, X-ray powder diffraction, IR spectroscopy and elemental analyses. If we arrange the order of these three factors upon their importance in formation compound 1 nanostructures, first we can select the type of solvent as the effective factor, then the concentration of initial reagents and finally the existence of ultrasonic irradiation which can change the morphology of 1 in low concentration of initial reagents. Thermal stability of these six samples was also studied by thermo gravimetric (TG) and differential thermal analyses (DTA).

  4. Microwave-Assisted Synthesis of Nanoporous Aluminum-Based Coordination Polymers as Catalysts for Selective Sulfoxidation Reaction

    Directory of Open Access Journals (Sweden)

    Madhan Vinu

    2017-10-01

    Full Text Available A series of aluminum-based coordination polymers or metal–organic frameworks (Al–MOFs, i.e., DUT-4, DUT-5, MIL-53, NH2-MIL-53, and MIL-100, have been facile prepared by microwave (MW-assisted reactions and used as catalysts for selective sulfoxidation reactions. The MW-assisted synthesis drastically reduced the reaction time from few days to hours. The prepared MOFs have smaller and uniform particle sizes and better yield compared to conventional hydrothermal method. Furthermore, the Al–MOFs have been successfully demonstrated as catalysts in oxidation reaction of methyl phenyl sulfide with H2O2 as oxidant, even under mild conditions, with more than 95% conversion.

  5. Highly Polarizable Triiodide Anions (I3(-)) as Cross-Linkers for Coordination Polymers: Closing the Semiconductive Band Gap.

    Science.gov (United States)

    He, Jun; Cao, Peng; Wu, Chao; Huang, Jiahong; Huang, Jian; He, Yonghe; Yu, Lin; Zeller, Matthias; Hunter, Allen D; Xu, Zhengtao

    2015-07-06

    From a hydrothermal reaction using CuI, KI, and 3,3'5,5'-tetramethyl-4,4'-bipyrazole (TMBP), the triiodide anion I3(-) has been integrated into the water-stable 2D coordination polymer Cu(TMBP)I3 (1). In contrast with other metal triiodide complexes, 1 features remarkably small distortions in the bond distances associated with the I3(-) units (i.e., the Cu-I and I-I bonds), which effectively link up the copper(I) centers into infinite CuI3 chains. The electronic band gaps and electrical conductivity data are also found to be consistent with the I3(-) ion acting as an effective linker across the copper(I) centers.

  6. Coordination polymer-derived nano-sized zinc ferrite with excellent performance in nitro-explosive detection.

    Science.gov (United States)

    Singha, Debal Kanti; Mahata, Partha

    2017-08-29

    Herein, a mixed metal coordination polymer, {(H 2 pip)[Zn 1/3 Fe 2/3 (pydc-2,5) 2 (H 2 O)]·2H 2 O} 1 {where H 2 pip = piperazinediium and pydc-2,5 = pyridine-2,5-dicarboxylate}, was successfully synthesized using a hydrothermal technique. To confirm the structure and phase purity of 1, single crystals of an isomorphous pure Fe compound, {(H 2 pip)[Fe(pydc-2,5) 2 (H 2 O)]·2H 2 O} 1a, were synthesized based on similar synthetic conditions. Single crystal X-ray data of 1a confirmed the one-dimensional anionic metal-organic coordination polymer hydrogen bonded with protonated piprazine (piperazinediium) and lattice water molecules. The phase purity of 1 and 1a were confirmed via powder X-ray diffraction. Compound 1 was systematically characterized using IR, TGA, SEM, and EDX elemental mapping analysis. Compound 1 was used as a single source precursor for the preparation of nano-sized ZnFe 2 O 4 via thermal decomposition. The as-obtained ZnFe 2 O 4 was fully characterized using PXRD, SEM, TEM, and EDX elemental mapping analysis. It was found that ZnFe 2 O 4 was formed in its pure form with particle size in the nano-dimension. The aqueous dispersion of nano-sized ZnFe 2 O 4 exhibits a strong emission at 402 nm upon excitation at 310 nm. This emissive property was employed for luminescence-based detection of nitroaromatic explosives in an aqueous medium through luminescence quenching for the first time. Importantly, selective detections have been observed for phenolic nitroaromatics based on differential luminescence quenching behaviour along with a detection limit of 57 ppb for 2,4,6-trinitrophenol (TNP) in water.

  7. Hydrothermal synthesis and crystal structure of a new lanthanum(III coordination polymer with fumaric acid

    Directory of Open Access Journals (Sweden)

    Hayet Anana

    2015-05-01

    Full Text Available The title compound, poly[diaquatris(μ4-but-2-enedioato(μ2-but-2-enedioic aciddilanthanum(III], [La2(C4H2O43(C4H4O4(H2O2]n, was synthesized by the reaction of lanthanum chloride pentahydrate with fumaric acid under hydrothermal conditions. The asymmetric unit comprises an LaIII cation, one and a half fumarate dianions (L2−, one a half-molecule of fumaric acid (H2L and one coordinated water molecule. Each LaIII cation has the same nine-coordinate environment and is surrounded by eight O atoms from seven distinct fumarate moieties, including one protonated fumarate unit and one water molecule in a distorted tricapped trigonal–prismatic environment. The LaO8(H2O polyhedra centres are edge-shared through three carboxylate bridges of the fumarate ligand, forming chains in three dimensions to construct the MOF. The crystal structure is stabilized by O—H...O hydrogen-bond interactions between the coordinated water molecule and the carboxylate O atoms, and also between oxygen atoms of fumaric acid

  8. BSA-assisted synthesis of ultrasmall gallic acid–Fe(III) coordination polymer nanoparticles for cancer theranostics

    Science.gov (United States)

    Mu, Xueling; Yan, Chenglin; Tian, Qiwei; Lin, Jiaomin; Yang, Shiping

    2017-01-01

    Protein-related nanotheranostic agents hold great promise as tools to serve many clinical applications. Proteins such as BSA are used to regulate the synthesis of nondegradable inorganic nanoparticles (NPs). To fully employ the potential of such proteins, a new type of biosafe nanotheranostic agent must be designed to optimize BSA as a biomineralization agent. Here, a straightforward BSA-assisted biomineralization method was developed to prepare gallic acid (GA)–Fe(III) coordination polymer NPs. BSA-coated GA-Fe (GA-Fe@BSA) NPs were ultrasmall (3.5 nm) and showed good biocompatibility, a lower r2:r1 ratio (1.06), and strong absorption in the visible near-infrared region. T1-weighted magnetic resonance imaging of tumor-bearing mice before and after intratumoral injection with GA-Fe@BSA NPs definitively demonstrated positive change. In a subsequent in vivo study, antitumor activity was precipitated by intratumoral injection of GA-Fe@BSA NPs combined with laser treatment, suggesting excellent outcomes with this treatment method. These results describe a successful protocol in which BSA regulated the synthesis of benign organic polymer NPs. GA-Fe@BSA NPs have the potential to be ideal agents to be used in clinical theranostic nanoplatforms. PMID:29042770

  9. BSA-assisted synthesis of ultrasmall gallic acid-Fe(III) coordination polymer nanoparticles for cancer theranostics.

    Science.gov (United States)

    Mu, Xueling; Yan, Chenglin; Tian, Qiwei; Lin, Jiaomin; Yang, Shiping

    2017-01-01

    Protein-related nanotheranostic agents hold great promise as tools to serve many clinical applications. Proteins such as BSA are used to regulate the synthesis of nondegradable inorganic nanoparticles (NPs). To fully employ the potential of such proteins, a new type of biosafe nanotheranostic agent must be designed to optimize BSA as a biomineralization agent. Here, a straightforward BSA-assisted biomineralization method was developed to prepare gallic acid (GA)-Fe(III) coordination polymer NPs. BSA-coated GA-Fe (GA-Fe@BSA) NPs were ultrasmall (3.5 nm) and showed good biocompatibility, a lower r 2 : r 1 ratio (1.06), and strong absorption in the visible near-infrared region. T 1 -weighted magnetic resonance imaging of tumor-bearing mice before and after intratumoral injection with GA-Fe@BSA NPs definitively demonstrated positive change. In a subsequent in vivo study, antitumor activity was precipitated by intratumoral injection of GA-Fe@BSA NPs combined with laser treatment, suggesting excellent outcomes with this treatment method. These results describe a successful protocol in which BSA regulated the synthesis of benign organic polymer NPs. GA-Fe@BSA NPs have the potential to be ideal agents to be used in clinical theranostic nanoplatforms.

  10. Flexible porous coordination polymer of Ni(II) for developing nanoparticles through acid formation and redox activity of the framework

    Science.gov (United States)

    Agarwal, Rashmi A.

    2017-10-01

    Immobilization of the nanoparticles (NPs) in a two dimensional porous coordination polymer (PCP) is currently an emerging field for a number of applications. But still it is a great challenge to fabricate any specified metal NPs in a single network. Herein the synthesis of Au, Pd, Mn, Fe, Cu, Zn, Mg, Li, Fe/Cu, Zn/Mg etc, NPs in a highly flexible PCP of Ni(II); {[Ni3(TBIB)2(BTC)2(H2O)6]·5C2H5OH·9H2O}n [TBIB = 1,3,5-tri(1H-benzo[d]imidazol-1-yl)benzene, H3BTC = 1,3,5-benzenetricarboxylic acid] have been reported. This universal host is able to grow mixed metal NPs from mixed metal precursors. Monodentate carboxylate groups of BTC linker act as anchoring sites for the metal ions of the metal precursors. This is the main driving force to grow NPs within the cavities along with the high flexibility of this polymer at room temperature. Mechanism involves acid formation followed by redox reaction to synthesize metal NPs explained by EPR and FTIR. Paramagnetic properties have been shown by as-synthesized Fe NPs integrated framework at room temperature under applied magnetic field up to 17,500 Oe.

  11. Enhancement of proton conduction at low humidity by incorporating imidazole microcapsules into polymer electrolyte membranes

    Energy Technology Data Exchange (ETDEWEB)

    Wang, Jingtao; Yue, Xiujun; Zhang, Zizhuo; Yang, Zheng; Li, Yifan; Wu, Hong; Jiang, Zhongyi [Key Laboratory for Green Chemical Technology, Ministry of Education, School of Chemical Engineering and Technology, Tianjin University, Tianjin 300072 (China); Zhang, Han; Yang, Xinlin [Key Laboratory of Functional Polymer Materials, Ministry of Education, Institute of Polymer Chemistry, Nankai University, Tianjin 300071 (China)

    2012-11-07

    Design and fabrication of hierarchically structured membranes with high proton conductivity is crucial to many energy-relevant applications including proton exchange membrane fuel cell (PEMFC). Here, a series of imidazole microcapsules (IMCs) with tunable imidazole group loading, shell thickness, and lumen size are synthesized and incorporated into a sulfonated poly(ether ether ketone) (SPEEK) matrix to prepare composite membranes. The IMCs play two roles: i) Improving water retention properties of the membrane. The IMCs, similar to the vacuoles in plant cells, can render membrane a stable water environment. The lumen of the IMCs acts as a water reservoir and the shell of IMCs can manipulate water release. ii) They form anhydrous proton transfer pathways and low energy barrier pathways for proton hopping, imparting an enhanced proton transfer via either a vehicle mechanism or Grotthuss mechanism. In particular, at the relative humidity (RH) as low as 20%, the composite membrane exhibits an ultralow proton conductivity decline and the proton conductivity is one to two orders of magnitude higher than that of SPEEK control membrane. The enhanced proton conductivity affords the composite membrane an elevated peak power density from 69.5 to 104.5 mW cm{sup -2} in a single cell. Moreover, the application potential of the composite membrane for CO{sub 2} capture is explored. (Copyright copyright 2012 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

  12. The Significance of Incorporating Nanoscale Fluctuations in a Constitutive Description of Glassy Polymers

    Science.gov (United States)

    Caruthers, James

    2015-03-01

    The current picture of the glass involves dynamic heterogeneity, where nanoscopic regions of the glass have order-of-magnitude differences in local mobility that evolve with time. Dynamic heterogeneity provides a critical challenge to the traditional nonlinear continuum models, where both temporal and spatial fluctuations are averaged as a result of the continuum postulate. In order to acknowledge dynamic heterogeneity, a Stochastic Constitutive Model (SCM) has been developed to describe the nonlinear viscoelastic behavior of polymeric glasses, where (i) temporal fluctuations are explicitly included and (ii) the local mobility depends upon the local state of the material (e.g. local stress and local entropy) vs. traditional viscoelastic/viscoelastic models where macroscopic mobility depends upon the macroscopic state. The SCM is able to describe a number of nonlinear relaxation phenomena that cannot be predicted by traditional nonlinear viscoelastic/viscoplastic models, including (i) post-yield stress softening and its dependence on annealing time, (ii) the inversion of the strain dependence of nonlinear stress relaxation with the loading rate, (iii) stress memory and (iv) tertiary creep and creep-recovery. This paper will argue that incorporation of nanoscopic fluctuations is a necessary component for a description of the thermomechanical behavior of polymeric glasses. Support from NSF Grant 1363326-CMMI.

  13. Structural variability in Cu(I) and Ag(I) coordination polymers with a flexible dithione ligand: Synthesis, crystal structure, microbiological and theoretical studies

    Energy Technology Data Exchange (ETDEWEB)

    Beheshti, Azizolla, E-mail: a.beheshti@scu.ac.ir [Department of Chemistry, Faculty of Sciences, Shahid Chamran University of Ahvaz, Ahvaz (Iran, Islamic Republic of); Nozarian, Kimia; Babadi, Susan Soleymani; Noorizadeh, Siamak [Department of Chemistry, Faculty of Sciences, Shahid Chamran University of Ahvaz, Ahvaz (Iran, Islamic Republic of); Motamedi, Hossein [Department of Biology, Faculty of Sciences, Shahid Chamran University of Ahvaz, Ahvaz (Iran, Islamic Republic of); Mayer, Peter [LMU München Department Chemie, Butenandtstr 5-13, D-81377 München (Germany); Bruno, Giuseppe [Dipartimento di Chimica Inorganica, Università di Messina, Vill. S. Agata, Salita Sperone 31, 98166 Messina (Italy); Rudbari, Hadi Amiri [Faculty of Chemistry, University of Isfahan, Isfahan 81746-73441 (Iran, Islamic Republic of)

    2017-05-15

    Two new compounds namely [Cu(SCN)(µ-L)]{sub n} (1) and ([Ag (µ{sub 2}-L)](ClO{sub 4})){sub n} (2) have been synthesized at room temperature by one-pot reactions between the 1,1-(1,4-butanediyl)bis(1,3-dihydro-3-methyl-1H-imidazole- 2-thione) (L) and appropriate copper(I) and silver(I) salts. These polymers have been characterized by single crystal X-ray diffraction, XRPD, TGA, elemental analysis, infrared spectroscopy, antibacterial activity and scanning probe microscopy studies. In the crystal structure of 1, copper atoms have a distorted trigonal planar geometry with a CuS{sub 2}N coordination environment. Each of the ligands in the structure of 1 acting as a bidentate S-bridging ligand to form a 1D chain structure. Additionally, the adjacent 1D chains are interconnected by the intermolecular C-H…S interactions to create a 2D network structure. In contrast to 1, in the cationic 3D structure of 2 each of the silver atoms exhibits an AgS{sub 4} tetrahedral geometry with 4-membered Ag{sub 2}S{sub 2} rings. In the structure of 2, the flexible ligand adopts two different conformations; gauche-anti-gauche and anti-anti-anti. The antibacterial studies of these polymers showed that polymer 2 is more potent antibacterial agent than 1. Scanning probe microscopy (SPM) study of the treated bacteria was carried out to investigate the structural changes cause by the interactions between the polymers and target bacteria. Theoretical study of polymer 1 investigated by the DFT calculations indicates that observed transitions at 266 nm and 302 nm in the UV–vis spectrum could be attributed to the π→π* and MLCT transitions, respectively. - Graphical abstract: Two new Cu(I) and Ag(I) coordination polymers have been have been synthesized by one-pot reactions. Copper complex has a 2D non-covalent structure, but silver compound is a 3D coordination compound. These compounds have effective antibacterial activity. - Highlights: • Cu(I) and Ag(I) based coordination polymers

  14. High Anodic Performance of Co 1,3,5-Benzenetricarboxylate Coordination Polymers for Li-Ion Battery.

    Science.gov (United States)

    Li, Chao; Lou, Xiaobing; Shen, Ming; Hu, Xiaoshi; Guo, Zhi; Wang, Yong; Hu, Bingwen; Chen, Qun

    2016-06-22

    We report the designed synthesis of Co 1,3,5-benzenetricarboxylate coordination polymers (CPs) via a straightforward hydrothermal method, in which three kinds of reaction solvents are selected to form CPs with various morphologies and dimensions. When tested as anode materials in Li-ion battery, the cycling stabilities of the three CoBTC CPs at a current density of 100 mA g(-1) have not evident difference; however, the reversible capacities are widely divergent when the current density is increased to 2 A g(-1). The optimized product CoBTC-EtOH maintains a reversible capacity of 473 mAh g(-1) at a rate of 2 A g(-1) after 500 galvanostatic charging/discharging cycles while retaining a nearly 100% Coulombic efficiency. The hollow microspherical morphology, accessible specific area, and the absence of coordination solvent of CoBTC-EtOH might be responsible for such difference. Furthermore, the ex situ soft X-ray absorption spectroscopy studies of CoBTC-EtOH under different states-of-charge suggest that the Co ions remain in the Co(2+) state during the charging/discharging process. Therefore, Li ions are inserted to the organic moiety (including the carboxylate groups and the benzene ring) of CoBTC without the direct engagement of Co ions during electrochemical cycling.

  15. Syntheses, structures, luminescence, and magnetic properties of one-dimensional lanthanide coordination polymers with a rigid 2,2'-bipyridine-3,3',6,6'-tetracarboxylic acid ligand.

    Science.gov (United States)

    Ji, Baoming; Deng, Dongsheng; He, Xiao; Liu, Bin; Miao, Shaobin; Ma, Ning; Wang, Weizhou; Ji, Liguo; Liu, Peng; Li, Xianfei

    2012-02-20

    A series of novel one-dimensional (1-D) lanthanide coordination polymers (CPs), with the general formula {[Ln(bptcH)(H(2)O)(2)]·H(2)O}(n) (Ln = Nd(III) (1), Eu(III) (2), Gd(III) (3), Tb(III) (4), Dy(III) (5), Ho(III) (6), or Er(III) (7)) have been synthesized by the solvothermal reactions of the corresponding lanthanide(III) picrates and 2,2'-bipyridine-3,3',6,6'-tetracarboxylic acid (bptcH(4)). These polymers have been structurally characterized by single-crystal X-ray diffraction, IR, PXRD, thermogravimetric (TGA), and elemental analysis. Coordination polymers 1-7 are isostructural; they possess the same 3D supramolecular architectures and crystallize in triclinic space group P1̅. The frameworks constructed from dinuclear lanthanide building blocks exhibit one-dimensional double-stranded looplike chain architectures, in which the bptcH(3-) ions adopted hexadentate coordination modes. The Eu(III) (2) and Tb(III) (4) polymers exhibit characteristic photoluminescence in the visible region. The magnetic properties of polymers 2, 3, and 5 have been investigated through the measurement of their magnetic susceptibilities over the temperature range of 1.8-300 K.

  16. Application of a novel red-emitting cationic iridium(III) coordination polymer in warm white light-emitting diodes

    Science.gov (United States)

    Chen, Mingxian; Sun, Riyong; Ye, Yanchun; Tang, Huaijun; Dong, Xueyan; Yan, Jialun; Wang, Kaimin; Zhou, Qiang; Wang, Zhengliang

    2018-02-01

    A novel red-emitting cationic iridium(III) coordination polymer using 2-(9-(2-ethylhexyl)-9H-carbazol-3-yl)benzo[d]thiazole as main ligands, 4,4‧-bipyridine as bridging auxiliary ligands and Clˉ as anions was synthesized. It had high thermal stability with a thermal decomposition temperature (Td) of 345 °C and low thermal quenching with an activation energy (Ea) of 0.2760 eV, with the temperature increasing from 20 °C to 100 °C, its photoluminescent intensity decreased to 76.7%. It can be efficiently excited by blue light of GaN chips, the cold white light of GaN-based LEDs using only Y3Al5O12:Ce3+ (YAG:Ce, 7.0 wt% in silicone) as phosphors can become warmer when it was blended in. When blending concentrations were 0.1 wt% and 0.2 wt%, the cold white light became neutral white light, the correlated color temperature (CCT) decreased from 6157 K to 5240 K, then to 4043 K, the color rendering index (CRI) changed from 72.7 to 81.3, then to 78.6, the luminous efficiency (ηL) changed from 134.1 lm·w-1 to 61.9 lm·w-1, then to 46.3 lm·w-1, the Commission Internationale de L'Eclairage (CIE) chromaticity coordinates changed from (0.32, 0.33) to (0.34, 0.33), then to (0.38, 0.36). At 0.3 wt%, the light became warm white light, the corresponding CCT was 3475 K, CRI was 75.6, ηL was 36.9 lm·w-1, and CIE value was (0.41, 0.40). The results suggest the coordination polymer is a promising red-emitting phosphor candidate for neutral and warm white LEDs, especially for warm white LEDs.

  17. COORDINATION COMPOUNDS OF OXOVANADIUM(IV BASED ON S-METHYLISOTHIOSEMICARBAZIDE AS DYES FOR THERMOPLASTIC POLYMERS

    Directory of Open Access Journals (Sweden)

    Maria Cocu

    2015-12-01

    Full Text Available We have investigated the properties as dyes of coordination compounds synthesized by us previously (8-(1',2'-naphthyl-1-R-3-methyl-6-thiomethyl-4,5,7-triazanona-1,3,5,7-tetraenato-1,1'-diolato(--O1, O1', N4, N7-vanadil, where R=CH3 (1 , C6H5 (2, which can be used for colouring thermoplastic masses. The compounds have a high photostability (7 points, thermostability (>250° and an intensity of colour that give a low consumption (0.006-0.010g.

  18. Cu(II) coordination polymers constructed by tetrafluoroterephthalic acid and varied imidazole-containing ligands: Syntheses, structures and properties

    Science.gov (United States)

    Liu, Kang; Sun, Yayong; Deng, Liming; Cao, Fan; Han, Jishu; Wang, Lei

    2018-02-01

    Six new copper(II) coordination polymers combining 2,3,5,6-tetrafluoroterephthalatic acid (H2tfBDC) and diverse imidazole-containing ligands, {[Cu(tfBDC)(1,2-bix)2]·2(H2O)}n (1), {Cu(tfBDC)(Im)2}n (2), {[Cu(1,4-bmimb)2(H2O)]·(tfBDC)·2(H2O)}n (3), {Cu(1,4-bimb)2(H2O)2·(tfBDC)}n (4), {[Cu(1,3-bix)2(H2O)2]·(tfBDC)·6(H2O)}n (5) and {[Cu(1,4-bix)2(H2O)2]·(tfBDC)·(1,4-bix)·4(H2O)}n (6) (1,2-bix = 1,2-bis(imidazole-1-ylmethyl)-benzene, Im = imidazole, 1,4-bmimb = 1,4-bis((2-methyl-1H-imidazol-1-yl)methyl)benzene, 1,4-bimb = 1,4-bis(imidazol-1-yl)-butane, 1,3-bix = 1,3-bis(imidazole-1-ylmethyl)-benzene, 1,4-bix = 1,4-bis(imidazole-1-ylmethyl)-benzene), have been obtained and structurally verified by single-crystal X-ray diffraction analyses and further characterized by powder X-ray diffraction (PXRD), elemental analyses and infrared spectroscopy (IR). Single crystal X-ray diffraction analysis revealed that 1 is 2D 4-connected sql topology (point symbol: {44·62}) based on a single metal ion node. Compound 2 is characterized as an infinite 1D chain structure, which is further extended into a 2D layer through N-H···O hydrogen bonds and then a 3D supramolecular architecture via π···π stacking interactions. Note that 2 was prepared through an in situ ligand reaction in which N,N'-carbonyldiimidazole (cdi) broke up into imidazole ligand. Compound 3 possesses a 3D 4-fold interpenetrated architecture with 4-connected dia topology (Schläfli symbol: {66}) in which tfBDC2- is stabilized in the channel by hydrogen bonds. Compounds 4-6 are all linear 1D coordination polymers. In 4, the free tfBDC2- ligand acts as a μ4-bridge to link four coordinated water molecules from the chain to construct a 2D structure via hydrogen bonds. While in 5 and 6, the uncoordinated tfBDC2- ligands and multimeric water clusters is responsible for the conversion of these 1D coordination polymers into 3D supramolecular assemblies through O-H⋯O hydrogen bonding interactions. Moreover

  19. A series of M-M' heterometallic coordination polymers: syntheses, structures and surface photoelectric properties (M=Ni/Co, M'=Cd/Zn)

    International Nuclear Information System (INIS)

    Li, Lei; Niu, Shu-Yun; Jin, Jing; Meng, Qin; Chi, Yu-Xian; Xing, Yong-Heng; Zhang, Guang-Ning

    2011-01-01

    Four new heterometallic polymers, [NiCd(mal) 2 (H 2 O) 2 ]n.2nH 2 O 1, [NiZn 2 (Hcit) 2 (H 2 O) 2 ]n 2, [CoCd 2 (Hcit) 2 (H 2 O) 2 ]n 3, [CoZn 2 (Hcit) 2 (H 2 O) 2 ]n 4 (H 2 mal=malonic acid, H 4 cit=citric acid) were synthesized and characterized. The photoelectric properties of the polymers were discussed by the surface photovoltage spectroscopy (SPS). The structural analyses indicate 1 is a Ni-Cd heterometallic polymer with 3D structure bridged by the mal 2- group. 2-4 are all heterometallic polymers with 2D structures bridged by the Hcit 3- group. The results of SPS for the four polymers reveal that there are wide photovoltage response bands in the range of 300-800 nm, which indicates that they all possess photoelectric conversion properties. By the introduction of the other metals, the SPS of heterometallic polymers are broadened obviously than the SPS of monometallic complexes. Moreover, the relationships between SPS and UV-Vis absorption spectra have been discussed. -- Graphical Abstract: Four heterometallic polymers, Ni-Cd, Ni-Zn, Co-Cd, Co-Zn, were synthesized and characterized. The photoelectric properties of heterometallic polymers were discussed by SPS. The introduction of heterometallic ions will broaden the SPS of corresponded monometallic complexes. Display Omitted Highlights: → Four new heterometallic coordination polymers were reported. → The surface photoelectric properties of heterometallic polymers were studied by SPS. → They all possess photoelectric conversion properties. → The SPS of heterometallic polymers are broadened than that of monometallic complexes.

  20. Synthesis, crystal structure, thermal and luminescence properties of CuX(2,3-dimethylpyrazine) (X=Cl, Br, I) coordination polymers.

    Science.gov (United States)

    Jess, Inke; Taborsky, Petr; Pospísil, Jirí; Näther, Christian

    2007-06-14

    Three new coordination polymers based on CuI and 2,3-dimethylpyrazine (2,3-dmpyz) were prepared, structurally characterized and investigated for their thermal and luminescence properties. In the ligand rich 2:3 compound [(CuI)2(2,3-dmpyz)3] (CuI)2 dimers are found, which are connected by the N-donor ligands into chains, whereas in the structure of the 1:1 intermediate [(CuI)(2,3-dmpyz)] (CuI)4 tetramers are found, which are also connected into chains. The crystal structure of the ligand deficient 2:1 compound [(CuI)2(2,3-dmpyz)] is built up of CuI double chains, which are connected by the 2,3-dmpyz ligands into layers. Thermal decomposition of results in its direct transformation into the ligand deficient compound , without the formation of the 1:1 compound as an intermediate. A similar thermal reactivity is found for compound , which transforms into on heating. Stirring of a crystalline suspension of pure or in acetonitrile, always leads to a transformation into the ligand deficient compound indicating that compound is the most stable of all the coordination polymers, whereas compounds and are metastable. The luminescence properties of the CuCl and CuI coordination polymers were investigated at 298 and 77K. It was observed that the emission maxima strongly depends on the nature of the halide atom and the composition and structure of the coordination polymers. In addition, several of these compounds show luminescence thermochromism. These results are compared with those obtained for the previously reported CuCl and CuBr(2,3-dimethylpyrazine) coordination polymers.

  1. Development of silica nanoparticles obtaintion process from renewable source waste and its incorporation in thermoplastic polymer for manufacturing a nanocomposite

    International Nuclear Information System (INIS)

    Ortiz, Angel Visentim

    2016-01-01

    The nanocomposite technology is applicable to a wide range of thermoplastic and thermoset polymers. The use of sugar cane byproducts has been extensively studied as a source of reinforcement for nanocomposites. The bagasse is widely used in cogeneration and as a result of the burning of this material, millions of tons of ash are produced. For this work, silica contained in the ashes of bagasse from sugarcane was extracted by chemical method and thermal method. The thermal method is more efficient leading to a purity of more than 93% of silica, while the chemical method generated silica contaminated with chlorine and sodium from the extraction reagents. The silica particles obtained were evaluated by dynamic light scattering (DSL) and presented an average size of 12 micrometers. These particles were submitted to grinding in a ball mill and then to a sonochemical treatment. Silica particles treated by the sonochemical process ( 20 kHz, 500 W and 90 minutes) had its dimensions reduced to nanometric scale of tenths of nanometers. The nanossílica obtained was then used as reinforcement in high density polyethylene (HDPE). Mechanical and thermo-mechanical properties were assessed and gains were shown for mechanical properties , except for the impact resistance. The distortion temperature (HDT) showed that the incorporation of the reinforcement in HDPE led to a small increase in this property compared to pure HDPE. The crystallinity of the nanocomposites generated was evaluated by differential scanning calorimetry (DSC) and it was observed a decrease of crystallinity in the material when the reinforcing incorporation was 3%. The material irradiated to 250 kGy with electron beam showed important property gains, mainly due to the high level of crosslinking of irradiated HDPE. (author)

  2. Two novel zinc(II) coordination polymers constructed from in situ amidation ligands

    Science.gov (United States)

    Yu, Xiao-Yang; Fu, Yao; Fu, Jian-Tao; Xu, Jia-Ning; Luo, Ya-Nan; Yang, Yan-Yan; Qu, Xiao-Shu; Zhang, Jing; Lu, Shu-Lai

    2018-04-01

    Two novel coordination compounds, [Zn(Hbimh) (H2O)]·H2O (1) and [Zn(Hbimh)]·(4,4ʹ-bpy)0.5 (2) (H3bimh = benzimidazole-5,6-hydrazide, 4,4ʹ-bpy = 4,4ʹ-bipyridine), have been prepared from the hydrothermal in situ amidation cyclization reactions of H3bimdc (H3bimdc = benzimidazole-5,6-dicarboxylic acid) and hydrazine hydrate (N2H4·H2O). Compound 1 exhibits a one-dimensional (1D) hexagon channel structure. Compound 2 is a three-dimensional (3D) framework structure, with 4,4ʹ-bpy fill the channels. We also obtained the ligand H3bimh. The compounds were characterized by IR, PXRD, TGA and elemental analysis. The fluorescence properties in the solid state at room temperature were also investigated.

  3. Structural characterization, electrochemical, photoluminescence and thermal properties of potassium ion-mediated coordination polymer.

    Science.gov (United States)

    Ceyhan, Gökhan; Köse, Muhammet; Tümer, Mehmet; Dal, Hakan

    2015-05-05

    A polymeric potassium complex of p-nitrophenol was synthesized and characterized by analytical and spectroscopic techniques. Molecular structure of the complex was determined by single crystal X-ray diffraction study. X-ray structural data show that crystals contain polymeric K(+) complex of p-nitrophenol. Asymmetric unit consists of one p-nitrophenolate, one K(+) ion and one water molecule. All bond lengths and angles in the phenyl rings have normal Csp2-Csp2 values and are in the expected ranges. The p-nitrophenolate is close to planar with small distortions by some atoms. Each potassium ion in the polymeric structure is identical and eight-coordinate, bonded to four nitro, two phenolate oxygen atoms from five p-nitrophenolate ligands and two oxygen atoms from two water molecules. Electronic, electrochemical, photoluminescence and thermal properties of the complex were also investigated. Copyright © 2015. Published by Elsevier B.V.

  4. A series of silver(I) coordination polymers with saccarinate and flexible aliphatic diamines

    Energy Technology Data Exchange (ETDEWEB)

    Yeşilel, Okan Zafer, E-mail: yesilel@ogu.edu.tr [Department of Chemistry, Faculty of Arts and Sciences, Eskişehir Osmangazi University, 26480 Eskişehir (Turkey); Karamahmut, Bingül [Department of Chemistry, Faculty of Arts and Sciences, Eskişehir Osmangazi University, 26480 Eskişehir (Turkey); Semerci, Fatih [Department of Energy Systems Engineering, Faculty of Technology, Kırklareli University, 39000 Kırklareli (Turkey); Darcan, Cihan [Department of Molecular Biology and Genetic, Faculty of Arts and Sciences, Bilecik Şeyh Edebali University, Gülümbe-Bilecik (Turkey); Yılmaz, Filiz [Department of Chemistry, Faculty of Sciences, Anadolu University, Eskişehir (Turkey)

    2017-05-15

    /DTA) of the complexes were investigated. - Graphical abstract: In this study, six new silver coordination compounds were synthesized by using saccharinate and flexible aliphatic diamine derivatives. All the compounds were characterized by elemental analysis, IR and single-crystal X-ray analysis. TG/DTA. Furthermore, biological activities, luminescence properties and thermal analysis (TG/DTA) of the complexes have been investigated. Complexes 1–5a and 6 were synthesized with the same reactant ratio and room temperature by using a mixture of AgNO{sub 3}, sac and different length diamine derivatives. The complex 5b is also synthesized was similar to that of 1 at 80 °C. In the complexes, the diamine derivatives ligands show bis(bridging) coordination mode. The sac ligand exhibits a µ-bridging coordination mode in 1 and N-donor monodentate coordination mode in 2–6. Complexes 1–5 exhibit 1D chain structure while complex 6 are tetranuclear structure. In the crystal packing of complexes, 3D supramolecular frameworks are formed via C-H···Ag, Ag···π and Ag···Ag interactions.

  5. An electrical-heating and self-sensing shape memory polymer composite incorporated with carbon fiber felt

    International Nuclear Information System (INIS)

    Gong, Xiaobo; Leng, Jinsong; Liu, Liwu; Liu, Yanju

    2016-01-01

    Shape memory polymers (SMPs) have the ability to adjust their stiffness, lock a temporary shape, and recover the permanent shape upon imposing an appropriate stimulus. They have found their way into the field of morphing structures. The electrically Joule resistive heating of the conductive composite can be a desirable stimulus to activate the shape memory effect of SMPs without external heating equipment. Electro-induced SMP composites incorporated with carbon fiber felt (CFF) were explored in this work. The CFF is an excellent conductive filler which can easily spread throughout the composite. It has a huge advantage in terms of low cost, simple manufacturing process, and uniform and tunable temperature distribution while heating. A continuous and compact conductive network made of carbon fibers and the overlap joints among them was observed from the microscopy images, and this network contributes to the high conductive properties of the CFF/SMP composites. The CFF/SMP composites can be electrical-heated rapidly and uniformly, and its’ shape recovery effect can be actuated by the electrical resistance Joule heating of the CFF without an external heater. The CFF/SMP composite get higher modulus and higher strength than the pure SMP without losing any strain recovery property. The high dependence of temperature and strain on the electrical resistance also make the composite a good self-sensing material. In general, the CFF/SMP composite shows great prospects as a potential material for the future morphing structures. (paper)

  6. Structural and electronic modulation of magnetic properties in a family of chiral iron coordination polymers.

    Science.gov (United States)

    Li, Lihong; Becker, Jan M; Allan, Laura E N; Clarkson, Guy J; Turner, Scott S; Scott, Peter

    2011-07-04

    The complexes FeL(2) [L = bidentate Schiff base ligands obtained from (R)-(+)-α-phenylethanamine and 4-substituted salicylaldehydes, substituent R = H, (t)Bu, NO(2), OMe, CN, OH] react with ditopic proligands 1,4-pyrazine (pz) or 4,4'-bipyridine (bpy), to give a family of optically pure Fe(II) polymeric chain complexes of formula {FeL(2)(μ-pz)}(∞) and {FeL(2)(μ-bpy)}(∞). Crystallographic studies show that a range of structures are formed including unidirectional and bidirectional linear polymers and canted zigzag chains. Interchain interactions via π-contacts and hydrogen bonding are also observed. SQuID magnetometry studies on all of the complexes reveal antiferromagnetic interactions, the magnitudes of which are rationalized on the basis of substituent electronic properties and bridging ligand identity. For complexes with bridging pz, the antiferromangnetic interaction is enhanced by electron-releasing substituents on the Fe units, and this is accompanied by a contraction in the intrachain distance. For complexes bridged with the longer bpy the intrachain antiferromagnetic couplings are much weaker as a result of the longer intrachain distance. The magnetic data for this series of chain complexes follow a Bonner-Fisher 1D chain model, alongside a zero field splitting (ZFS) model for Fe(II) (S = 2) as appropriate. The intrachain antiferromagnetic coupling J values, g-factors, and the axial ZFS parameter D were obtained. © 2011 American Chemical Society

  7. Secondary ligand-directed assembly of Co(II) coordination polymers based on a pyridine carboxylate ligand

    International Nuclear Information System (INIS)

    Cao, Ke-Li; Zhang, Yi-Ping; Cai, Yi-Ni; Xu, Xiao-Wei; Feng, Yun-Long

    2014-01-01

    To investigate the influence of hydrogen bonds and secondary ligands on the structures and properties of the resulting frameworks, five new Co(II) compounds have been synthesized by the reactions of Co(II) salts and 3,5-bis(pyridin-4-ylmethoxy)benzoic acid (HL) with four rationally selected dicarboxylic acid ligands. Without secondary ligand, we got one compound [CoL 2 (H 2 O) 2 ] n ·2nH 2 O (1), which possesses a 1D chain structure. In the presence of ancillary ligands, namely, 1,3-adamantanedicarboxylic acid (H 2 adbc), terephthalic acid (H 2 tpa), thiophene-2,5-dicarboxylic acid (H 2 tdc) and 1,4-benzenedithioacetic acid (H 2 bdtc), four 3D structures [Co 2 L 2 (adbc)] n ·nH 2 O (2), [Co 2 L 2 (tpa)] n (3), [Co 2 L 2 (tdc)] n (4), [Co 2 L 2 (bdtc)(H 2 O)] n (5) were obtained, respectively. It can be observed from the architectures of 1–5 that hydrogen bonds and secondary ligands both have great effects on the spatial connective fashions, resulting in the formation of various dimensional compounds. The XRPD, TGA data of title polymers and the magnetic properties for 2 and 5 have also been investigated. - Graphical abstract: The structural differences show that the ancillary ligands have great effects on the spatial connective fashions, resulting in the formation of various dimensional compounds. - Highlights: • Five new Co(II) coordination polymers have been synthesized by solvothermal reactions based on 3,5-bis(pyridin-4-ylmethoxy)benzoic acid (HL). • The long-flexible ligand (HL) is a good candidate to produce interpenetrating architectures. • The secondary dicarboxylic acid ligands play important roles in the spatial connective fashions and the formation of various dimensional compounds. • The magnetism studies show that both 2 and 5 exhibit antiferromagnetic interactions

  8. Robust Cross-Linked Stereocomplexes and C60 Inclusion Complexes of Vinyl-Functionalized Stereoregular Polymers Derived from Chemo/Stereoselective Coordination Polymerization.

    Science.gov (United States)

    Vidal, Fernando; Falivene, Laura; Caporaso, Lucia; Cavallo, Luigi; Chen, Eugene Y-X

    2016-08-03

    The successful synthesis of highly syndiotactic polar vinyl polymers bearing the reactive pendant vinyl group on each repeat unit, which is enabled by perfectly chemoselective and highly syndiospecific coordination polymerization of divinyl polar monomers developed through this work, has allowed the construction of robust cross-linked supramolecular stereocomplexes and C60 inclusion complexes. The metal-mediated coordination polymerization of three representative polar divinyl monomers, including vinyl methacrylate (VMA), allyl methacrylate (AMA), and N,N-diallyl acrylamide (DAA) by Cs-ligated zirconocenium ester enolate catalysts under ambient conditions exhibits complete chemoselectivity and high stereoselectivity, thus producing the corresponding vinyl-functionalized polymers with high (92% rr) to quantitative (>99% rr) syndiotacticity. A combined experimental (synthetic, kinetic, and mechanistic) and theoretical (DFT) investigation has yielded a unimetallic, enantiomorphic-site-controlled propagation mechanism. Postfunctionalization of the obtained syndiotactic vinyl-functionalized polymers via the thiol-ene click and photocuring reactions readily produced the corresponding thiolated polymers and flexible cross-linked thin-film materials, respectively. Complexation of such syndiotactic vinyl-functionalized polymers with isotactic poly(methyl methacrylate) and fullerene C60 generates supramolecular crystalline helical stereocomplexes and inclusion complexes, respectively. Cross-linking of such complexes affords robust cross-linked stereocomplexes that are solvent-resistant and also exhibit considerably enhanced thermal and mechanical properties compared with the un-cross-linked stereocomplexes.

  9. Robust Crosslinked Stereocomplexes and C60 Inclusion Complexes of Vinyl-Functionalized Stereoregular Polymers Derived from Chemo/Stereoselective Coordination Polymerization

    KAUST Repository

    Vidal, Fernando

    2016-07-07

    The successful synthesis of highly syndiotactic polar vinyl polymers bearing the reactive pendant vinyl group on each repeat unit, which is enabled by perfectly chemoselective and highly syndiospecific coordination polymerization of divinyl polar monomers developed through this work, has allowed the construction of robust crosslinked supramolecular stereocomplexes and C60 inclusion complexes. The metal-mediated coordination polymerization of three representative polar divinyl monomers, including vinyl methacrylate (VMA), allyl methacrylate (AMA), and N,N-diallyl acrylamide (DAA) by Cs-ligated zirconocenium ester enolate catalysts under ambient conditions exhibits complete chemoselectivity and high stereoselectivity, thus producing the corresponding vinyl-functionalized polymers with high (92% rr) to quantitative (>99% rr) syndiotacticity. A combined experimental (synthetic, kinetic, and mechanistic) and theoretical (DFT) investigation has yielded a unimetallic, enantiomorphic-site controlled propagation mechanism. Post-functionalization of the obtained syndiotactic vinyl-functionalized polymers via the thiol-ene click and photocuring reactions readily produced the corresponding thiolated polymers and flexible crosslinked thin film materials, respectively. Complexation of such syndiotactic vinyl-functionalized polymers with isotactic poly(methyl methacrylate) and fullerene C60 generates supramolecular crystalline helical stereocomplexes and inclusion complexes, respectively. Crosslinking of such complexes afforded robust crosslinked stereocomplexes that are solvent resistant and also exhibit considerably enhanced thermal and mechanical properties as compared to the uncrosslinked stereocompexes.

  10. Three 3D metal coordination polymers based on triazol-functionalized rigid ligand: Synthesis, topological structure and properties

    Science.gov (United States)

    Meng, Lingkun; Liu, Kang; Liang, Chen; Guo, Xiaolei; Han, Xu; Ren, Siyuan; Ma, Dingxuan; Li, Guanghua; Shi, Zhan; Feng, Shouhua

    2018-02-01

    By using a triazol-functionalized tricarboxylate, three novel metal coordination polymers, namely, [Zn2L(OH)]·0.5H2O (1), [Co2L(OH)(H2O)]·5.5H2O (2), [Cu2(HL)] (3) L = [5-(3-(4-carboxyphenyl)-5-methyl-4H-1,2,4-triazol-4-yl)isophthalate] were synthesized under hydrothermal reactions. All the compounds were characterized by element analysis, IR spectroscopy, thermogravimetric analysis, power X-ray diffrcation and single-crystal X-ray diffrcation. Structural analysis reveals that compounds 1 and 2 have 3D networks with flu topologies where rigid trizaol-functionalized ligands as 4-connected nodes and Zn4(COO)6 or Co4(COO)6 clusters serves as 8-connected secondary building units. Compound 3 has 3D network with pcu topology where Cu4(COO)4 clusters serve as 6-connected secondary building units. Gas adsorption studies reveal that desolvated compoud 1 exhibits high H2 absorption capacity at 77 K and highly selective separation abilities of CO2 and C3H8 over CH4 at room temperature. The results suggest that 1 has potential application in gas storage and separation. In addition, the magnetic properties of compound 2 were also investigated.

  11. Rectangular coordination polymer nanoplates: large-scale, rapid synthesis and their application as a fluorescent sensing platform for DNA detection.

    Directory of Open Access Journals (Sweden)

    Yingwei Zhang

    Full Text Available In this paper, we report on the large-scale, rapid synthesis of uniform rectangular coordination polymer nanoplates (RCPNs assembled from Cu(II and 4,4'-bipyridine for the first time. We further demonstrate that such RCPNs can be used as a very effective fluorescent sensing platform for multiple DNA detection with a detection limit as low as 30 pM and a high selectivity down to single-base mismatch. The DNA detection is accomplished by the following two steps: (1 RCPN binds dye-labeled single-stranded DNA (ssDNA probe, which brings dye and RCPN into close proximity, leading to fluorescence quenching; (2 Specific hybridization of the probe with its target generates a double-stranded DNA (dsDNA which detaches from RCPN, leading to fluorescence recovery. It suggests that this sensing system can well discriminate complementary and mismatched DNA sequences. The exact mechanism of fluorescence quenching involved is elucidated experimentally and its use in a human blood serum system is also demonstrated successfully.

  12. Ratiometric fluorescence detection of superoxide anion based on AuNPs-BSA@Tb/GMP nanoscale coordination polymers.

    Science.gov (United States)

    Liu, Nan; Hao, Juan; Cai, Keying; Zeng, Mulan; Huang, Zhenzhong; Chen, Lili; Peng, Bingxian; Li, Ping; Wang, Li; Song, Yonghai

    2018-02-01

    A novel ratiometric fluorescence nanosensor for superoxide anion (O 2 •- ) detection was designed with gold nanoparticles-bovine serum albumin (AuNPs-BSA)@terbium/guanosine monophosphate disodium (Tb/GMP) nanoscale coordination polymers (NCPs) (AuNPs-BSA@Tb/GMP NCPs). The abundant hydroxyl and amino groups of AuNPs-BSA acted as binding points for the self-assembly of Tb 3+ and GMP to form core-shell AuNPs-BSA@Tb/GMP NCP nanosensors. The obtained probe exhibited the characteristic fluorescence emission of both AuNPs-BSA and Tb/GMP NCPs. The AuNPs-BSA not only acted as a template to accelerate the growth of Tb/GMP NCPs, but also could be used as the reference fluorescence for the detection of O 2 •- . The resulting AuNPs-BSA@Tb/GMP NCP ratiometric fluorescence nanosensor for the detection of O 2 •- demonstrated high sensitivity and selectivity with a wide linear response range (14 nM-10 μM) and a low detection limit (4.7 nM). Copyright © 2017 John Wiley & Sons, Ltd.

  13. Synthesis, crystal structures, luminescence and catalytic properties of two d¹⁰ metal coordination polymers constructed from mixed ligands.

    Science.gov (United States)

    Wang, Xiao-xiao; Zhang, Ming-xi; Yu, Baoyi; Van Hecke, Kristof; Cui, Guang-hua

    2015-03-15

    Two new coordination polymers [Cd(bmb)(hmph)]n (1), {[Ag(bmb)]·H2btc}n (2) (bmb=1,4-bis(2-methylbenzimidazol-1-ylmethyl)benzene, H2hmph=homophthalic acid, H3btc=1,3,5-benzenetetracarboxylic acid) were synthesized under hydrothermal conditions and characterized by single-crystal X-ray diffraction methods, IR spectroscopy, TGA, XRPD and elemental analysis. Complex 1 features a 3D threefold interpenetrating dia array with a 4-connected 6(6) topology. Complex 2 shows a 1D helix chain structure connected by L1 ligands, which is finally extended into a rarely 2D 4L2 supramolecular network via C-H⋯O hydrogen bond interactions. In addition, the luminescence and catalytic properties of the two complexes for the degradation of the methyl orange azo dye in a Fenton-like process were presented. The degradation efficiency of the methyl orange azo dye for 1 and 2 are 56% and 96%, respectively. Copyright © 2014 Elsevier B.V. All rights reserved.

  14. Syntheses, crystal structures, and water adsorption behaviors of jungle-gym-type porous coordination polymers containing nitro moieties

    Science.gov (United States)

    Uemura, Kazuhiro; Onishi, Fumiaki; Yamasaki, Yukari; Kita, Hidetoshi

    2009-10-01

    NO 2 containing dicarboxylate bridging ligands, nitroterephthalate (bdc-NO 2) and 2,5-dinitroterephthalate (bdc-(NO 2) 2), afford porous coordination polymers, {[Zn 2(bdc-NO 2) 2(dabco)]· solvents} n ( 2⊃ solvents) and {[Zn 2(bdc-(NO 2) 2) 2(dabco)]· solvents} n ( 3⊃ solvents). Both compounds form jungle-gym-type regularities, where a 2D square grid composed of dinuclear Zn 2 units and dicarboxylate ligands is bridged by dabco molecules to extend the 2D layers into a 3D structure. In 2⊃ solvents and 3⊃ solvents, a rectangle pore surrounded by eight Zn 2 corners contains two and four NO 2 moieties, respectively. Thermal gravimetry (TG) and X-ray powder diffraction (XRPD) measurements reveal that both compounds maintain the frameworks regularities without guest molecules and with solvents such as MeOH, EtOH, i-PrOH, and Me 2CO. Adsorption measurements reveal that dried 2 and 3 adsorb H 2O molecules to be {[Zn 2(bdc-NO 2) 2(dabco)]·4H 2O} n ( 2⊃4H 2O) and {[Zn 2(bdc-(NO 2) 2) 2(dabco)]·6H 2O} n ( 3⊃6H 2O), showing the pore hydrophilicity enhancement caused by NO 2 group introduction.

  15. Two New Preyssler-Type Polyoxometalate-Based Coordination Polymers and Their Application in Horseradish Peroxidase Immobilization.

    Science.gov (United States)

    Du, Jing; Cao, Mei-Da; Feng, Shu-Li; Su, Fang; Sang, Xiao-Jing; Zhang, Lan-Cui; You, Wan-Sheng; Yang, Mei; Zhu, Zai-Ming

    2017-10-17

    Enzyme immobilization is of increasing importance for biocatalysis, for which good supports are critical. Herein, two new Preyssler-type polyoxometalate (POM)-based coordination polymers, namely, {[Cu(H 2 biim) 2 ][{Cu(H 2 biim) 2 (μ-H 2 O)} 2 Cu(H 2 biim)(H 2 O) 2 ]H[({Cu(H 2 biim)(H 2 O) 2 } 0.5 ) 2 ((μ-C 3 HN 2 Cl 2 ){Cu(H 2 biim)} 2 ){Z(H 2 O)P 5 W 30 O 110 }]⋅x H 2 O} n (1: Z=Na, x=9; 2: Z=Ag, x=10; H 2 biim=2,2'-biimidazole) were designed and synthesized. Compounds 1 and 2 exhibit the same skeletons, which contain multiple Cu II complex fragments and penta-supported {ZP 5 W 30 } (Z=Na, Ag) clusters. They were first employed to immobilize horseradish peroxidase (HRP). Results show that compounds 1 and 2 are good supports for HRP immobilization, and exhibit higher enzyme loading, lower loading times, and excellent reusability. The immobilized HRP (HRP/1 or HRP/2) was further applied to detect H 2 O 2 , and good sensitivity, wide linear range, low detection limit, and fast response were achieved. This work shows that POM-based hybrid materials are a new kind of promising support for enzyme immobilization. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  16. Mixed Cu(i)/Au(i) coordination polymers as reversible turn-on vapoluminescent sensors for volatile thioethers.

    Science.gov (United States)

    Varju, Bryton R; Ovens, Jeffrey S; Leznoff, Daniel B

    2017-06-13

    Vapour-phase thioethers play an important role in a wide number of fields, including plant biology, chemical weapon disposal, and brewing but few sensor materials are known. The emissive coordination polymer Cu 1/2 Au 1/2 CN does not react with vapour phase dimethyl sulphide (DMS) or diethyl sulphide (DES) despite the independent synthesis of emissive [Cu 1/2 Au 1/2 CN] 2 (DMS) and [Cu 1/2 Au 1/2 CN] 2 (DES) from their constituent components in solution. However, the doped Cu 2/3 Au 1/3 CN rapidly reacts in the solid state with both of these vapour phase thioethers reversibly, with a change in emission from 380/560 nm to 460 nm (DMS) or 420 nm (DES), illustrating that doping the inactive parent Cu 1/2 Au 1/2 CN with Cu(i) generates an active sensor material. This response can be thermally cycled with little to no loss in functionality. [Cu 1/2 Au 1/2 CN] 2 (DMS), [Cu 2/3 Au 1/3 CN] 2 (DMS), and [Cu 2/3 Au 1/3 CN] 2 (DES) were structurally characterized as 3-D network structures supported by aurophilic interactions.

  17. Sonochemical synthesis of two nanostructured silver(I) coordination polymers based on semi-rigid bis(benzimidazole) ligands.

    Science.gov (United States)

    Hao, Shao Yun; Li, Yue Hua; Hao, Zeng Chuan; Cui, Guang Hua

    2017-11-01

    Nanoparticles of two silver(I) coordination polymers (CPs), [Ag 2 (L1) 2 (DCTP)] n (1) and [Ag 2 (L2)(DCTP)] n (2) (L1=1,3-bis(5,6-dimethylbenzimidazol-1-ylmethyl)benzene, L2=1,4-bis(benzimidazol-1-yl)-2-butene, H 2 DCTP=2,5-dichloroterephthalic acid), were synthesized by the sonochemical approach and hydrothermal method. Both CPs were characterized by elemental analysis, IR spectra, single-crystal X-ray diffraction, scanning electron microscopy (SEM), and thermogravimetric analyses (TGA). CP 1 exhibits a 2D 4-connected sql net with the point symbol {4 4 .6 2 }. While CP 2 displays a 2D 3,4-connected 3,4L13 net with the point symbol {4.6 2 } 2 {4 2 .6 2 .8 2 }. The structural diversity indicates that semi-rigid bis(benzimidazole) co-ligands play important roles in tuning the structures of the mixed Ag(I) CPs. The ultrasound irradiation time, temperature, and power showed significant effects on the morphology and growth process of the nanoparticles of two silver(I) CPs. The luminescence and photocatalytic properties of the nanoparticles of CPs 1-2 on the degradation of methyl blue (MB) were also investigated in detail. Copyright © 2017 Elsevier B.V. All rights reserved.

  18. Supramolecular isomerism in cadmium (II) coordination polymers from benzene-1,3,5-tribenzoate (BTB): Syntheses, structures and luminescent properties

    Science.gov (United States)

    Zhang, Jian-Yong; Cui, Peng-Hui; Shi, Jun-Xia; Zhang, Na; Deng, Wei

    2017-12-01

    By tuning the solvent mixture, four CdII-based compounds, [Cd3(BTB)2(DMA)4]·2DMA (1α), [Cd3(BTB)2(DMA)4]·2DMA (1β), [Cd3(BTB)2(DMF)4]·2DMF (1γ), Cd2(BTB)(HCOO)(DMF)3 (2) have been successfully separated from H3BTB ligand and Cd(NO3)2 salts. Structural analyses revealed that compounds 1α, 1β and 1γ are iso-structural and have essentially identical local and two-dimensional structures constructed from trinuclear Cd3(OCO)6 unit. Their structural differences only arise from the different packing fashions, which are novel modes of supramolecular isomerism in coordination polymers. Compound 2 displays 3D two-fold interpenetrated network based on 1D infinite Cd3(μ1,1,3-OCO)2(HCOO) chains containing mixed BTB3- and formate ligands. The fluorescence measurements show that compounds 2 exhibit red-shifts (about 25 nm) in the solid state, compared with three iso-structural 1α, 1β and 1γ, and this can be attributed to the cooperative effects of intraligand π-π* transitions and ligand-to-metal charge transfer (LMCT).

  19. High-energy coordination polymers (CPs) exhibiting good catalytic effect on the thermal decomposition of ammonium dinitramide

    Science.gov (United States)

    Li, Xin; Han, Jing; Zhang, Sheng; Zhai, Lianjie; Wang, Bozhou; Yang, Qi; Wei, Qing; Xie, Gang; Chen, Sanping; Gao, Shengli

    2017-09-01

    High-energy coordination polymers (CPs) not only exhibit good energetic performances but also have a good catalytic effect on the thermal decomposition of energetic materials. In this contribution, two high-energy CPs Cu2(DNBT)2(CH3OH)(H2O)3·3H2O (1) and [Cu3(DDT)2(H2O)2]n (2) (H2DNBT = 3,3‧-dinitro-5,5‧-bis(1H-1,2,4-triazole and H3DDT = 4,5-bis(1H-tetrazol-5-yl)-2H-1,2,3-triazole) were synthesized and structurally characterized. Furthermore, 1 was thermos-dehydrated to produce Cu2(DNBT)2(CH3OH)(H2O)3 (1a). The thermal decomposition kinetics of 1, 1a and 2 were studied by Kissinger's method and Ozawa's method. Thermal analyses and sensitivity tests show that all compounds exhibit high thermal stability and low sensitivity for external stimuli. Meanwhile, all compounds have large positive enthalpy of formation, which are calculated as being (1067.67 ± 2.62) kJ mol-1 (1), (1464.12 ± 3.12) kJ mol-1 (1a) and (3877.82 ± 2.75) kJ mol-1 (2), respectively. The catalytic effects of 1a and 2 on the thermal decomposition of ammonium dinitramide (ADN) were also investigated.

  20. Neutral and anionic duality of 1,2,4-triazole α-amino acid scaffold in 1D coordination polymers

    International Nuclear Information System (INIS)

    Naik, Anil D.; Dîrtu, Marinela M.; Garcia, Yann

    2012-01-01

    A tiny supramolecular synthon, 4H-1,2,4-triazol-4-yl acetic acid (HGlytrz) which is bifunctional by design having an electronic asymmetry and conformational flexibility has been introduced to synthesize iron(II) complexes. Having 1,2,4-triazole or carboxylic extremities on the same framework HGlytrz could display dual functionality by acting as a neutral as well as anionic ligand based on the possibility of deprotonation of carboxylic group. Four new iron(II) HGlytrz complexes with ClO 4 - (1), NO 3 -bar (2), BF 4 - (3) and CF 3 SO 3b ar (4) anions were prepared. Formulation of their composition which is complicated due to ligand deprotonation is discussed. Unlike its ester protected counterpart ethyl-4H-1,2,4-triazol-4-yl-acetate (αGlytrz) which show hysteretic room temperature spin crossover, 1–4 remain in the high-spin state as revealed by 57 Mössbauer spectroscopy. Prospects of such 1D coordination polymers with dangling unbounded carboxylic entities in the realm of self-assembled monolayer (SAM) are discussed.

  1. Neutral and anionic duality of 1,2,4-triazole {alpha}-amino acid scaffold in 1D coordination polymers

    Energy Technology Data Exchange (ETDEWEB)

    Naik, Anil D.; Dirtu, Marinela M.; Garcia, Yann, E-mail: yann.garcia@uclouvain.be [Universite Catholique de Louvain, Institute of Condensed Matter and Nanosciences, MOST - Inorganic Chemistry (Belgium)

    2012-03-15

    A tiny supramolecular synthon, 4H-1,2,4-triazol-4-yl acetic acid (HGlytrz) which is bifunctional by design having an electronic asymmetry and conformational flexibility has been introduced to synthesize iron(II) complexes. Having 1,2,4-triazole or carboxylic extremities on the same framework HGlytrz could display dual functionality by acting as a neutral as well as anionic ligand based on the possibility of deprotonation of carboxylic group. Four new iron(II) HGlytrz complexes with ClO{sub 4{sup -}} (1), NO{sub 3}-bar (2), BF{sub 4{sup -}} (3) and CF{sub 3}SO{sub 3b}ar (4) anions were prepared. Formulation of their composition which is complicated due to ligand deprotonation is discussed. Unlike its ester protected counterpart ethyl-4H-1,2,4-triazol-4-yl-acetate ({alpha}Glytrz) which show hysteretic room temperature spin crossover, 1-4 remain in the high-spin state as revealed by {sup 57}Moessbauer spectroscopy. Prospects of such 1D coordination polymers with dangling unbounded carboxylic entities in the realm of self-assembled monolayer (SAM) are discussed.

  2. Self-assembled Nanoscale Coordination Polymers Carrying siRNAs and Cisplatin for Effective Treatment of Resistant Ovarian Cancer

    Science.gov (United States)

    He, Chunbai; Liu, Demin; Lin, Wenbin

    2014-01-01

    Resistance to the chemotherapeutic agent cisplatin is a major limitation for the successful treatment of many cancers. Development of novel strategies to overcome intrinsic and acquired resistance to chemotherapy is of critical importance to effective treatment of ovarian cancer and other types of cancers. We have sought to re-sensitize resistant ovarian cancer cells to chemotherapy by co-delivering chemotherapeutics and pooled siRNAs targeting multi-drug resistance (MDR) genes using self-assembled nanoscale coordination polymers (NCPs). In this work, NCP-1 particles with trigger release properties were first constructed by linking cisplatin prodrug-based bisphosphonate bridging ligands with Zn2+ metal-connecting points and then coated with a cationic lipid layer, followed by the adsorption of pooled siRNAs targeting three MDR genes including survivin, Bcl-2, and P-glycoprotein via electrostatic interactions. The resulting NCP-1/siRNA particles promoted cellular uptake of cisplatin and siRNA and enabled efficient endosomal escape in cisplatin-resistant ovarian cancer cells. By down-regulating the expression of MDR genes, NCP-1/siRNAs enhanced the chemotherapeutic efficacy as indicated by cell viability assay, DNA ladder, and flow cytometry. Local administration of NCP-1/siRNAs effectively reduced tumor sizes of cisplatin-resistant SKOV-3 subcutaneous xenografts. This work shows that the NCP-1/siRNA platform holds great promise in enhancing chemotherapeutic efficacy for the effective treatment of drug-resistant cancers. PMID:25315138

  3. Nitrate-Bridged One-Dimension Coordination Polymer Self-Assembled from a N4O2-Tetraiminodiphenolate Dicopper(II Macrocyclic Complex

    Directory of Open Access Journals (Sweden)

    Julio Cesar da Rocha

    2015-01-01

    Full Text Available Herein we report on the synthesis and single crystal X-ray structure characterization of [{Cu2(tidf(μ-NO3}∞]ClO4 (tidf = a Robson type macrocyclic ligand obtained upon condensation of 2,6-diformyl-4-methylphenol and 1,3-diaminopropane. The coordination geometry around the copper(II is square-pyramidal and has [Cu2(tidf]2+ units connected to each other through nitrate bridges extending as a one-dimension coordination polymer. The compound exhibits an extensive supramolecular structure supported by nonclassic hydrogen bonding between C-H⋯Operchlorate and C-H⋯Onitrate.

  4. X-ray Structure and Magnetic Properties of two new iron(II) 1D Coordination Polymers with Bis(imidazolyle)methane as bridging ligand

    OpenAIRE

    Weber , Birgit

    2009-01-01

    Abstract The reaction of iron(II) acetate with the tetradentate Schiff base like ligands H2L1 ((E,E)-[{diethyl 2,2'-[1,2-phenylenebis-(iminomethyl-idyne)]bis[3-oxobutanato]}]) and H2L2 ([([3,3']-[1,2-phenylene-bis(iminomethylidyne)]bis(2,4-pentane-dionato)(2-)-N,N',O2,O2']) leads to the formation of the octahedral N2O4 coordinated iron complexes [FeL1(MeOH)2] and [FeL2(MeOH)2], respectively. Conversion of both with bimm (bis(1-imidazolyle)methane) leads to the 1D coordination polym...

  5. Synthesis and Molecular Structures of Two [1,4-bis(3-pyridyl)-2,3-diazo-1,3-butadiene]-dichloro-Zn(II) Coordination Polymers

    OpenAIRE

    Lee, Gene-Hsiang; Wang, Hsin-Ta

    2006-01-01

    Two novel coordination polymers with 3D metal-organic frameworks (MOFs) have been synthesized by reacting 1,4-bis(3-pyridyl)-2,3-diazo-1,3-butadiene (L) with zinc dichloride. Both compounds have the same repeating unit consisting of a distorted tetrahedral Zn(II) center coordinated by two chlorides and two pyridyl nitrogen atoms of two bridging bismonodentate L ligands, however, different structural conformations have been found, one forming a helical chain and the other producing a square-wa...

  6. Thermally activated 3D to 2D structural transformation of [Ni2(en)2(H2O)6(pyr)]·4H2O flexible coordination polymer

    International Nuclear Information System (INIS)

    Begović, Nebojša N.; Blagojević, Vladimir A.; Ostojić, Sanja B.; Radulović, Aleksandra M.; Poleti, Dejan; Minić, Dragica M.

    2015-01-01

    Thermally activated 3D to 2D structural transformation of the binuclear [Ni 2 (en) 2 (H 2 O) 6 (pyr)]·4H 2 O complex was investigated using a combination of theoretical and experimental methods. Step-wise thermal degradation (dehydration followed by release of ethylene diamine) results in two layered flexible coordination polymer structures. Dehydration process around 365 K results in a conjugated 2D structure with weak interlayer connectivity. It was shown to be a reversible 3D to 2D framework transformation by a guest molecule, and rehydration of the dehydration product occurs at room temperature in saturated water vapor. Rehydrated complex exhibits lower dehydration temperature, due to decreased average crystalline size, with higher surface area resulting in easier release and diffusion of water during dehydration. Thermal degradation of dehydration around 570 K, results in loss of ethylene diamine, producing a related 2D layered polymer structure, without interconnectivity between individual polymer layers. - Highlights: • Reversible 3D to 2D framework topochemical transformation on dehydration around 365 K. • Resulting polymer exhibits 2D layered structure with weak interlayer connectivity. • Dehydration is fully reversible in saturated water vapor at room temperature. • Further degradation around 570 K yields 2D polymer without interlayer connectivity. • 2D polymer exhibits conjugated electronic system

  7. Studies on the relation between the size and dispersion of metallic silver nanoparticles and morphologies of initial silver(I) coordination polymer precursor

    Science.gov (United States)

    Moradi, Zhaleh; Akhbari, Kamran; Phuruangrat, Anukorn; Costantino, Ferdinando

    2017-04-01

    Micro and nano-structures of [Ag2(μ2-dcpa)2]n (1), [Hdcpa = 2,4-dichlorophenoxyacetic acid] which is a one-dimensional coordination polymer with corrugated tape chains, were synthesized as the bulk sample (1B), by sonochemical process (1S) and from mechanochemical reaction (1M). These three samples have been used as new precursors for fabricating silver nanoparticles via direct calcination at 300 °C and also thermal decomposition in oleic acid (OA) as a surfactant at 180 °C. In the presence of OA less agglomerated nanostructures were formed. It seems that the size, dispersion, morphology and agglomeration of initial precursor have direct influence on size, dispersion, morphology and agglomeration of metallic silver. This coordination polymer with various micro and nano morphologies were characterized by X-ray powder diffraction (XRD) and scanning electron microscopy (SEM). Thermal stability of these samples were studied and compared with each other, too.

  8. Synthesis, Crystal Structure, and Electroconducting Properties of a 1D Mixed-Valence Cu(I–Cu(II Coordination Polymer with a Dicyclohexyl Dithiocarbamate Ligand

    Directory of Open Access Journals (Sweden)

    Kenji Nakatani

    2015-04-01

    Full Text Available A new mixed-valence Cu(I–Cu(II 1D coordination polymer, [CuI4CuIIBr4(Cy2dtc2]n, with an infinite chain structure is synthesized by the reaction of Cu(Cy2dtc2 (Cy2dtc− = dicyclohexyl dithiocarbamate, C13H22NS2 with CuBr·S(CH32. The as-synthesized polymer consists of mononuclear copper(II units of CuII(Cy2dtc2 and tetranuclear copper(I cluster units, CuI4Br4. In the cluster unit, all the CuI ions have distorted trigonal pyramidal coordination geometries, and the CuI–CuI or CuI–CuII distances between the nearest copper ions are shorter than the sum of van der Waals radii for Cu–Cu.

  9. [Study on the Eu-containing coordination polymer. I. Structural characterization of Eu (III)-thienyltrifluroacetone-poly (styrene-acrylic acid)].

    Science.gov (United States)

    Xiao, Li-ren; Gao, Feng; Tang, Jie-yuan; Zhang, Wen-gong

    2004-06-01

    Three samples (a), (b) and (c) of luminescent Eu-containing copolymer (NaEu(III)-TTA-PSAA) were synthesized through the reaction of copolymer of acrylic acid and styrene (Mw = 3000) with metalorganic complex (NaEu(TTA)4) obtained from Eu and thienyltrifluroacetone. These samples of coordination polymers were characterized by FTIR, UV and XPS, and their composition and structures were determined. The results of electrical conductivity methods and elemental analysis indicated that there were different compositions and structures of these coordination polymers in different pH. The results of elemental analysis also showed that the content of Eu3+ in sample (a), (b) and (c) was 11.89%, 12.55% and 13.41%, respectively.

  10. Three dimensional nano-assemblies of noble metal nanoparticle-infinite coordination polymers as specific oxidase mimetics for degradation of methylene blue without adding any cosubstrate.

    Science.gov (United States)

    Wang, Lihua; Zeng, Yi; Shen, Aiguo; Zhou, Xiaodong; Hu, Jiming

    2015-02-07

    Novel three-dimensional (3D) nano-assemblies of noble metal nanoparticle (NP)-infinite coordination polymers (ICPs) are conveniently fabricated through the infiltration of HAuCl4 into hollow Au@Ag@ICPs core-shell nanostructures and its replacement reaction with Au@Ag NPs. The present 3D nano-assemblies exhibit highly efficient and specific intrinsic oxidase-like activity even without adding any cosubstrate.

  11. Two-dimensional lanthanide coordination polymers with bis(diphenylphosphino)hexane dioxide. The determination of the polymeric structure from twinned crystals

    Czech Academy of Sciences Publication Activity Database

    Spichal, Z.; Petříček, Václav; Pinkas, J.; Nečas, M.

    2008-01-01

    Roč. 27, č. 1 (2008), s. 283-288 ISSN 0277-5387 R&D Projects: GA ČR GA202/06/0757 Institutional research plan: CEZ:AV0Z10100521 Keywords : bis(diphenylphosphino) hexane dioxide * coordination polymers * X-ray crystallography * twinning * lanthanides Subject RIV: BM - Solid Matter Physics ; Magnetism Impact factor: 1.801, year: 2008

  12. Series of coordination polymers based on 4-(5-sulfo-quinolin-8-yloxy) phthalate and bipyridinyl coligands: Structure diversity and properties

    Energy Technology Data Exchange (ETDEWEB)

    Feng, Xun [College of Chemistry and Chemical Engineering, Luoyang Normal University, Luoyang 471022 (China); Liu, Jing [College of Chemistry and Molecular Engineering, Zhengzhou University, Zhengzhou 450001 (China); College of Chemistry and Chemical Engineering, Luoyang Normal University, Luoyang 471022 (China); Li, Jin; Ma, Lu-Fang [College of Chemistry and Chemical Engineering, Luoyang Normal University, Luoyang 471022 (China); Wang, Li-Ya, E-mail: wlya@lynu.edu.cn [College of Chemistry and Chemical Engineering, Luoyang Normal University, Luoyang 471022 (China); College of Chemistry and Pharmacy Engineering, Nanyang Normal University, Nanyang 473601 (China); Ng, Seik-Weng [Department of Chemistry, University of Malaya, Kuala Lumpur 50603 (Malaysia); Chemistry Department, Faculty of Science, King Abdulaziz University, Jeddah 80203 (Saudi Arabia); Qin, Guo-Zhan [College of Chemistry and Chemical Engineering, Luoyang Normal University, Luoyang 471022 (China)

    2015-10-15

    Reactions between later metal salts and conjugational N-hetrocyclic sulfonate/ carboxylic acid under the presence of bipyridyl auxiliary ligands afforded a series of manganese, nickel, zinc, silver, cadmium coordination polymers bearing with phenyl pendant arm attached to quinoline skeletons, and they have been characterized by elements analysis, thermogravimetry, infrared spectroscopy and single-crystal X-ray diffraction studying. The series of polymers show interesting structural diversity in coordination environment, dimensions and topologies. They are all built from 2-D networks constructed from metal cluster through sulfonate or carboxylate groups, as the secondary building unit (SBU). The thermalgravimetric analyses show that they display framework stabilities in solid state. Variable-temperature magnetic susceptibility studies reveal the existence of antiferromagnetic interactions between adjacent Mn (II) ions in 1, and ferromagnetic interactions between Ni(II) ions for 2, respectively. The photo-luminescence properties of 3-5 have also been investigated systemically. - Highlights: • A series of coordination polymers based on later transition metal ions have been obtained. • They contain conjugational N-hetrocyclic sulfonate-carboxylic acid and bipyridyl auxiliary ligands. • They have been characterized systemically. • They exhibit structure diversity and interesting properties.

  13. Metallogels derived from silver coordination polymers of C3-symmetric tris(pyridylamide) tripodal ligands: synthesis of Ag nanoparticles and catalysis.

    Science.gov (United States)

    Paul, Mithun; Sarkar, Koushik; Dastidar, Parthasarathi

    2015-01-02

    By applying a recently developed crystal engineering rationale, four C3 symmetric tris(pyridylamide) ligands namely 1,3,5-tris(nicotinamidomethyl)-2,4,6-triethylbenzene, 1,3,5-tris(isonicotinamidomethyl)-2,4,6-triethylbenzene, 1,3,5-tris(nicotinamidomethyl)-2,4,6-trimethylbenzene, and 1,3,5-tris(isonicotinamidomethyl)-2,4,6-trimethylbenzene, which contain potential hydrogen-bonding sites, were designed and synthesized for generating Ag(I) coordination polymers and coordination-polymer-based gels. The coordination polymers thus obtained were characterized by single-crystal X-ray diffraction. The silver metallogels were characterized by transmission electron microscopy (TEM) and dynamic rheology. Upon exposure to visible light, these silver metallogels produced silver nanoparticles (AgNPs), which were characterized by TEM, powder X-ray diffraction, energy dispersive X-ray and X-ray photoelectron spectroscopy. These NPs were found to be effectively catalyzed the reduction of 4-nitrophenolate to 4-aminophenolate without the use of any exogenous reducing agent. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  14. Vapochromic luminescence and flexibility control of porous coordination polymers by substitution of luminescent multinuclear Cu(I) cluster nodes.

    Science.gov (United States)

    Hayashi, Takahiro; Kobayashi, Atsushi; Ohara, Hiroki; Yoshida, Masaki; Matsumoto, Takeshi; Chang, Ho-Chol; Kato, Masako

    2015-09-21

    Two luminescent porous coordination polymers (PCPs), i.e., [Cu2(μ2-I)2ctpyz]n and [Cu4(μ3-I)4ctpyz]n (Cu2 and Cu4, respectively; ctpyz = cis-1,3,5-cyclohexanetriyl-2,2',2″-tripyrazine), were successfully synthesized and characterized by single-crystal X-ray diffraction and luminescence spectroscopic measurements. Cu2 consists of rhombus-type dinuclear {Cu2I2} cores bridged by ctpyz ligands, while Cu4 is constructed of cubane-type tetranuclear {Cu4I4} cores bridged by ctpyz ligands. The void fraction of Cu4 is estimated to be 48.0%, which is significantly larger than that of Cu2 (19.9%). Under UV irradiation, both PCPs exhibit red luminescence at room temperature in the solid state (λem values of 660 and 614 nm for Cu2 and Cu4, respectively). Although the phosphorescence of Cu2 does not change upon removal and/or adsorption of EtOH solvent molecules in the porous channels, the solid-state emission maximum of Cu4 red-shifts by 36 nm (λem = 650 nm) upon the removal of the adsorbed benzonitrile (PhCN) molecules from the porous channels (and vice versa). This large difference in the vapochromic behavior of Cu2 and Cu4 is closely related to the framework flexibility. The framework of Cu2 is sufficiently rigid to retain the porous structure without solvated EtOH molecules, whereas the porous structure of Cu4 collapses easily after removal of the adsorbed PhCN molecules to form a nonporous amorphous phase. The original vapor-adsorbed porous structure of Cu4 is regenerated by exposure of the amorphous solid to not only PhCN vapor but also tetrahydrofuran, acetone, ethyl acetate, and N,N-dimethylformamide vapors. The Cu4 structures with the various adsorbed solvents showed almost the same emission maxima as the original PhCN-adsorbed Cu4, except for DMF-adsorbed Cu4, which showed no luminescence probably because of weak coordination of the DMF vapor molecules to the Cu(I) centers of the tetranuclear {Cu4I4} core.

  15. Stability and stabilization of polymers under irradiation. Final report of a co-ordinated research project, 1994-1997

    International Nuclear Information System (INIS)

    1999-01-01

    The contributions presented in this technical publication describe progress in understanding and controlling the degradation of polymeric materials induced by exposure to ionizing radiation. This subject area is of widespread importance to industrial use of radiation for two classes of applications: (1) the processing and production of polymeric materials by means of irradiation facilities, and (2) the use of polymeric materials in applications for which they must withstand irradiation throughout the course of their useful lifetimes. Due to extensive and still-growing use of polymeric materials for technological applications of immense variety, and the fact that radiation-processing has the potential to play an expanding role in polymer manufacturing (current uses include crosslinking, curing, sterilization, surface modification, lithography, etc.), the ability to inhibit unwanted material property changes which often occur when materials are irradiated, and to predict useful lifetimes, remains a limiting factor in a number of existing radiation technologies. Additionally, the ability to control unwanted degradation will be necessary for successful implementation of future, more advanced, radiation processing schemes. This co-ordinated research project (CRP) was established for the purpose of focusing the attention of appropriate technical experts on the complex task of establishing a better fundamental basis for understanding and attacking problems or radiation degradation of materials. The group dynamics have been designed to achieve a synergistic interaction among worldwide research facilities for the purposes of identifying degradation problems, exchanging ideas and results on the solution of these problems, and making the emerging information available in an organized and accessible format. From this meeting, it is clear that much remains to be learnt in terms of understanding degradation mechanisms and phenomena. It also appears that important new

  16. Syntheses, structures, molecular and cationic recognitions and catalytic properties of two lanthanide coordination polymers based on a flexible tricarboxylate

    International Nuclear Information System (INIS)

    Zhu, Yu; Wang, Yan-Mei; Xu, Ji; Liu, Pan; Weththasinha, H.A.B.M.D.; Wu, Yun-Long; Lu, Xiao-Qing; Xie, Ji-Min

    2014-01-01

    Two lanthanide coordination polymers, namely, ([La(TTTA)(H 2 O) 2 ]·2H 2 O) n (La-TTTA) and [Nd(TTTA)(H 2 O) 2 ]·2H 2 O) n (Nd-TTTA) have been hydrothermally synthesized through the reaction of lanthanide ions (La 3+ and Nd 3+ ) with the flexible tripodal ligand 2,2′,2″-[1,3,5-triazine-2,4,6-triyltris(thio)]tris-acetic acid (H 3 TTTA). La-TTTA and Nd-TTTA are isostructural and both show three dimensional structures. La-TTTA and Nd-TTTA show good recognition of amine molecules via quenching the luminescent intensities in amines emulsions. They can also recognize Fe 3+ , Cu 2+ , Mg 2+ , Cr 3+ and Co 2+ ions with the quenching the peak around 361 nm when the compounds immersed in ionic solutions. The two compounds act as efficient Lewis acid catalysts for the cyanosilylation of benzaldehyde and derivatives in high yields shortly due to the strong Lewis acidity and the possible open sites of the lanthanide ions. - Graphical abstract: We have synthesized two isostructural 3D compounds based on H 3 TTTA. They are chemical sensor of amine solvents and cations. They have higher yields and TOFs to catalyze cyanosilylation reactions. - Highlights: • The compounds show recognition of amine molecules via quenching luminescent intensities. • The compounds recognize Fe 3+ , Cu 2+ , Mg 2+ , Cr 3+ and Co 2+ ions via quenching the peak around 361 nm. • They act as efficient Lewis acid catalysts for the cyanosilylation reactions in high yields

  17. Synchrotron X-Ray Charge-Density Study of Coordination Polymer (Mn(HCOO)2(H2O)2)∞

    International Nuclear Information System (INIS)

    Poulsen, Rasmus D.; Jorgensen, Mads R.V.; Overgaard, Jacob; Larsen, Finn K.; Morgenroth, Wolfgang; Graber, Timothy; Chen, Yu-Sheng; Iversen, Bo B.

    2007-01-01

    Three high-quality single-crystal X-ray diffraction data sets have been measured under very different conditions on a structurally simple, but magnetically complex, coordination polymer, (Mn(HCOO) 2 (H 2 O) 2 )∞ (1). The first data set is a conventional 100(2) K Mo Kα data set, the second is a very high resolution 100(2) K data set measured on a second-generation synchrotron source, while the third data set was measured with a tiny crystal on a high brilliance third-generation synchrotron source at 16(2) K. Furthermore, the magnetic susceptibility (χ) and the heat capacity (C p ) have been measured from 2 to 300 K on pressed powder. The charge density of 1 was determined from multipole modeling of the experimental structure factors, and overall there is good agreement between the densities obtained separately from the three data sets. When considering the fine density features, the two 100 K data sets agree well with each other, but show small differences to the 16 K data set. Comparison with ab initio theory suggests that the 16 K APS data set provides the most accurate density. Topological analysis of the metal-ligand bonding, experimental 3d orbital populations on the Mn atoms, and Bader atomic charges indicate quite ionic, high-spin metal atoms. This picture is supported by the effective moment estimated from the magnetization measurements (5.840(2)μ B ), but it is at variance with earlier spin density measurements from polarized neutron diffraction. The magnetic ordering originates from superexchange involving covalent interactions with the ligands, and non-ionic effects are observed in the static deformation density maps as well as in plots of the valence shell charge concentrations. Overall, the present study provides a benchmark charge density that can be used in comparison with future metal formate dihydrate charge densities.

  18. Synchrotron X-ray charge-density study of coordination polymer [Mn(HCOO)2(H2O)2]infinity.

    Science.gov (United States)

    Poulsen, Rasmus D; Jørgensen, Mads R V; Overgaard, Jacob; Larsen, Finn K; Morgenroth, Wolfgang; Graber, Timothy; Chen, Yu-Sheng; Iversen, Bo B

    2007-01-01

    Three high-quality single-crystal X-ray diffraction data sets have been measured under very different conditions on a structurally simple, but magnetically complex, coordination polymer, [Mn(HCOO)(2)(H(2)O)(2)](infinity) (1). The first data set is a conventional 100(2) K Mo(Kalpha) data set, the second is a very high resolution 100(2) K data set measured on a second-generation synchrotron source, while the third data set was measured with a tiny crystal on a high brilliance third-generation synchrotron source at 16(2) K. Furthermore, the magnetic susceptibility (chi) and the heat capacity (C(p)) have been measured from 2 to 300 K on pressed powder. The charge density of 1 was determined from multipole modeling of the experimental structure factors, and overall there is good agreement between the densities obtained separately from the three data sets. When considering the fine density features, the two 100 K data sets agree well with each other, but show small differences to the 16 K data set. Comparison with ab initio theory suggests that the 16 K APS data set provides the most accurate density. Topological analysis of the metal-ligand bonding, experimental 3d orbital populations on the Mn atoms, and Bader atomic charges indicate quite ionic, high-spin metal atoms. This picture is supported by the effective moment estimated from the magnetization measurements (5.840(2) mu(B)), but it is at variance with earlier spin density measurements from polarized neutron diffraction. The magnetic ordering originates from superexchange involving covalent interactions with the ligands, and non-ionic effects are observed in the static deformation density maps as well as in plots of the valence shell charge concentrations. Overall, the present study provides a benchmark charge density that can be used in comparison with future metal formate dihydrate charge densities.

  19. Syntheses, crystal structures, and properties of four coordination polymers based on mixed multi-N donor and polycarboxylate ligands

    Science.gov (United States)

    Chen, Shui-Sheng; Guo, Xing-Zhe; Zhao, Yue; Li, Wei-Dong

    2018-02-01

    Four new coordination polymers [Ni2(HL1)2(L1)3(BTC)2]·6H2O (1), [Ni2(L1)3(HBTC)2]·4H2O (2), [Cd2(L2)(BTC)(H2O)3]·2H2O (3) and [Cd2(HL2)(BTCA)] (4) were synthesized by reactions of nickel(II)/ cadmium(II) salts with rigid ligands of 1,4-di(1H-imidazol-4-yl)benzene (L1), 1,3-di(1-imidazolyl)-5-(4H-tetrazol-5-yl)benzene (HL2) and polycarboxylic acids of 1,3,5-benzenetricarboxylic acid (H3BTC), 1,2,4,5-benzenetetracarboxylic acid (H4BTCA), respectively. The structures of the complexes were determined by single crystal X-ray diffraction analysis. The complex 1 is one-dimensional (1D) chain while 2 is a (4, 4)-connected two-dimensional (2D) layered structure with 2D → 2D parallel interpenetration. Complex 3 is a rare tetranodal (3,4)-connected three-dimensional (3D) CrVTiSc architecture with Point (Schläfli) symbol of (4·82)(4·84·10)(42·82·102)(83), and compound 4 has the 2D network with (4,4) topology based on the [Cd2(COO)4] SBUs. The weak interactions such as hydrogen bonds and π···π stacking contribute to stabilize crystal structure and extend the low-dimensional entities into high-dimensional frameworks. The UV-vis absorption spectra of 1 - 4 are discussed. Moreover, the photo luminescent properties of 3 and 4 and gas sorption property of 2 have been investigated.

  20. Chelating Schiff base assisted azide-bridged Mn(II), Ni(II) and Cu(II) magnetic coordination polymers.

    Science.gov (United States)

    Bai, Shi-Qiang; Fang, Chen-Jie; He, Zheng; Gao, En-Qing; Yan, Chun-Hua; Hor, T S Andy

    2012-11-21

    Four new Mn(II), Ni(II) and Cu(II) coordination polymers [Mn2(L1)(μ(1,1)-N3)2(μ(1,3)-N3)2]n (1), [Ni(L2)2(μ(1,3)-N3)]n(ClO4)n (2), [Cu(L3)(μ(1,1)-N3)(N3)]n (3) and [Cu(L4)(μ(1,1)-N3)2]n (4) (L1 = N,N′-bis(2-pyridylmethylene)ethane-1,2-diamine, L2 = N-(2-pyridylmethylene)methylamine, L3 = N-(2-pyridylmethylene)-3-pyridylamine, L4 = N-(2-pyridylmethylene)-tbutylamine) have been synthesized and characterized by single-crystal X-ray analysis and magnetic measurements. Complex 1 indicates a stoichiometry-dependent structural change (based on Mn:L1:N3 = 2:1:4 molar ratio) and consists of two-dimensional (2-D) (4,4) net layers, in which Mn(II) centers are co-bridged by single end-to-end (EE), double end-on (EO) azide and chelate-bridging L1 ligands. Complex 2 shows a single EE azide-bridged one-dimensional (1-D) Ni(II) chain. Complexes 3 and 4 indicate single EO and double EO azide-bridged 1-D Cu(II) chains, respectively. Complex 1 exhibits weak ferromagnetism due to its intra-layer spin-canting with T(c) = 20 K. Complex 2 shows an unusual intra-chain ferromagnetic coupling and spin-canting behaviour. Both complexes 3 and 4 exhibit intra-chain antiferromagnetic interactions. Magneto-structural parameters for these related complexes were also discussed.

  1. Cyanide-Assembled d10Coordination Polymers and Cycles: Excited State Metallophilic Modulation of Solid-State Luminescence.

    Science.gov (United States)

    Belyaev, Andrey; Eskelinen, Toni; Dau, Thuy Minh; Ershova, Yana Yu; Tunik, Sergey P; Melnikov, Alexei S; Hirva, Pipsa; Koshevoy, Igor O

    2018-01-26

    The series of cyanide-bridged coordination polymers [(P 2 )CuCN] n (1), [(P 2 )Cu{M(CN) 2 }] n (M=Cu 3, Ag 4, Au 5) and molecular tetrametallic clusters [{(P 4 )MM'(CN)} 2 ] 2+ (MM'=Cu 2 6, Ag 2 7, AgCu 8, AuCu 9, AuAg 10) were obtained using the bidentate P 2 and tetradentate P 4 phosphane ligands (P 2 =1,2-bis(diphenylphosphino)benzene; P 4 =tris(2-diphenylphosphinophenyl)phosphane). All title complexes were crystallographically characterized to reveal a zig-zag chain arrangement for 1 and 3-5, whereas 6-10 possess metallocyclic frameworks with different degree of metal-metal bonding. The d 10 -d 10 interactions were evaluated by the quantum theory of atoms in molecules (QTAIM) computational approach. The photophysical properties of 1-10 were investigated in the solid state and supported by theoretical analysis. The emission of compounds 1 and 3-5, dominated by metal-to-ligand charge transfer (MLCT) transitions located within {CuP 2 } motifs, is compatible with thermally activated delayed fluorescence (TADF) behaviour and a small energy gap between the T 1 and S 1 excited states. The luminescence characteristics of 6-10 are strongly dependent on the composition of the metal core; the emission band maxima vary in the range 484-650 nm with quantum efficiency reaching 0.56 (6). The origin of the emission for 6-8 and 10 at room temperature is assigned to delayed fluorescence. AuCu cluster 9, however, exhibits only phosphorescence that corresponds to theoretically predicted large value ΔE(S 1 -T 1 ). DFT simulation highlights a crucial impact of metallophilic bonding on the nature and energy of the observed emission, the effect being greatly enhanced in the excited state. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  2. Mixed sulfoisophthalate and 1,2,4-triazole directed d10 metal coordination polymers: Synthesis, property and structural diversity

    Science.gov (United States)

    Liu, Bing; Guo, Kai; Feng, Hui-Jun; Miao, Wei-Ni; He, Ting-Ting; Xu, Ling

    2017-10-01

    This work presents six d10-metal coordination polymers based on mixed ligands of 5-sulfoisophthalate (H2SIP-) and 1,2,4-triazoles (1H-1,2,4-triazole (Htr), 3-amino-1H-1,2,4-triazole (Hatr)), 3D [Zn7(SIP)2(tr)8(H2O)4]·4H2O (1), 3D [Zn4(SIP)(atr)5(H2O)2]·3H2O (2), 2D [Zn2(SIP)(atr)(H2O)3]·2H2O (3), 2D [Ag(H2SIP)(Hatr)] (4 and 5), and 3D [Cd3(SIP)(tr)2(OH)]·H2O (6) under hydrothermal conditions. The structural analysis indicates a ligand directed structural diversity in the metal-(H)SIP-triazole system. The characterizations of 1-6 indicate that the bulk samples are pure phases, the thermal decomposition temperatures are beyond 300 °C, and the fluorescence are blue. The maximum emissions of 1-3 and 6 at around 410 nm are related with the intraligand π→π* transitions of 1,2,4-triazole moieties, and those at ca. 350 nm in 4 and 5 are assigned to intraligand transitions of (H)SIP ligands. The temperature-dependent fluorescence of 1-6 show thermal quenchings with fluorescence quenching rates ranging 22.9-74.2%, and the fluorescence cannot recover fully when it is back to ambient temperature.

  3. SYNTHESIS AND STRUCTURAL CHARACTERIZATION OF A Zn(II COORDINATION POLYMER BASED ON 4,4’-BIPYRIDINE AND ACETATO

    Directory of Open Access Journals (Sweden)

    LI-HUA WANG

    2015-05-01

    Full Text Available A novel Zn(II coordination polymer, [Zn(bpy(acetato2]n (bpy = 4,4’-bipyridine, has been synthesized and characterized by elemental analysis and single-crystal X-ray diffraction. The Zn(II coordination polymer is triclinic, space group P-1 with a = 8.046(3 Å, b = 9.161(3 Å, c = 10.663(3 Å, α = 109.769(4º, β = 99.966(5º, γ = 101.666(5º, V= 699.1(4 Å3, Z = 2, Dc = 1.614 mg·m-3, μ = 1.774 mm-1, F(000 = 348, and final R1 = 0.0541, ωR2 = 0.1605. X-ray diffraction analysis reveals that the Zn(II center is six-coordination with a N2O4 distorted octahedral coordination environment. The Zn(II complex forms 1D chain structure by the bridge of 4,4’-bipyridine and acetato.

  4. Facile synthesis of 2D Zn(II) coordination polymer and its crystal structure, selective removal of methylene blue and molecular simulations

    Science.gov (United States)

    Sezer, Güneş Günay; Yeşilel, Okan Zafer; Şahin, Onur; Arslanoğlu, Hasan; Erucar, İlknur

    2017-09-01

    A new coordination polymer {[Zn(μ3-ppda)(H2O)(μ-bpa)Zn(μ-ppda)(μ-bpa)]·4H2O}n (1) (ppda = 1,4-phenylenediacetate, bpa = 1,2-bis(4-pyridyl)ethane) has been synthesized by microwave-assisted reaction and characterized by elemental analysis, IR spectroscopy, single-crystal and powder X-ray diffractions. The asymmetric unit of 1 consists of two Zn(II) ions, two bpa ligands, two ppda ligands, one coordinated and four non-coordinated water molecules. In 1, ppda2- anions are linked the adjacent Zn(II) centers to generate 1D double-stranded chains. These chains are connected into 2D sheets by the bridging bpa ligands. Atomically detailed modeling was performed to compute single and binary component adsorption isotherms of H2, CO2, CH4 and N2 in complex 1. Results showed that 1 exhibits a high adsorption selectivity towards CO2 due to its high affinity for CO2. Results of this study will be helpful to guide the microwave-assisted reaction of coordination polymers to design promising adsorbents for gas storage and gas separation applications. The luminescent property of 1 and the selective removal of dyes in 1 have been also discussed. Results showed that 1 can be a potential candidate for luminescence applications and can selectively adsorb methylene blue (MB) dye molecules.

  5. Mercury coordination polymers with flexible ethane-1,2-diyl-bis-(pyridyl-3-carboxylate): Synthesis, structures, thermal and luminescent properties

    Energy Technology Data Exchange (ETDEWEB)

    Vallejos, Javier [Departamento de Química, Universidad Católica del Norte, Av. Angamos 0610, Antofagasta (Chile); Brito, Iván, E-mail: ivanbritob@yahoo.com [Departamento de Quimica, Universidad de Antofagasta, Av. Angamos 601, Antofagasta (Chile); Cárdenas, Alejandro [Departamento de Física, Universidad de Antofagasta, Av. Angamos 601, Antofagasta (Chile); Llanos, Jaime [Departamento de Química, Universidad Católica del Norte, Av. Angamos 0610, Antofagasta (Chile); Bolte, Michael [Institut für Anorganische Chemie der Goethe—Universität Frankfurt, Max-von-Laue-Strasse 7, D-60438 Frankfurt am Main (Germany); López-Rodríguez, Matías [Instituto de Bio-Orgánica “Antonio González”, Universidad de La Laguna, Astrofísico Francisco Sánchez N° 2, La Laguna, Tenerife (Spain)

    2015-03-15

    The reaction of the flexible ligand, ethane-1,2-diyl-bis-(pyridyl-3-carboxylate), (L) with HgI{sub 2} and HgBr{sub 2} salts under the same experimental conditions leads to the formation of two coordination polymers with different motifs: ([Hg(L)(Br{sub 2})]){sub n}(1) and ([Hg(L)(I{sub 2})]){sub n}(2). In both compounds, the ligand, (L) acts in a μ2-N:N′-bidentate fashion to link HgBr{sub 2} and HgI{sub 2} units to form a linear and helical chain motif, along [1 0 0] for (1) and [0 0 1] for (2). The ethylene moiety of (L) has gauche and trans conformation in compounds (1) and (2), respectively. The flexible conformation of L produces differences in the optical and crystal properties of the two compounds. - Graphical abstract: This work demonstrates how the HgX{sub 2} units are coordinates by bi-dentate ligand forming polymeric coordination complexes by self-assembly of both chemical units.- Highlights: • News 1-D d{sup 10} transition metal coordination polymers. • The photoluminescent properties have been measured. • The thermal properties have been measured.

  6. Syntheses, structures, and magnetic properties of cobalt(II) and nickel(II) coordination polymers based on a V-shaped ligand

    Energy Technology Data Exchange (ETDEWEB)

    Yao, Shuang [State Key Laboratory of Rare Earth Resource Utilization, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, 5625 Renmin Street, Changchun 130022 (China); Yi, Fei-Yan [The School of Materials Science and Chemical Engineering, Ningbo University, Ningbo 315211 (China); Li, Guanghua [State Key Laboratory of Inorganic Synthesis & Preparative Chemistry, College of Chemistry, Jilin University, Changchun 130012 (China); Yu, Yang [State Key Laboratory of Rare Earth Resource Utilization, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, 5625 Renmin Street, Changchun 130022 (China); Wang, Jing-yuan, E-mail: jywang@mail.ipc.ac.cn [Technical Institute of Physics and Chemistry of the Chinese Academy of Sciences, 29 Zhongguancun East Road, Haidian District, Beijing 100190 (China); Liu, Dan, E-mail: liudan2007@ciac.ac.cn [State Key Laboratory of Rare Earth Resource Utilization, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, 5625 Renmin Street, Changchun 130022 (China); Song, Shu-Yan [State Key Laboratory of Rare Earth Resource Utilization, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, 5625 Renmin Street, Changchun 130022 (China)

    2017-06-15

    Two coordination polymers [Co{sub 2}(TA)(4,4′-bipy){sub 2}(H{sub 2}O){sub 2}]·H{sub 2}O (1) and [Ni{sub 2}(TA)(4,4′-bipy){sub 2}(H{sub 2}O){sub 4}]·3H{sub 2}O (2) were prepared by hydrothermal reactions of MCl{sub 2}·6H{sub 2}O (M = Co, Ni) with a V-shaped ligand TDPA (3,3′,4,4′-thiodiphthalic anhydride) and a I-shaped N-donor co-ligand (4,4′-bipy). They were characterized by elemental analyses, thermogravinetric analyses, and magnetic behavior. As is expected, TDPA hydrolyzes into the corresponding tetra-carboxylate acid H{sub 4}TA (3,3′,4,4′-thiodiphthalic acid) during the reactions. Co{sub 2} dimer and Ni mononuclear center are connected into two-dimensional (2D) layers by H{sub 4}TA and 4,4′-bipy bridge in 1 and 2, respectively. The most amazing feature is that 1 and 2 exhibit interesting spin-canting metamagnetism and weak ferromagnetic behavior, respectively, with the critical Néel temperature of T{sub N} =4 K for 1 and T{sub N} =13 K for 2, based on variable temperature magnetic susceptibility measurements. In low mono- or dinuclear metal system, such magnetic behaviors have rare been observed. Furthermore, complex 1 will be a potential metamagnet material. - Graphical abstract: Two Co(II) and Ni(II) coordination polymers were synthesized by hydrothermal reactions from a V-shape ligand (3,3′,4,4′-thiodiphthalic anhydride) and a I-shape ligand (4,4′-bipy), which were characterized by single crystal X-ray diffraction, elemental analyses, thermogravinetric analyses, and magnetic behavior, and exhibit interesting spin-canting metamagnetism and weak ferromagnetic behavior, respectively. - Highlights: • Two Co(II) and Ni(II) coordination polymers were successfully synthesized. • Co(II) coordination polymer shows an interesting spin-canting metamagnetism. • Ni(II) coordination polymer exhibits a weak ferromagnetic behavior.

  7. Recent advances in polymer solar cells: realization of high device performance by incorporating water/alcohol-soluble conjugated polymers as electrode buffer layer.

    Science.gov (United States)

    He, Zhicai; Wu, Hongbin; Cao, Yong

    2014-02-01

    This Progress Report highlights recent advances in polymer solar cells with special attention focused on the recent rapid-growing progress in methods that use a thin layer of alcohol/water-soluble conjugated polymers as key component to obtain optimized device performance, but also discusses novel materials and device architectures made by major prestigious institutions in this field. We anticipate that due to drastic improvements in efficiency and easy utilization, this method opens up new opportunities for PSCs from various material systems to improve towards 10% efficiency, and many novel device structures will emerge as suitable architectures for developing the ideal roll-to-roll type processing of polymer-based solar cells. © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  8. Two-dimensional Zn(II) and one-dimensional Co(II) coordination polymers based on benzene-1,4-dicarboxylate and pyridine ligands.

    Science.gov (United States)

    Zhou, Li-Juan; Han, Chang-Bao; Wang, Yu-Ling

    2016-02-01

    Coordination polymers constructed from metal ions and organic ligands have attracted considerable attention owing to their diverse structural topologies and potential applications. Ligands containing carboxylate groups are among the most extensively studied because of their versatile coordination modes. Reactions of benzene-1,4-dicarboxylic acid (H2BDC) and pyridine (py) with Zn(II) or Co(II) yielded two new coordination polymers, namely, poly[(μ4-benzene-1,4-dicarboxylato-κ(4)O:O':O'':O''')(pyridine-κN)zinc(II)], [Zn(C8H4O2)(C5H5N)]n, (I), and catena-poly[aqua(μ3-benzene-1,4-dicarboxylato-κ(3)O:O':O'')bis(pyridine-κN)cobalt(II)], [Co(C8H4O2)(C5H5N)2(H2O)]n, (II). In compound (I), the Zn(II) cation is five-coordinated by four carboxylate O atoms from four BDC(2-) ligands and one pyridine N atom in a distorted square-pyramidal coordination geometry. Four carboxylate groups bridge two Zn(II) ions to form centrosymmetric paddle-wheel-like Zn2(μ2-COO)4 units, which are linked by the benzene rings of the BDC(2-) ligands to generate a two-dimensional layered structure. The two-dimensional layer is extended into a three-dimensional supramolecular structure with the help of π-π stacking interactions between the aromatic rings. Compound (II) has a one-dimensional double-chain structure based on Co2(μ2-COO)2 units. The Co(II) cations are bridged by BDC(2-) ligands and are octahedrally coordinated by three carboxylate O atoms from three BDC(2-) ligands, one water O atom and two pyridine N atoms. Interchain O-H...O hydrogen-bonding interactions link these chains to form a three-dimensional supramolecular architecture.

  9. Construction of new 1D and 2D coordination polymers generated from rigid N,N′-bis(4-pyridylmethylene)-1,5-naphthalenediamine ligand : Syntheses, crystal structures and luminescence properties

    NARCIS (Netherlands)

    Shaabani, Behrouz; Rad-Yousefnia, Negar; Zahedi, Mansoureh; Ertan, Şahin; Blake, Graeme R.; Zakerhamidi, Mohammad Sadegh

    2017-01-01

    Treatment of N,N′-bis(4-pyridylmethylene)-1,5-naphthalenediamine (L) with Pb(OAc)2/KBr, Cu(acac)2, and Cu(OAc)2 afforded three new coordination polymers [Pb(μ-L)(μ-Br)2]n (1), [Cu(μ-L)(acac)2]n (2), and [Cu2(μ-L)(μ-OAc)4]n (3). These coordination polymers have been structurally characterized by

  10. Effects of Cholesterol Incorporation on the Physicochemical, Colloidal, and Biological Characteristics of pH-sensitive AB2 Miktoarm Polymer-Based Polymersomes

    Science.gov (United States)

    Yin, Haiqing; Kang, Han Chang; Huh, Kang Moo; Bae, You Han

    2014-01-01

    In our previous study, a histidine-based AB2 miktoarm polymer, methoxy poly(ethylene glycol)-b-poly(l-histidine)2 (mPEG-b-(PolyHis)2), was designed to construct pH-sensitive polymersomes that transform in acidic pH; the polymer self-assembles into a structure that mimics phospholipids. In this study, the polymersomes further imitated liposomes due to the incorporation of cholesterol (CL). The hydrodynamic radii of the polymersomes increased with increasing CL wt% (e.g., 70 nm for 0 wt% vs. 91 nm for 1 wt%), resulting in an increased capacity for encapsulating hydrophilic drugs (e.g., 0.92 µL/mg for 0 wt% vs. 1.42 µL/mg for 1 wt%). The CL incorporation enhanced the colloidal stability of the polymersomes in the presence of serum protein and retarded their payload release. However, CL-incorporating polymersomes still demonstrated accelerated release of a hydrophilic dye (e.g., 5(6)-carboxyfluorescein (CF)) below pH 6.8 without losing their desirable pH sensitivity. CF-loaded CL-incorporating polymersomes showed better cellular internalization than the hydrophilic CF, whereas doxorubicin (DOX)-loaded CL-incorporating polymersomes presented similar or somewhat lower anti-tumor effects than free hydrophobic DOX. The findings suggest that CL-incorporating mPEG-b-(PolyHis)2-based polymersomes may have potential for intracellular drug delivery of chemical drugs due to their improved colloidal stability, lower drug loss during circulation, acidic pH-induced drug release, and endosomal disruption. PMID:24463148

  11. Low band-gap polymers incorporating benzotriazole and 5,6-dialkoxy-benzothiadiazole as solution processable electrochromic materials

    Directory of Open Access Journals (Sweden)

    W. T. Neo

    2015-06-01

    Full Text Available Two series of donor-acceptor type conjugated polymers bearing benzotriazole or 5,6-dialkoxy-benzothiadiazole as acceptors unit are synthesized via Stille coupling. The optical, electrochemical, spectroelectrochemical characterizations and theoretical calculations are carried out. The polymers display excellent solubility in common organic solvents upon the introduction of long aliphatic side chains. The electrochromic performances of the polymers are also studied. Upon oxidation, the polymers switch from magenta or blue to a transmissive light blue state. In particular, respectable optical contrasts of about 44 and 40% are obtained in the visible and near infrared (NIR region respectively for P2. The polymers also reveal fast switching of about from one second to a few seconds. In addition, P2 exhibits a high coloration efficiency of 518 and 561 cm2/C in the visible and NIR region respectively. The promising electrochromic behaviour of these polymers, together with the enhanced solubility will allow large-scale processing and advancement towards real applications.

  12. Thiourea incorporated poly(ethylene oxide) as transparent gel polymer electrolyte for dye sensitized solar cell applications

    Science.gov (United States)

    Pavithra, Nagaraj; Velayutham, David; Sorrentino, Andrea; Anandan, Sambandam

    2017-06-01

    A new series of transparent gel polymer electrolytes are prepared by adding various weight percent of thiourea coupled with poly(ethylene oxide) for the application of dye-sensitized solar cells. Coupling of thiourea in the presence of iodine undergoes dimerization reaction to produce formamidine disulfide. Fourier Transform Infrared spectroscopy shows that the interactions of thiourea and formamidine disulfide with electronegative ether linkage of poly(ethylene oxide) results in conformational changes of gel polymer electrolytes. Electrochemical impedance spectroscopy and linear sweep voltammetry experiments reveal an increment in ionic conductivity and tri-iodide diffusion coefficient, for thiourea modified gel polymer electrolytes. Finally, the prepared electrolytes are used as a redox mediator in dye-sensitized solar cells and the photovoltaic properties were studied. Apart from transparency, the gel polymer electrolytes with thiorurea show higher photovoltaic properties compared to bare gel polymer electrolyte and a maximum photocurrent efficiency of 7.17% is achieved for gel polymer electrolyte containing 1 wt% of thiourea with a short circuit current of 11.79 mA cm-2 and open circuit voltage of 834 mV. Finally, under rear illumination, almost 90% efficiency is retained upon compared to front illumination.

  13. Synthesis, Structural Characterization and Catalytic Activity of A Cu(II Coordination Polymer Constructed from 1,4-Phenylenediacetic Acid and 2,2’-Bipyridine

    Directory of Open Access Journals (Sweden)

    Wang Li-Hua

    2017-04-01

    Full Text Available In order to study the catalytic activity of Cu(II coordination polymer material, a novel 1D chained Cu(II coordination polymer material, [CuL(bipy(H2O5]n (A1 (H2L = 1,4-phenylenediacetic acid, bipy = 2,2’-bipyridine, has been prepared by the reaction of 1,4-phenylenediacetic acid, 2,2’-bipyridine, Cu(CH3COO2·H2O and NaOH. The composition of A1 was determined by elemental analysis, IR spectra and single crystal X-ray diffraction. The results of characterization show that each Cu(II atom adopts six-coordination and forms a distorted octahedral configuration. The catalytic activity and reusability of A1 catalyst for A3 coupling reaction of benzaldehyde, piperidine, and phenylacetylene have been investigated. And the results show that the Cu(II complex catalyst has good catalytic activity with a maximum yield of 54.3% and stability. Copyright © 2017 BCREC GROUP. All rights reserved Received: 21st October 2016; Revised: 17th November 2016; Accepted: 22nd November 2016 How to Cite: Li-Hua, W., Lei, L., Xin, W. (2017. Synthesis, Structural Characterization and Catalytic Activity of A Cu(II Coordination Polymer Constructed from 1,4-Phenylenediacetic Acid and 2,2’-Bipyridine. Bulletin of Chemical Reaction Engineering & Catalysis, 12 (1: 113-118 (doi:10.9767/bcrec.12.1.735.113-118 Permalink/DOI: http://dx.doi.org/10.9767/bcrec.12.1.735.113-118

  14. 2-(hydroxymethyl)-1H-benzo[d]imidazole-5-carboxylic acid as linker for Co(II)/Ni(II)/Cu(II) coordination polymers: Synthesis, structures and properties

    Science.gov (United States)

    Wang, Duo-Zhi; Wang, Xin-Fang; Du, Jia-Qiang; Dong, Jun-Liang; Xie, Fei

    2018-02-01

    We report the synthesis and characterization of five transition metal coordination polymers (CPs) based on M(II) (M: Co, Ni and Cu), 2-(hydroxymethyl)-1H-benzo[d]imidazole-5-carboxylic acid (H2L) ligand. They are formulated as {[Co2(HL)2(H2O)3(SO4)]·H2O}n (1), {[Co2(HL)2(H2O)2]·SiF6}n (2), {[Ni2(HL)2(H2O)3(SO4)]·2H2O}n (3), {[Ni2(HL)2(H2O)4]·H2O·SiF6}n (4), {[Cu2(HL)2(H2O)2]·SiF6}n (5). The complexes 1-5 structure were characterized by single-crystal X-ray diffraction, elemental analyses, infrared spectroscopy (IR), powder X-ray diffraction (PXRD), and thermogravimetric analyses (TGA). Complexes 1-5 are two-dimensional (2D) network type coordination polymers that 1-3, 5 crystallize in monoclinic system within the centrosymmetric space group P2(1)/c, and 4 in triclinic system P-1 space group, they show the same coordination modes (κ1-κ1)-(κ1)-(κ1)-μ3 in coordination polymers. Complexes 1 and 3 expand to three-dimensional framework by means of hydrogen bond interactions, and can be rationalized to be three-connected {63} topological network, while 2, 4, 5 exhibit the topological network with a four-connected {44·62} topological sql network. The luminescent properties (for complexes 1, 2) and UV diffuse reflectance (for complexes 1-5) in the solid state at room temperature were also investigated and discussed. Complexes 1-5 act as effective heterogeneous catalysts, under mild conditions, for the homocoupling reaction of 4-substituted aryl iodides bearing electron-donating groups (-CH3, -OCH3).

  15. A two-dimensional zinc(II) coordination polymer based on mixed dimethyl succinate and bipyridine ligands: synthesis, structure, thermostability and luminescence properties.

    Science.gov (United States)

    Liu, Yang; Feng, Yong Lan; Fu, Wei Wei

    2016-04-01

    From the viewpoint of crystal engineering, the construction of crystalline polymeric materials requires a rational choice of organic bridging ligands for the self-assembly process. Multicarboxylate ligands are of particular interest due to their strong coordination activity towards metal ions, as well as their various coordination modes and versatile conformations. The structural chemistry of dicarboxylate-based coordination polymers of transition metals has been developed through the grafting of N-containing organic linkers into carboxylate-bridged transition metal networks. A new luminescent two-dimensional zinc(II) coordination polymer containing bridging 2,2-dimethylsuccinate and 4,4'-bipyridine ligands, namely poly[[aqua(μ2-4,4'-bipyridine-κ(2)N:N')bis(μ3-2,2-dimethylbutanedioato)-κ(4)O(1),O(1'):O(4):O(4');κ(5)O(1):O(1),O(4):O(4),O(4')-dizinc(II)] dihydrate], {[Zn2(C6H8O4)2(C10H8N2)(H2O)]·2H2O}n, has been synthesized under hydrothermal conditions and characterized by single-crystal X-ray diffraction and elemental, IR and thermogravimetric analyses. In the structure, the 2,2-dimethylsuccinate ligands link linear tetranuclear Zn(II) subunits into one-dimensional chains along the c axis. 4,4'-Bipyridine acts as a tethering ligand expanding these one-dimensional chains into a two-dimensional layered structure. Hydrogen-bonding interactions between the water molecules (both coordinated and free) and carboxylate O atoms strengthen the packing of the layers. Furthermore, the luminescence properties of the complex were investigated. The compound exhibits a blue photoluminescence in the solid state at room temperature and may be a good candidate for potential hybrid inorganic-organic photoactive materials.

  16. Hydrothermal synthesis and crystal structure of a europium(III) coordination polymer with 5-sulfoisophthalate trivalent anions and free 4, 4'-bipyridine molecules

    International Nuclear Information System (INIS)

    Lin Humao; Qing Caixiao; Qian Miao; Ping Xiaohong

    2005-01-01

    A novel europium(III) coordination polymer [Eu(Sip)(H 2 O) 5 ] n · nH 2 O · 1.5 n(Bipy) (I) (Sip is 5-sulfoisophthalate trivalent anion and Bipy is 4,4'-bipyridine) is hydrothermally synthesized and determined by the single crystal X-ray diffraction method. Polymer I crystallizes in the monoclinic system, space group C2/c with a = 30.7515(6), b = 10.9577(2), c = 17.5545(4) A, β = 112.040(1) deg, Z = 4. In I, each Eu 3+ ion is coordinated by four oxygen atoms from two carboxylate groups of two different Sip anions and five oxygen atoms from five coordinated water molecules to complete a deformed mono-cap square antiprism. Moreover, each Sip anion acts as a tetradentate ligand to connect two adjacent Eu 3+ ions through its two chelating carboxylate groups, resulting in one-dimensional linear chains. In addition, fifteen different kinds of hydrogen-bonding interactions link the chains, lattice water molecules, and free Bipy molecules to engender a complicated hydrogen-bonding network [ru

  17. Synthesis and Molecular Structures of Two [1,4-bis(3-pyridyl-2,3-diazo-1,3-butadiene]-dichloro-Zn(II Coordination Polymers

    Directory of Open Access Journals (Sweden)

    Hsin-Ta Wang

    2006-08-01

    Full Text Available Two novel coordination polymers with 3D metal-organic frameworks (MOFs have been synthesized by reacting 1,4-bis(3-pyridyl-2,3-diazo-1,3-butadiene (L with zinc dichloride. Both compounds have the same repeating unit consisting of a distorted tetrahedral Zn(II center coordinated by two chlorides and two pyridyl nitrogen atoms of two bridging bismonodentate L ligands, however, different structural conformations have been found, one forming a helical chain and the other producing a square-wave chain. The intermolecular C−H···Cl hydrogen bonds in 1 and 2 play important roles in the formation of three-dimensional coordination polymers. Compound 1 crystallized in an orthorhombic space group Pna21 with a = 7.9652(3, b = 21.4716(7, c = 8.2491(3Å, V = 1410.81(9 Å 3 and Z = 4. Compound 2 crystallized in a monoclinic space group P21/n with a = 9.1752(3, b = 14.5976(4, c = 10.3666(3 Å , β = 98.231(2°, V = 1374.16(7 Å 3 and Z = 4.

  18. One novel 1D coordination polymer with parallel dinuclear copper(II) macrocyclic platforms bridged by trans dimeric half-water molecules and two dinuclear copper(II) macrocyclic complexes with different coordination geometry obtained from different solvents

    Science.gov (United States)

    Chu, Zhaolian; You, Wei; Huang, Wei

    2009-02-01

    Three dinuclear copper(II) macrocyclic complexes, formulated as [Cu 2L(N 3) 2(0.5H 2O) 2] n ( 1), [Cu 2L(ClO 4) 2(CH 3CH 2OH)] ( 2) and [Cu 2L(CH 3OH) 2](ClO 4) 2 ( 3) (LH 2 = [2+2] Schiff base macrocyclic ligand condensed from 4-chloro-2,6-diformylphenol and 1,3-diaminopropane), have been prepared and determined by X-ray single-crystal diffraction. Complex 1 shows two six-coordinate Cu(II) centers in which two monodentate N3- anions and two half-water molecules are bonded at the apical positions in the trans configuration. Furthermore, the dimeric half-water molecules serve as a μ2-bridge linking adjacent macrocyclic units together with the multiple O sbnd H…N hydrogen bonds with azide anions, forming a novel 1D chain-like coordination polymer. Complexes 2 and 3 are obtained from different solvents (ethanol and methanol) and they can be converted into each other. The molecular structures and packing mode of 2 and 3 are different where six-coordinate and five-coordinate copper(II) centers are present, respectively.

  19. Heterobimetallic thiocyanato-bridged coordination polymers based on [Hg(SCN)4]2-: Synthesis, crystal structure, magnetic properties and ESR studies

    International Nuclear Information System (INIS)

    Jian Fangfang; Xiao Hailian; Liu Faqian

    2006-01-01

    Three new M/Hg bimetallic thiocyanato-bridged coordination polymers; [Hg(SCN) 4 Ni(Im) 3 ] ∞ 1, [Hg(SCN) 4 Mn(Im) 2 ] ∞ 2, and [Hg(SCN) 4 Cu(Me-Im) 2 Hg(SCN) 4 Cu(Me-Im) 4 ] ∞ 3, (Im=imidazole, Me-Im=N-methyl-imidazole), have been synthesized and characterized by means of elemental analysis, ESR, and single-crystal X-ray. X-ray diffraction analysis reveals that these three complexes all form 3D network structure, and their structures all contain a thiocyanato-bridged Hg...Hg chain (M=Mn, Ni, Cu) in which the metal and mercury centers exhibit different coordination environments. In complex 1, the [Hg(SCN) 4 ] 2- anion connects three [Ni(Im) 3 ] 2+ using three SCN ligands giving rise to a 3D structure, and in complex 2, four SCN ligands bridge [Hg(SCN) 4 ] 2- and [Mn(Im) 2 ] 2+ to form a 3D structure. The structure of 3 contains two copper atoms with distinct coordination environment; one is coordinated by four N-methyl-imidazole ligands and two axially elongated SCN groups, and another by four SCN groups (two elongated) and two N-methyl-imidazole ligands. The magnetic property of complex 1 has been investigated. The spin state structure in hetermetallic NiHgNi systems of complex 1 is irregular. The ESR spectra results of complex 3 demonstrate Cu 2+ ion lie on octahedral environment. -- Graphical abstract: Three new M/Hg bimetallic thiocyanato-bridged coordination polymers; [Hg(SCN) 4 Ni(Im) 3 ] ∞ 1, [Hg(SCN) 4 Mn(Im) 2 ] ∞ 2, and [Hg(SCN) 4 Cu(Me-Im) 2 Hg(SCN) 4 Cu(Me-Im) 4 ] ∞ 3, (Im=imidazole, Me-Im=N-methyl-imidazole), have been synthesized and characterized by single-crystal X-ray. All coordination polymers possess 3-D structures, and consist of organic base neutral ligands (imidazole and N-methyl-imidazole) and SCN -1 anions. Their structural difference is mainly caused by the role of the organic base and metal ions. The complex 1 shows the irregular spin state structure

  20. Specific features of absorption and DSC for the DEA-CuCl4 nanoparticles incorporated into the PMMA polymer matrices

    Czech Academy of Sciences Publication Activity Database

    Ozga, K.; Piasecki, M.; Tkaczyk, S.; Kapustianyk, B.; Bragiel, P.; Reshak, Ali H; Brig, M.G.; Kityk, I. V.

    2008-01-01

    Roč. 403, č. 17 (2008), s. 2561-2566 ISSN 0921-4526 Institutional research plan: CEZ:AV0Z60870520 Keywords : nanocrystallites * polymer nanocomposites * optical materials Subject RIV: BO - Biophysics Impact factor: 0.822, year: 2008

  1. Radiation synthesis and modification of polymers for biomedical applications. Final results of a co-ordinated research project. 1996-2000

    CERN Document Server

    2002-01-01

    Radiation techniques are being used for synthesis of hydrogels, functional polymers, interpenetrating systems, chemical modification of surfaces, immobilization of bioactive materials, synthesis of functional micro- and nanospheres and processing of naturally derived biomaterials. Potential medical applications of these biomaterials include implants, topical dressings, treatment devices and drug delivery systems. Biotechnological applications include diagnostic assays, separation and purification systems, immobilized enzyme and cell bioprocesses and cell culture surfaces. The main objective of the CRP on The use of Radiation Processing to Prepare Biomaterials for Application in Medicine was to co-ordinate the research carried out in the participating countries, to ensure that different research programmes complement each other and the information exchange is available to all. Furthermore, the objective was to expand the use of ionizing radiation in two major areas: synthesis of polymers and gels for medical a...

  2. Hydrostatic Stress Effects Incorporated Into the Analysis of the High-Strain-Rate Deformation of Polymer Matrix Composites

    Science.gov (United States)

    Goldberg, Robert K.; Roberts, Gary D.

    2003-01-01

    Procedures for modeling the effect of high strain rate on composite materials are needed for designing reliable composite engine cases that are lighter than the metal cases in current use. The types of polymer matrix composites that are likely to be used in such an application have a deformation response that is nonlinear and that varies with strain rate. The nonlinearity and strain rate dependence of the composite response is primarily due to the matrix constituent. Therefore, in developing material models to be used in the design of impact-resistant composite engine cases, the deformation of the polymer matrix must be correctly analyzed. However, unlike in metals, the nonlinear response of polymers depends on the hydrostatic stresses, which must be accounted for within an analytical model. An experimental program has been carried out through a university grant with the Ohio State University to obtain tensile and shear deformation data for a representative polymer for strain rates ranging from quasi-static to high rates of several hundred per second. This information has been used at the NASA Glenn Research Center to develop, characterize, and correlate a material model in which the strain rate dependence and nonlinearity (including hydrostatic stress effects) of the polymer are correctly analyzed. To obtain the material data, Glenn s researchers designed and fabricated test specimens of a representative toughened epoxy resin. Quasi-static tests at low strain rates and split Hopkinson bar tests at high strain rates were then conducted at the Ohio State University. The experimental data confirmed the strong effects of strain rate on both the tensile and shear deformation of the polymer. For the analytical model, Glenn researchers modified state variable constitutive equations previously used for the viscoplastic analysis of metals to allow for the analysis of the nonlinear, strain-rate-dependent polymer deformation. Specifically, we accounted for the effects of

  3. A new (4, 6)-connected Cu(I) coordination polymer based on rare tetranuclear [Cu4I2] clusters: Synthesis, crystal structure, luminescent and photocatalytic properties

    Science.gov (United States)

    Cui, Li-Jing; Liu, Chun-Yan; Bian, Ming; Yu, Li-Jun

    2018-03-01

    A new Cu(I) coordination polymer, namely [Cu5I3(L)2]n (1 HL = 3-(4-pyridyl)-5-(3-pyridyl)-1,2,4-triazolyl), was solvothermally synthesized using CuI, HL and NaI as the starting materials. Single crystal X-ray structural analysis shows that compound 1 features a (4, 6)-connected 3D framework employing rare tetranuclear [Cu4I2] clusters as building subunits. It exhibits intense metal-to-ligand luminescence and excellent photocatalytic activity on degradation of methylene blue (MB).

  4. A two-dimensional bismuth coordination polymer with tartaric acid: synthesis, characterization and thermal decomposition to Bi.sub.2./sub.O.sub.3./sub. nanoparticles

    Czech Academy of Sciences Publication Activity Database

    Ahadiat, G.; Tabatabaee, M.; Gholivand, K.; Zare, K.; Dušek, Michal; Kučeráková, Monika

    2017-01-01

    Roč. 16, č. 1 (2017), s. 7-16 ISSN 1024-1221 R&D Projects: GA ČR(CZ) GA15-12653S; GA MŠk LO1603 EU Projects: European Commission(XE) CZ.2.16/3.1.00/24510 Institutional support: RVO:68378271 Keywords : bismuth coordination polymer * tartrate ligand * thermal decomposition * alpha-Bi 2 O 3 nanoparticles Subject RIV: BM - Solid Matter Physics ; Magnetism OBOR OECD: Condensed matter physics (including formerly solid state physics, supercond.) Impact factor: 0.565, year: 2016

  5. Syntheses, crystal structures and luminescent properties of two new 1D d 1 coordination polymers constructed from 2,2'-bibenzimidazole and 1,4-benzenedicarboxylate

    International Nuclear Information System (INIS)

    Wen Lili; Li Yizhi; Dang Dongbin; Tian Zhengfang; Ni Zhaoping; Meng Qingjin

    2005-01-01

    Two novel interesting d 1 metal coordination polymers, [Zn(H 2 bibzim)(BDC)] n (1) and [Cd(H 2 bibzim)(BDC)] n (2) [H 2 bibzim=2,2'-bibenzimidazole, BDC=1,4-benzenedicarboxylate] have been synthesized under solvothermal conditions and structurally characterized. Both 1 and 2 are constructed from infinite neutral zigzag-like one-dimensional (1D) chains. The π-π interactions and interchain hydrogen-bonding interactions further extend the 1D arrangement to generate a 3D supramolecular architecture for 1 and 2. Both complexes have high thermal stability and display strong blue fluorescent emissions in the solid state upon photo-excitation at 365 nm at room temperature. They are the first two examples that 2,2'-bibenzimidazole has been introduced into the d 1 coordination polymeric framework

  6. 1D Cu(II) coordination polymer derived from 2-(2-(2,4-dioxopentan-3-ylidene)hydrazinyl)benzenesulfonate chelator and pyrazine spacer

    Science.gov (United States)

    Mahmudov, Kamran T.; Haukka, Matti; Sutradhar, Manas; Mizar, Archana; Kopylovich, Maximilian N.; Pombeiro, Armando J. L.

    2013-02-01

    Reaction of 2-(2-(2,4-dioxopentan-3-ylidene)hydrazinyl)benzenesulfonic acid (H2L) with copper(II) nitrate hydrate in the presence of pyrazine (pz) in methanol affords the coordination polymer [Cu2(μ-L)2(H2O)2(μ-pz)]n (1), where the bidentate pz molecule links two Cu(II) centres of two different dimeric units, giving rise to a one-dimensional chain. The dimeric unit [Cu2(μ-L)2(H2O)2] consists of two distorted octahedral Cu(II) centres connected via oxygen atoms of the sulfo group of the bridging L2- ligand. The extensive hydrogen bonding between the coordinated water and pz molecules leads to the formation of a supramolecular 3D associate. Compound 1 has been characterized by elemental analysis, ESI-MS, IR spectroscopy and single-crystal X-ray diffraction analysis.

  7. 1-D linear coordination polymers of Cu(II) with N4-substituted 1,2,4-triazoles and 4,4‧-bipyridine

    Science.gov (United States)

    Białońska, Agata; Ciunik, Zbigniew; Drabent, Krzysztof

    2010-04-01

    The reaction of N-[( E)-(4-chlorophenyl)methylidene]-4 H-1,2,4-triazol-4-amine (ClPhtrz), 4,4'-bipyridine (4,4'-bipy) and Cu(An) 2·6H 2O (An = ClO 4- or BF 4-) in MeCN/H 2O yields two 1-D coordination polymers, namely ∞1{[Cu(4,4'-bipy)(ClPhtrz)2(HO)2](An)2·2CHCN}, (An = ClO 4- ( 1), BF 4- ( 2). In both compounds triazole ligands are monodently coordinated to metal center. Similar reaction with Cu(NO 3) 2·3H 2O affords ∞1{[Cu(4,4'-bipy)(CHCN)(HO)(NO)](NO)} ( 3). Unexpectedly the triazole ligand is not observed in the final product.

  8. Hydrothermal syntheses and structures of first examples of lanthanide 7,8,4‧-tricarboxymethoxyisoflavone coordination polymers

    Science.gov (United States)

    Wang, Yibo; Gao, Lihua; Han, Lijun; Zhang, Suojiang; Feng, Lujia

    2009-12-01

    Two novel isostructure open frameworks of Ln(III), [Ln(L)(H 2O)·1.5H 2O] n, [Ln = Pr( 1), Eu( 2)], have been successfully synthesized using multifunctional organic compound 7,8,4'-tricarboxymethoxyisoflavone (L) as a linker through hydrothermal technique. Compounds 1 and 2 consist of 2D networks, which are further assembled into 3D architecture with 1D channels constructed by coordination bonds and the lattice water molecules array in lines occupying these voids via hydrogen bonds. In these compounds, L only exhibit one coordination mode coordinating to Ln(III), and four oxygen atoms from two carboxylate groups and two carboxymethoxy groups of one L coordinate to one Ln(III), simultaneously. The thermogravimetric analyses of these compounds show that the coordinated water and lattice water are lost in two steps, and the final residues are lanthanide oxides.

  9. Coordination polymers of Fe(iii) and Al(iii) ions with TCA ligand: distinctive fluorescence, CO2 uptake, redox-activity and oxygen evolution reaction.

    Science.gov (United States)

    Dhara, Barun; Sappati, Subrahmanyam; Singh, Santosh K; Kurungot, Sreekumar; Ghosh, Prasenjit; Ballav, Nirmalya

    2016-04-28

    Fe and Al belong to different groups in the periodic table, one from the p-block and the other from the d-block. In spite of their different groups, they have the similarity of exhibiting a stable 3+ oxidation state. Here we have prepared Fe(iii) and Al(iii) based coordination polymers in the form of metal-organic gels with the 4,4',4''-tricarboxyltriphenylamine (TCA) ligand, namely Fe-TCA and Al-TCA, and evaluated some important physicochemical properties. Specifically, the electrical conductivity, redox-activity, porosity, and electrocatalytic activity (oxygen evolution reaction) of the Fe-TCA system were noted to be remarkably higher than those of the Al-TCA system. As for the photophysical properties, almost complete quenching of the fluorescence originating from TCA was observed in case of the Fe-TCA system, whereas for the Al-TCA system a significant retention of fluorescence with red-shifted emission was observed. Quantum mechanical calculations based on density functional theory (DFT) were performed to unravel the origin of such discriminative behaviour of these coordination polymer systems.

  10. Three d10 coordination polymers assembled from 3,5-bis(imidazole-1-yl)pyridine and different polycarboxylates: Syntheses, structures and luminescence properties

    Science.gov (United States)

    Pan, Jie; Zhang, Di; Xue, Zhen-Zhen; Wei, Li; Han, Song-De; Wang, Guo-Ming

    2017-11-01

    Three novel Zn(II)/Cd(II) coordination polymers, [Cd2(bip)2(m-bdc)2(H2O)2·3H2O]n (1), [Zn2(bip)2(p-bdc)2·2.5H2O]n (2) and [Zn(bip) (p-bdc)·3H2O]n (3), where bip = 3,5-bis(imidazole-1-yl)pyridine, m-H2bdc = 1,3-benzenedicarboxylic acid, p-H2bdc = 1,4-benzenedicarboxylic acid, have been successfully synthesized under solvothermal conditions. The linkage of different ligands with Cd(II) ions in compound 1 affords a (3,5)-connected layer. Furthermore, 2D→3D parallel polycatenation occurs wherein the layers are polycatenated with the adjacent two parallel layers to form a 3D framework. In 2 and 3, the polycarboxylates act as pillars to combine the metal-bip chains, yielding the layered structures. These 2D networks are extended to the final 3D supramolecular architectures by π-π stacking interactions. The results show that bip can act as a versatile building block for the construction of various coordination polymers. Moreover, the fluorescent properties of 1-3 in the solid state at room temperature have been investigated.

  11. Dicynamide bridged two new zig-zag 1-D Zn(II) coordination polymers of pyrimidine derived Schiff base ligands: Synthesis, crystal structures and fluorescence studies

    Science.gov (United States)

    Konar, Saugata

    2015-07-01

    Two new zigzag 1-D polymeric Zn(II) coordination polymers {[Zn(L1)(μ1,5-dca)](H2O)}n (1), {[Zn(L2)(μ1,5-dca)](ClO4)}n (2) of two potentially tridentate NNO-, NNN-, donor Schiff base ligands [2-(2-(4,6-dimethylpyrimidin-2-yl)hydrazono)methyl)phenol] (L1), [1-(4,6-dimethylpyrimidin-2-yl)-2-(dipyridin-2ylmethylene)hydrazine] (L2) have been synthesized and characterized by elemental analyses, IR and 1H NMR, fluorescence spectroscopy and single crystal X-ray crystallography. The dicyanamide ions act as linkers (μ1,5 mode) in the formation of these coordination polymers. Both the complexes 1 and 2 have same distorted square pyramidal geometry around the Zn(II) centres. The weak forces like π⋯π, Csbnd H⋯π, anion⋯π interactions lead to various supramolecular architectures. Complex 1 shows high chelation enhanced fluorescence compared to that of 2. The fluorescence spectral changes observed high selectivity towards Zn(II) over other metal ions such as Mn(II), Co(II), Ni(II), Cu(II).

  12. A new set of Cd(ii)-coordination polymers with mixed ligands of dicarboxylate and pyridyl substituted diaminotriazine: selective sorption towards CO2and cationic dyes.

    Science.gov (United States)

    Chand, Santanu; Elahi, Syed Meheboob; Pal, Arun; Das, Madhab C

    2017-08-01

    On the basis of a mixed ligand system of L(NH 2 ) 2 (6-(pyridin-4-yl)-1,3,5-triazine-2,4-diamine) and dicarboxylic acids, three new Cd(ii) coordination polymers viz. {[Cd 0.5 (tdc) 0.5 (L(NH 2 ) 2 ) 0.5 (H 2 O)]·DMF·H 2 O} n (1), {[Cd 0.5 (bdc) 0.5 (L(NH 2 ) 2 )(H 2 O)]·DMF·H 2 O} n (2), and {[Cd(ipa)(L(NH 2 ) 2 )(DMF)]·H 2 O} n (3) (tdcH 2 = thiophene-2,5-dicarboxylic acid, bdcH 2 = benzene-1,4-dicarboxylic acid, ipaH 2 = benzene-1,3-dicarboxylic acid) were synthesized under diverse reaction conditions and characterized by single crystal X-ray diffraction, PXRD, elemental analysis, IR spectroscopy and TGA. While 1 and 2 revealed 1D chain structures, 3 acquired a 2D square net structural arrangement. Gas adsorption measurements of the desolvated framework 3 showed a moderate uptake of CO 2 under ambient conditions with good selectivity over N 2 and CH 4 . The solid state luminescence properties were studied for all three coordination polymers. Moreover, a dye adsorption study on 3 exhibited selective adsorption towards a cationic dye.

  13. CdO-NPs; synthesis from 1D new nano Cd coordination polymer, characterization and application as anti-cancer drug for reducing the viability of cancer cells

    Science.gov (United States)

    Afzalian Mend, Behnaz; Delavar, Mahmoud; Darroudi, Majid

    2017-04-01

    The hexagonal CdO nano-particles (CdO-NPs) was prepared using new nano Cd coordination polymer, [Cd(NO3)(bipy)(pzca)]n (1) as a precursor, through direct calcination process at 500 °C. The precursor (1) was synthesized by sonochemical method. The new nano compound (1) was characterized by IR spectroscopy, elemental analyses, X-ray powder diffraction (XRD), transmission electron microscopy (TEM) and thermal gravimetric analyses. The structure of nano coordination polymer was determined by comparing the XRD pattern of nano and single-crystal of compound (1). The nano CdO was characterized by scanning electron microscopy (SEM) and X-ray powder diffraction (XRD). In addition, the activity and efficiency of nano CdO as an anti-cancer drug was studied on cancer cells with different concentration. The results shows that the viability of cancer cells reduced above 2 μg/mL of CdO-NPs concentration.

  14. Two interpenetrating Cu{sup II}/Ni{sup II}-coordinated polymers based on an unsymmetrical bifunctional N/O-tectonic: Syntheses, structures and magnetic properties

    Energy Technology Data Exchange (ETDEWEB)

    Liu, Yong-Liang [College of Materials & Chemical Engineering, China Three Gorges University, Yichang 443002 (China); Department of Chemistry and Chemical Engineering, Shaanxi Key Laboratory of Comprehensive Utilization of Tailings Resources, Shang Luo University, Shang Luo 726000 (China); Wu, Ya-Pan [College of Materials & Chemical Engineering, China Three Gorges University, Yichang 443002 (China); Li, Dong-Sheng, E-mail: lidongsheng1@126.com [College of Materials & Chemical Engineering, China Three Gorges University, Yichang 443002 (China); Dong, Wen-Wen [College of Materials & Chemical Engineering, China Three Gorges University, Yichang 443002 (China); Zhou, Chun-Sheng [Department of Chemistry and Chemical Engineering, Shaanxi Key Laboratory of Comprehensive Utilization of Tailings Resources, Shang Luo University, Shang Luo 726000 (China)

    2015-03-15

    Two new interpenetrating Cu{sup II}/Ni{sup II} coordination polymers, based on a unsymmetrical bifunctional N/O-tectonic 3-(pyrid-4′-yl)-5-(4″-carbonylphenyl)-1,2,4-triazolyl (H{sub 2}pycz), ([Cu-(Hpycz){sub 2}]·2H{sub 2}O){sub n} (1) and ([Ni(Hpycz){sub 2}]·H{sub 2}O){sub n} (2), have been solvothermally synthesized and structure characterization. Single crystal X-ray analysis indicates that compound 1 shows 2-fold parallel interpenetrated 4{sup 4}-sql layers with the same handedness. The overall structure of 1 is achiral—in each layer of doubly interpenetrating nets, the two individual nets have the opposite handedness to the corresponding nets in the adjoining layers—while 2 features a rare 8-fold interpenetrating 6{sup 6}-dia network that belongs to class IIIa interpenetration. In addition, compounds 1 and 2 both show similar paramagnetic characteristic properties. - Graphical abstract: Two new Cu(II)/Ni(II) coordination polymers present 2D parallel 2-fold interpenetrated 4{sup 4}-sql layers and a rare 3D 8-fold interpenetrating 6{sup 6}-dia network. In addition, magnetic susceptibility measurements show similar paramagnetic characteristic for two complexes. - Highlights: • A new unsymmetrical bifunctional N/O-tectonic as 4-connected spacer. • A 2-fold parallel interpenetrated sql layer with the same handedness. • A rare 8-fold interpenetrating dia network (class IIIa)

  15. Construction of double-stranded metallosupramolecular polymers with a controlled helicity by combination of salt bridges and metal coordination.

    Science.gov (United States)

    Ikeda, Masato; Tanaka, Yoshie; Hasegawa, Takashi; Furusho, Yoshio; Yashima, Eiji

    2006-05-31

    We describe the construction of the first double-stranded metallosupramolecular helical polymers. We designed and synthesized a supramolecular duplex comprised of complementary m-terphenyl-based strands bearing a chiral amidine or achiral carboxylic acid together with two pyridine groups at the four ends. Supramolecular polymerization of the duplex with cis-PtPh2(DMSO)2 in 1,1,2,2-tetrachloroethane produced the double-stranded metallosupramolecular polymer with a controlled helicity of which the two complementary metallostrands are intertwined through the amidinium-carboxylate salt bridges. The structures and hydrodynamic dimensions of the metallosupramolecular polymers were characterized by 1H NMR, diffusion-ordered NMR, dynamic light scattering, absorption, and CD measurements. The polymeric structure was also visualized by atomic force microscopy.

  16. Coordination Chemistry Inside Polymeric Nanoreactors: Interparticle Metal Exchange and Ionic Compound Vectorization in Phosphine-Functionalized Amphiphilic Polymer Latexes.

    Science.gov (United States)

    Chen, Si; Gayet, Florence; Manoury, Eric; Joumaa, Ahmad; Lansalot, Muriel; D'Agosto, Franck; Poli, Rinaldo

    2016-04-25

    Stable latexes of hierarchically organized core-cross-linked polymer micelles that are functionalized at the core with triphenylphosphine (TPP@CCM) have been investigated by NMR spectroscopic analysis at both natural (ca. pH 5) and strongly basic (pH 13.6) pH values after core swelling with toluene. The core-shell interface structuring forces part of the hydrophilic poly(ethylene oxide) (PEO) chains to reside inside the hydrophobic core at both pH values. Loading the particle cores with [Rh(acac)(CO)2 ] (acac=acetylacetonate) at various Rh/P ratios yielded polymer-supported [Rh(acac)(CO)(TPP)] (TPP=triphenylphosphine). The particle-to-particle rhodium migration is very fast at natural pH, but slows down dramatically at high pH, whereas the size distribution of the nanoreactors remains unchanged. The slow migration at pH 13.6 leads to the generation of polymer-anchored [Rh(OH)(CO)(TPP)2 ], which is also generated immediately upon the addition of NaOH to the particles with a [Rh(acac)(CO)] loading of 50 %. Similarly, treatment of the same particles with NaCl yielded polymer-anchored [RhCl(CO)(TPP)2 ]. Interparticle coupling occurs during these rapid processes. These experiments prove that the major contribution to metal migration is direct core-core contact. The slow migration at the high pH value, however, must result from a pathway that does not involve core-core contact. The facile penetration of the polymer cores by NaOH and NaCl results from the presence of shell-linked poly(ethylene oxide) methyl ether functions both outside and inside the polymer core-shell interface. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  17. A Novel Coordination Polymer Constructed by Hetero-Metal Ions and 2,3-Pyridine Dicarboxylic Acid: Synthesis and Structure of [NiNa2(PDC)2(μ-H2O)(H2O)2] n

    Science.gov (United States)

    Dou, Ming-Yu; Lu, Jing

    2017-12-01

    A novel coordination polymer containing hetero-metal ions, [NiNa2(PDC)2(μ-H2O)(H2O)2] n , where PDC is 2,3-pyridine dicarboxylate ion, has been synthesized. In the structure, the PDC ligand chelates and bridges two Ni(II) and two Na(I) centers. Two kinds of metal centers are connected by μ4-PDC and μ2-H2O to form 2D coordination layers. Hydrogen bonds between coordination water molecules and carboxylate oxygen atoms further link these 2D coordination layers to form 3D supramolecular network.

  18. Syntheses, crystal structures and characterizations of three new copper(II) azide coordination polymers with 1,2,4-triazole ligands

    Science.gov (United States)

    Liu, Jing-Jing; He, Xiang; Shao, Min; Li, Ming-Xing

    2009-02-01

    Three new copper(II) azide coordination polymers with derivatives of 1,2,4-triazole as bridging coligands, namely [Cu 2(admtrz) 2(N 3) 4] n ( 1) (admtrz = 4-amino-3,5-dimethyl-1,2,4-triazole), [Cu(4-abpt)(N 3) 2] n·2 nH 2O ( 2) (4-abpt = 4-amino-3,5-bis(4-pyridyl)-1,2,4-triazole) and [Cu 3(2-ptrz) 2(N 3) 6] n ( 3) (2-ptrz = 4-(2-pyridyl)-1,2,4-triazole), were prepared and characterized by elemental analyses, IR spectra and X-ray structural analyses. Compound 1 has a 1D chain structure in which Cu(II) ions are bridged by end-on (EO) azides and admtrz ligands. This compound contains three kinds of coordination modes for Cu(II) ions, including tetrahedral, square pyramidal and octahedral geometries. Compound 2 displays an interesting 3D framework structure, in which the azide ligands link Cu(II) ions in end-to-end (EE) mode affording a 2D square layer. This 2D layers are further bridged by bent 4-abpt ligands to form an interesting 3D framework. Furthermore, this structure also exhibits an alpha-Po net topology. Compound 3 displays a 1D rectangle-like chain structure linked by azides adopting end-on (EO) and end-to-end (EE) modes and 2-ptrz ligands. The IR and thermal stabilities of these coordination polymers 1-3 have also been studied.

  19. Conformational supramolecular isomerism in one-dimensional silver(I) coordination polymer of a flexible bis(bidentate) N,N-donor ligand with p-xylyl spacer.

    Science.gov (United States)

    Chakraborty, Biswarup; Halder, Partha; Paine, Tapan Kanti

    2011-04-14

    The isolation and structural characterisation of three isomeric silver(I) complexes, 1a, 1b and 2 with the general formula {[AgL(1)]ClO(4)}(n) (where L(1) is a bis(bidentate) N,N-donor ligand derived from the Schiff-base condensation of α,α'-diamino-p-xylene and pyridine-2-carboxaldehyde) are discussed. Single-crystal X-ray structures reveal the polymeric nature for the complexes where all the silver ions are in pseudotetrahedral geometry with the AgN(4) coordination environment. Isomers 1a (Pc space group) and 1b (Cc space group) were crystallised from acetonitrile whereas 2 (C2/c space group) was crystallised during the synthesis from a solvent mixture of dicholormethane and methanol. The flexible ligand (L(1)) adopts only an anti conformation in 1b and the presence of two different anti conformations in the repeating unit results in the formation of a trapezoidal wave polymeric chain. However, both gauche and anti conformations of the ligand are found to be present in the polymeric chains of 1a. In the polymeric chain of 2, only one anti isomer of the ligand is present in the repeating unit resulting in a triangular wave chain. The structure of isomer 1a is solvent induced and solvent plays a major role in the crystal packing of this isomer. One-dimensional coordination polymers 1a, 1b and 2 are related to each other as conformational supramolecular isomers. Additionally, two independent polymeric chains parallel to each other: one triangular wave consisting of only an anti conformation and a trapezoidal wave chain consisting of alternate gauche and anti conformations of the ligand are observed in 1a. This is a rare example of two supramolecular isomers present in the same crystal. Six different conformers of the flexible ligand are observed in the crystals of coordination polymers. © The Royal Society of Chemistry 2011

  20. Sonochemical Synthesis of a New Nano Lead(II Coordination Polymer with 2,5-bis(2-pyridyl-3,4-diaza-2,4- hexadiene ligand: A Precursor to Produce Pure Phase Nano- sized Lead(II Oxide

    Directory of Open Access Journals (Sweden)

    A. Morsali

    2011-04-01

    Full Text Available A new nano-sized lead(II coordination polymer, [Pb(2-bpdh(NO32]n (1; (2-bpdh = 2,5-bis(2-pyridyl-3,4-diaza-2,4-hexadiene}, was synthesized by a sonochemical method. The structure of 1 may be considered coordination polymer of lead(II consist of metallocyclicchains formed by bridging NO3- and 2-bpdh ligands. The thermal stability of compound was studied by thermal gravimetric and differential thermal analyses. The new nano-structure coordination polymer was characterized by scanning electron microscopy, powder X-ray diffraction, elemental analyses and IR spectroscopy. The size of the samples was about 50 nm. Nano-particles of PbO were obtained by thermolysis of compound 1in oleic acid as a surfactant at 180 °C under air atmosphere and the size of this PbO particles were about 50 nm.

  1. Ultrasonic synthesis of two new zinc(II) bipyridine coordination polymers: New precursors for preparation of zinc(II) oxide nano-particles.

    Science.gov (United States)

    Fard, Mohammad Jaafar Soltanian; Hayati, Payam; Firoozadeh, Azita; Janczak, Jan

    2017-03-01

    Nanoparticles of two zinc(II) coordination polymers (CPs), [Zn(μ-4,4'-bipy)Cl 2 ] n (1) and [Zn(μ-4,4'-bipy)Br 2 ] n (2) L=bpy=4,4'-bipyridine ligand, have been synthesized by use of a sonochemical process and characterized by scanning electron microscopy (SEM), X-ray powder diffraction (XRPD), Fourier transform infrared spectroscopy (FTIR) spectroscopy and elemental analyses. The single crystal X-ray data of compounds 1 and 2 imply that the Zn +2 ions are four coordinated. Topological analysis shows that 1D coordination networks of 1 and 2 can be classified as underlying nets of topological types 2C1. Nanoparticles of zinc(II) oxide have been prepared by calcination of two different zinc (II) CPs at 450°C that were characterized by scanning electron microscopy (SEM), X-ray powder diffraction (XRD) and IR spectroscopy. Copyright © 2016 Elsevier B.V. All rights reserved.

  2. Cd (II) and holodirected lead (II) 3D-supramolecular coordination polymers based on nicotinic acid: Structure, fluorescence property and photocatalytic activity

    Science.gov (United States)

    Etaiw, Safaa El-din H.; Abd El-Aziz, Dina M.; Marie, Hassan; Ali, Elham

    2018-05-01

    Two new supramolecular coordination polymers namely {[Cd(NA)2(H2O)]}, SCP 1 and {[Pb(NA)2]}, SCP 2, (NA = nicotinate ligand) were synthesized by self-assembly method and structurally characterized by different analytical and spectroscopic methods. Single-crystal X-ray diffraction showed that SCP 1 extend in three dimensions containing bore structure where the 3D- network is constructed via interweaving zigzag chains. The Cd atom coordinates to (O4N2) atoms forming distorted-octahedral configuration. The structure of SCP 2 extend down the projection of the b-axis creating parallel zigzag 1D-chains connected by μ2-O2 atoms and H-bonds forming a holodirected lead (II) hexagonal bi-pyramid configuration. SCP 2 extend to 3D-network via coordinate and hydrogen bonds. The thermal stability, photoluminescence properties, photocatalytic activity for the degradation of methylene blue dye (MB) under UV-irradiation and sunlight irradiation were also studied.

  3. Crystal structure of a mixed-ligand terbium(III coordination polymer containing oxalate and formate ligands, having a three-dimensional fcu topology

    Directory of Open Access Journals (Sweden)

    Chainok Kittipong

    2016-01-01

    Full Text Available The title compound, poly[(μ3-formato(μ4-oxalatoterbium(III], [Tb(CHO2(C2O4]n, is a three-dimensional coordination polymer, and is isotypic with the LaIII, CeIII and SmIII analogues. The asymmetric unit contains one TbIII ion, one formate anion (CHO2− and half of an oxalate anion (C2O42−, the latter being completed by application of inversion symmetry. The TbIII ion is nine-coordinated in a distorted tricapped trigonal–prismatic manner by two chelating carboxylate groups from two C2O42− ligands, two carboxylate oxygen atoms from another two C2O42− ligands and three oxygen atoms from three CHO2− ligands, with the Tb—O bond lengths and the O—Tb—O bond angles ranging from 2.4165 (19 to 2.478 (3 Å and 64.53 (6 to 144.49 (4°, respectively. The CHO2− and C2O42− anions adopt μ3-bridging and μ4-chelating-bridging coordination modes, respectively, linking adjacent TbIII ions into a three-dimensional 12-connected fcu topology with point symbol (324.436.56. The title compound exhibits thermal stability up to 623 K, and also displays strong green photoluminescence in the solid state at room temperature.

  4. Near-infrared light stimuli-responsive synergistic therapy nanoplatforms based on the coordination of tellurium-containing block polymer and cisplatin for cancer treatment.

    Science.gov (United States)

    Li, Feng; Li, Tianyu; Cao, Wei; Wang, Lu; Xu, Huaping

    2017-07-01

    Cisplatin (CDDP) has received worldwide approval for clinical use in the past decades. However, its development in cancer chemotherapy was overshadowed by severe side effects and drug resistance. Herein, we developed a CDDP drug delivery system with high encapsulation efficiency and near-infrared light stimuli-responsive drug release properties based on the coordination of novel tellurium-containing block polymer (PEG-PUTe-PEG) and CDDP. The nanocarriers made from PEG-PUTe-PEG were loaded with CDDP and indocyanine green (ICG) simultaneously. The coordination chemistry between CDDP and tellurium guaranteed the nanocarrier a high stability in plasma and prolonged circulation time in vivo by reducing possible penetration of water molecule into the nanoparticles. Under the stimuli of a near-infrared laser, an amount of ROS can be generated by irradiation of ICG. The tellurium is easily oxidized by ROS because of the low electronegativity of tellurium. The CDDP could be rapidly released from the nanocarriers along with the oxidation of the tellurium at the tumor sites as the oxidized tellurium will weaken the coordination interaction with CDDP. In addition, the encapsulated ICG played a synergistic antitumor effect through photothermal effect with mild laser irradiation. The integrated strategy achieved higher antitumor efficacy and showed minimal side effects compared with the CDDP alone. Copyright © 2017 Elsevier Ltd. All rights reserved.

  5. Crystal structure of a heterometallic coordination polymer: poly[diaquabis(μ7-benzene-1,3,5-tricarboxylatodicalcium(IIcopper(II

    Directory of Open Access Journals (Sweden)

    Feng Zhang

    2017-06-01

    Full Text Available In the title complex, [Ca2Cu(C9H3O62(H2O2]n, the CaII and CuII cations are bridged by the benzene-1,3,5-tricarboxylate anions (BTC3− to form the coordination polymer, in which each BTC3− anion bridges two CuII and five CaII cations with a μ7 coordination mode. The CuII cation, located at an inversion centre, is in a nearly square-planar geometry defined by four O atoms from four bridging BTC3− anions, while the CaII cation is in a distorted octahedral geometry defined by five O atoms from bridging BTC3− anions and one water molecule. O—H...O hydrogen bonds between coordinating water molecules and carboxyl groups further stabilize the structure; π–π stacking is also observed between parallel benzene rings, the centroid-to-centroid distance being 3.357 (2 Å.

  6. Possible mechanism(s) behind recently observed effects of incorporating gold nanoparticles into a polymer-dispersed liquid crystal

    Science.gov (United States)

    Hinojosa, Alfonso; Sharma, Suresh

    2010-10-01

    Recently we reported that addition of relatively small concentrations of about 14-nm diameter gold nanoparticles (Au NPs) to a polymer-dispersed liquid crystal (PDLC) produces rather large changes in the electro-optical properties of the PDLC. For example, addition of Au NPs to PDLC microstructure lowers its threshold voltage by almost 50% and increases optical transmission in a manner that depends on NPs concentration and applied electric field.ootnotetextA. Hinojosa and S. C. Sharma, Applied Physics Letters, 97, 081114 (2010) In order to understand these observations, we have carried out electro-optical measurements on several PDLCs as functions of the polarization of the incident laser beam and applied electric field. In this presentation, we will discuss the results obtained from these experiments and suggest mechanism(s), which might explain NPs-induced changes in the electro-optical properties of PDLCs.

  7. Thermally Stable Mesoporous Perovskite Solar Cells Incorporating Low-Temperature Processed Graphene/Polymer Electron Transporting Layer.

    Science.gov (United States)

    Tong, Shi Wun; Balapanuru, Janardhan; Fu, Deyi; Loh, Kian Ping

    2016-11-02

    In the short time since its discovery, perovskite solar cells (PSCs) have attained high power conversion efficiency but their lack of thermal stability remains a barrier to commercialization. Among the experimentally accessible parameter spaces for optimizing performance, identifying an electron transport layer (ETL) that forms a thermally stable interface with perovskite and which is solution-processable at low-temperature will certainly be advantageous. Herein, we developed a mesoporous graphene/polymer composite with these advantages when used as ETL in CH 3 NH 3 PbI 3 PSCs, and a high efficiency of 13.8% under AM 1.5G solar illumination could be obtained. Due to the high heat transmission coefficient and low isoelectric point of mesoporous graphene-based ETL, the PSC device enjoys good chemical and thermal stability. Our work demonstrates that the mesoporous graphene-based scaffold is a promising ETL candidate for high performance and thermally stable PSCs.

  8. IR Laser-Induced Breakdown in Thiirane for Gas-Phase Deposition of Conjugated Organosulfur Polymer Incorporating Cycloheptasulfur

    Czech Academy of Sciences Publication Activity Database

    Blazevska-Gilev, J.; Urbanová, Markéta; Pokorná, Dana; Šubrt, Jan; Pola, Josef

    2012-01-01

    Roč. 93, - (2012), s. 165-169 ISSN 0165-2370 R&D Projects: GA ČR GA203/09/0931 Institutional research plan: CEZ:AV0Z40720504; CEZ:AV0Z40320502 Keywords : dielectric breakdown * thiirane * organosulfur polymer Subject RIV: CH - Nuclear ; Quantum Chemistry Impact factor: 2.560, year: 2012 http://www.scopus.com/record/display.url?eid=2-s2.0-84155172324&origin=resultslist&sort=plf-f&src=s&st1=pola%2cj&sid=ikNGw6d45E-yyuMoDwlGiWn%3a360&sot=b&sdt=b&sl=19&s=AUTHOR-NAME%28pola%2cj%29&relpos=1&relpos=1&searchTerm=AUTHOR-NAME(pola,j)

  9. Investigation of interfacial shear stresses, shape fixity, and actuation strain in composites incorporating shape memory polymers and shape memory alloys

    Science.gov (United States)

    Park, Jungkyu; Headings, Leon; Dapino, Marcelo; Baur, Jeffery; Tandon, Gyaneshwar

    2015-03-01

    Shape memory composites (SMCs) based on shape memory alloys (SMAs) and shape memory polymers (SMPs) allow many design possibilities due to their controllable temperature-dependent mechanical properties. The complementary characteristics of SMAs and SMPs can be utilized in systems with shape recovery created by the SMA and shape fixity provided by the SMP. In this research, three SMC operating regimes are identified and the behavior of SMC structures is analyzed by focusing on composite shape fixity and interfacial stresses. Analytical models show that SMPs can be used to adequately fix the shape of SMA actuators and springs. COMSOL finite element simulations are in agreement with analytical expressions for shape fixity and interfacial stresses. Analytical models are developed for an end-coupled linear SMP-SMA two-way actuator and the predicted strain is shown to be in good agreement with experimental test results.

  10. Synthesis and photoluminescence properties of Eu3+-doped silica@coordination polymer core-shell structures and their calcinated silica@Gd2O3:Eu and hollow Gd2O3:Eu microsphere products.

    Science.gov (United States)

    Lee, Hee Jung; Park, Ju-Un; Choi, Sora; Son, Juhee; Oh, Moonhyun

    2013-02-25

    The conjugation of Eu(3+)-doped coordination polymers constructed from Gd(3+) and isophthalic acid (H(2)IPA) with silica particles is investigated for the production of luminescent microspheres. A series of doping ratio-controlled silica@coordination polymer core-shell spheres is easily synthesized by altering the amounts of metal nodes used in the reactions, where the ratios of Gd(3+) and Eu(3+) are 10:0 (1a), 9:1 (1b), 8:2 (1c), 7:3 (1d), 5:5 (1e), and 0:10 (1f). The formation of monodisperse uniform core-shell structures is achieved throughout the entirety of a series. Investigations of the photoluminescence property of the resulting series of silica@coordination polymer core-shell spheres reveal that 20% Eu(3+)-doped product (1c) has the strongest emission intensity. The subsequent calcination process on the silica@coordination polymer core-shell structures (1a-f) results in the formation of a series of doping ratio-controlled silica@Gd(2)O(3):Eu core-shell microspheres (2a-f) with uniform shell thickness. During the calcination step, the coordination polymers within silica@coordination polymer core-shells are transformed into metal oxides, resulting in silica@Gd(2)O(3):Eu core-shell structures. The final etching process on the silica@Gd(2)O(3):Eu core-shell microspheres (2a-f) produces a series of hollow Gd(2)O(3):Eu microspheres (3a-f) as a result of the elimination of silica cores. The luminescence intensities of silica@Gd(2)O(3):Eu core-shell (2a-f) and hollow Gd(2) O(3):Eu microspheres (3a-f) also vary depending upon the doping ratio of Eu(3+) ions. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  11. Incorporation of ionic liquid into porous polymer monoliths to enhance the separation of small molecules in reversed-phase high-performance liquid chromatography.

    Science.gov (United States)

    Wang, Jiafei; Bai, Ligai; Wei, Zhen; Qin, Junxiao; Ma, Yamin; Liu, Haiyan

    2015-06-01

    An ionic liquid was incorporated into the porous polymer monoliths to afford stationary phases with enhanced chromatographic performance for small molecules in reversed-phase high-performance liquid chromatography. The effect of the ionic liquid in the polymerization mixture on the performance of the monoliths was studied in detail. While monoliths without ionic liquid exhibited poor resolution and low efficiency, the addition of ionic liquid to the polymerization mixture provides highly increased resolution and high efficiency. The chromatographic performances of the monoliths were demonstrated by the separations of various small molecules including aromatic hydrocarbons, isomers, and homologues using a binary polar mobile phase. The present column efficiency reached 27 000 plates/m, which showed that the ionic liquid monoliths are alternative stationary phases in the separation of small molecules by high-performance liquid chromatography. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  12. Rational assembly of Pb(II)/Cd(II)/Mn(II) coordination polymers based on flexible V-shaped dicarboxylate ligand: Syntheses, helical structures and properties

    Energy Technology Data Exchange (ETDEWEB)

    Yang, Gao-Shan [School of Environment and Chemical Engineering, Nanchang Hangkong University, Nanchang 330063 (China); Liu, Chong-Bo, E-mail: cbliu@nchu.edu.cn [School of Environment and Chemical Engineering, Nanchang Hangkong University, Nanchang 330063 (China); School of Chemistry and Biochemistry, Georgia Institute of Technology, Atlanta, GA 30332 (United States); Liu, Hong [School of Environment and Chemical Engineering, Nanchang Hangkong University, Nanchang 330063 (China); Robbins, Julianne; Zhang, Z. John [School of Chemistry and Biochemistry, Georgia Institute of Technology, Atlanta, GA 30332 (United States); Yin, Hong-Shan [School of Environment and Chemical Engineering, Nanchang Hangkong University, Nanchang 330063 (China); Wen, Hui-Liang [State Key Laboratory of Food Science and Technology, Nanchang University, Nanchang 330047 (China); Wang, Yu-Hua [School of Environment and Chemical Engineering, Nanchang Hangkong University, Nanchang 330063 (China)

    2015-05-15

    Six new coordination polymers, namely, [Pb(L)(H{sub 2}O)] (1), [Pb(L)(phen)] (2), [Pb{sub 2}(L){sub 2}(4,4′-bipy){sub 0.5}] (3), [Cd(L)(phen)] (4), [Cd(L)(4,4′-bipy)]·H{sub 2}O (5) and [Mn(L)(4,4′-bipy)]·H{sub 2}O (6) have been synthesized by the hydrothermal reaction of 2,2′-[hexafluoroisopropylidenebis(p-phenyleneoxy)]diacetic acid (H{sub 2}L) with Pb(II)/Cd(II)/Mn(II) in the presence of ancillary ligands 4,4′-bipyridine (4,4′-bipy) or 1,10-phenanthroline (phen). Complexes 1 and 4–6 exhibit 2-D structures, and complexes 2–3 display 3-D frameworks, of which L{sup 2−} ligands join metal ions to single-stranded helical chains of 1, 3–6 and double-stranded helical chains of 2. Complexes 2 and 3 also contain double-stranded Metal–O helices. Topology analysis reveals that complexes 1 and 4 both represent 4-connected sql net, 2 represents 6-connected pcu net, 3 exhibits a novel (3,12)-connected net, while 5 and 6 display (3,5)-connected gek1 net. The six complexes exhibit two kinds of inorganic–organic connectivities: I{sup 0}O{sup 2} for 1, 4–6, and I{sup 1}O{sup 2} for 2–3. The photoluminescent properties of 4–5 and the magnetic properties of 6 have been investigated. - Graphical abstract: Six new Pb(II)/Cd(II)/Mn(II) coordination polymers with helical structures based on flexible V-shaped dicarboxylate ligand have been synthesized and structurally characterized. Photoluminescent and magnetic properties have been investigated. - Highlights: • Six novel M(II) coordination polymers with 2,2′-[hexafluoroisopropylidenebis(p-phenyleneoxy)]diacetic acid and N-donor ligands. • Complexes 1–6 show diverse intriguing helical characters. • The luminescent properties of complexes 1–5 were investigated. • Complex 6 shows antiferromagnetic coupling.

  13. N-donor co-ligands driven two new Co(II)- coordination polymers with bi- and trinuclear units: Crystal structures, and magnetic properties

    Energy Technology Data Exchange (ETDEWEB)

    Zhou, Zhi-Hang [College of Materials and Chemical Engineering, Hubei Provincial Collaborative Innovation Center for New Energy Microgrid, Key Laboratory of Inorganic Non-metallic Crystalline and Energy Conversion Materials, China Three Gorges University, Yichang 443002 (China); Han, Min-Le [College of Chemistry and Chemical Engineering, Henan Key Laboratory of Function-Oriented Porous Materials, Luoyang Normal University, Luoyang 471022 (China); Wu, Ya-Pan; Dong, Wen-Wen [College of Materials and Chemical Engineering, Hubei Provincial Collaborative Innovation Center for New Energy Microgrid, Key Laboratory of Inorganic Non-metallic Crystalline and Energy Conversion Materials, China Three Gorges University, Yichang 443002 (China); Li, Dong-Sheng, E-mail: lidongsheng1@126.com [College of Materials and Chemical Engineering, Hubei Provincial Collaborative Innovation Center for New Energy Microgrid, Key Laboratory of Inorganic Non-metallic Crystalline and Energy Conversion Materials, China Three Gorges University, Yichang 443002 (China); Lu, Jack Y., E-mail: lu@uhcl.edu [Department of Chemistry, University of Houstons-Clear Lake, Houston, TX 77058 (United States)

    2016-10-15

    Two new Co(II) coordination polymers(CPs), namely [Co{sub 2}(bpe){sub 2}(Hbppc)]{sub n} (1) and [Co{sub 3}(μ{sub 3}-OH)(bppc)(bpm)(H{sub 2}O)]·3H{sub 2}O (2) (H{sub 5}bppc=biphenyl-2,4,6,3′,5′-pentacarboxylic acid, bpe=1,2-bis(4-pyridyl)ethene, bpm=bis(4-pyridyl)amine), have been obtained and characterized by elemental analysis, single-crystal X-ray diffraction, powder X-ray diffraction (PXRD), IR spectra and thermogravimetric analysis (TGA). 1 shows a binodal (4,6)-connected fsc net with a (4{sup 4}·6{sup 10}·8)(4{sup 4}·6{sup 2}) topology, while 2 shows a binodal (5,7)-connected 3D network based on trinuclear [Co{sub 3}(μ{sub 3}-OH)]{sup 5+} units with unusual (3.4{sup 6}.5{sup 2}.6)(3{sup 2}.4{sup 6}.5{sup 7}.6{sup 5}.7) topology. Variable-temperature magnetic susceptibility measurements reveals that complex 1 shows ferromagnetic interactions between the adjacent Co(II) ions, whereas 2 is a antiferromagnetic system. - Graphical abstract: Two new Co(II) coordination polymers with bi- and trinuclear units have been obtained. 1 shows a binodal (4,6)-connected fsc net with a (4{sup 4}·6{sup 10}·8)(4{sup 4}·6{sup 2}) topology and antiferromagnetic interactions between the adjacent Co(II) ions, while 2 is a binodal (5,7)-connected 3D network with unusual (3.4{sup 6}.5{sup 2}.6)(3{sup 2}.4{sup 6}.5{sup 7}.6{sup 5}.7) topology and a ferromagnetic system. - Highlights: • Two Co(II) coordination polymers with different multimetallic clusters as building units. • A (4,6)-connected fsc net and a (5,7)-connected 3D network. • A antiferromagnetic coupling for 1 and A ferromagnetic coupling for 2.

  14. Four thiophene-pyridyl-amide-based Zn{sup II}/Cd{sup II} coordination polymers: Assembly, structures, photocatalytic properties and fluorescent recognition for Fe{sup 3+}

    Energy Technology Data Exchange (ETDEWEB)

    Wang, Xiu-Li; Wu, Xiao-Mei; Liu, Guo-Cheng; Li, Qiao-Min; Lin, Hong-Yan; Wang, Xiang

    2017-05-15

    By tuning metal ions and combining with different dicarboxylates, four new semi-rigid thiophene-bis-pyridyl-bis-amide-based coordination polymers, namely, [Zn(3-bptpa)(1,3-BDC)]·DMA·2H{sub 2}O (1), [Zn(3-bptpa)(5-MIP)] (2), [Cd(3-bptpa)(1,3-BDC)]·2H{sub 2}O (3) and [Cd(3-bptpa)(5-MIP)]·4H{sub 2}O (4) (3-bptpa=N,N′-bis(pyridine-3-yl)thiophene-2,5-dicarboxamide, 1,3-H{sub 2}BDC=1,3-benzenedicarboxylic acid, 5-H{sub 2}MIP=5-methylisophthalic acid, DMA=N,N-dimethylacetamide), were solvothermally/hydrothermally synthesized and structurally characterized by single-crystal X-ray diffraction analyses, IR spectra, UV–vis diffuse-reflectance spectra (DRS), powder X-ray diffraction (PXRD) and thermal gravimetric analyses (TG). The structural analysis reveals that Zn-complexes 1 and 2 are similar 2D networks. While Cd-complexes 3 and 4 exhibit similar 2-fold interpenetrating 3D α-Po frameworks with the (4{sup 12}·6{sup 3}) topology. The photocatalytic properties for the degradation of methylene blue (MB) under ultraviolet light irradiation of the title complexes have been investigated in detail. Furthermore, the luminescent sensing behaviors for metal cations of 1–4 have been studied, the results indicate that 3 is an excellent fluorescent probe, with high sensitivity, selectivity, and simple regeneration, for environmentally relevant Fe{sup 3+} ions. - Graphical abstract: Four Zn{sup II}/Cd{sup II} coordination polymers with a thiophene-pyridyl-amide ligand have been prepared. The photocatalytic activities and fluorescent sensing properties for metal ions of the title complexes have been investigated. - Highlights: • Four coordination polymers with thiophene-pyridyl-amide ligands have been obtained. • The central metal ions play an important role in the formation of the frameworks. • The photoluminescent sensing and the photocatalytic properties have been investigated.

  15. Ion induced transformation of polymer films into diamond-like carbon incorporating silver nano particles; Ioneninduzierte Umwandlung von Polymerschichten zu diamantaehnlichem Kohlenstoff mit darin enthaltenen Silber-Nanopartikeln

    Energy Technology Data Exchange (ETDEWEB)

    Schwarz, Florian P.

    2010-03-26

    Silver containing diamond-like carbon (DLC) is an interesting material for medical engineering from several points of view. On the one hand DLC provides high mechanical robustness. It can be used as biocompatible and wear resistant coating for joint replacing implants. On the other hand silver has antimicrobial properties, which could reduce post-operative inflammations. However conventional production of Ag-DLC by co-deposition of silver and carbon in a plasma process is problematic since it does not allow for a separate control of nano particle morphology and matrix properties. In this work an alternative production method has been developed to circumvent this problem. In metall-DLC-production by ion implantation into a nano composite, silver nano particles are initially formed in solution and then incorporated within a polymer matrix. Finally the polymer is transformed into DLC by ion implantation. The aspects and single steps of this method were investigated with regard to the resulting material's properties. The goal was to design an economically relevant deposition method. Based on experimental results a model of the transformation process has been established, which has also been implemented in a computer simulation. Finally the antibacterial properties of the material have been checked in a biomedical test. Here a bacterial killing rate of 90% could be achieved. (orig.)

  16. A one-dimensional ladder-like coordination polymer: poly[[hexa-aqua-bis(μ-5-nitro-benzene-1,3-dicarboxyl-ato-κO,O',O'')(μ-oxalato-κO,O':O'',O''')diyttrium(III)] trihydrate].

    Science.gov (United States)

    Fu, Zhong; Lin, Ying; Zhou, Yun-You; Zhang, Hong-Tao

    2007-12-06

    In the crystal structure of the title one-dimensional coordination polymer, [Y(2)(C(8)H(3)NO(6))(2)(C(2)O(4))(H(2)O)(6)]·3H(2)O, each Y(III) ion is bridged to its neighbours by two 5-nitro-benzene-1,3-dicarboxyl-ate (nbdc) dianions and one oxalate dianion (located on an inversion centre) to form a ladder-like polymeric structure. The two carboxylate groups of nbdc assume different modes of coordination, one is chelating whereas the other is monodentate. Three water mol-ecules coordinate to the Y(III) ion to complete an eight-coordinate distorted dodecahedral geometry. The ladder-like polymers are assembled together by hydrogen bonding and π-π stacking [centrio-centriod distance = 3.819 (9) Å] in the crystal structure.

  17. Incorporating an Inert Polymer into the Interlayer Passivates Surface Defects in Methylammonium Lead Halide Perovskite Solar Cells.

    Science.gov (United States)

    Bi, Shiqing; Zhang, Xuning; Qin, Liang; Wang, Rong; Zhou, Jiyu; Leng, Xuanye; Qiu, Xiaohui; Zhang, Yuan; Zhou, Huiqiong; Tang, Zhiyong

    2017-10-17

    The hysteresis effect and instability are important concerns in hybrid perovskite photovoltaic devices that hold great promise in energy conversion applications. In this study, we show that the power conversion efficiency (PCE), hysteresis, and device lifetime can be simultaneously improved for methylammoniumlead halide (CH 3 NH 3 PbI 3-x Cl x ) solar cells after incorporating poly(methyl methacrylate) (PMMA) into the PC 61 BM electron extraction layer (EEL). By choosing appropriate molecular weights of PMMA, we obtain a 30 % enhancement of PCE along with effectively lowered hysteresis and device degradation, adopting inverted planar device structure. Through the combinatorial study using Kelvin probe force microscopy, diode mobility measurements, and irradiation-dependent solar cell characterization, we attribute the enhanced device parameters (fill factor and open circuit voltage) to the surface passivation of CH 3 NH 3 PbI 3-x Cl x , leading to mitigating charge trapping at the cathode interface and resultant Shockley-Read-Hall charge recombination. Beneficially, modified by inert PMMA, CH 3 NH 3 PbI 3-x Cl x solar cells display a pronounced retardation in performance degradation, resulting from improved film quality in the PC 61 BM layer incorporating PMMA which increases the protection for underneath perovskite films. This work enables a versatile and effective interface approach to deal with essential concerns for solution-processed perovskite solar cells by air-stable and widely accessible materials. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  18. Ag/N-doped reduced graphene oxide incorporated with molecularly imprinted polymer: An advanced electrochemical sensing platform for salbutamol determination.

    Science.gov (United States)

    Li, Junhua; Xu, Zhifeng; Liu, Mengqin; Deng, Peihong; Tang, Siping; Jiang, Jianbo; Feng, Haibo; Qian, Dong; He, Lingzhi

    2017-04-15

    In this work, the metallic silver and non-metallic nitrogen co-doped reduced graphene oxide (Ag-N-RGO) was first synthesized by a simple and cost-effective strategy, and then a molecularly imprinted polymer (MIP) was formed in situ at the surface of the prepared composite via electropolymerization of o-phenylenediamine in the presence of salbutamol as the template molecule. The electrochemical characterizations demonstrate that the bifunctional graphene-based composite shows improved catalytic performance than that of pristine graphene doped with one-component or none. The MIP sensor based on Ag-N-RGO owns high porous surface structure, resulting in the increased current response and enhanced recognition capacity than that of non-imprinted sensor. The outstanding performance of the developed sensor derives from the combined advantages of Ag-N-RGO with effective catalytic property and MIP with excellent selectivity. Under the optimal conditions, the electrochemical response of the developed sensor is linearly proportional to the concentration of salbutamol in the range of 0.03-20.00µmolL -1 with a low detection limit of 7 nmol L -1 . The designed sensor has exhibited the multiple advantages such as low cost, simple manufacture, convenient use, excellent selectivity and good reproducibility. Finally, the proposed method has been extended for the determinations of salbutamol in human urine and pork samples, and the satisfactory recoveries between 98.9-105.3% are achieved. Copyright © 2016 Elsevier B.V. All rights reserved.

  19. Two new coordination polymers with flexible alicyclic carboxylate and bipyridyl co-ligands bearing trinuclear [Ni3(COO)6] SBUs: Synthesis, crystal structures, and magnetic properties

    Science.gov (United States)

    Zhu, Xian-Dong; Li, Yong; Gao, Jian-Gang; Wang, Fen-Hua; Li, Qing-Hai; Yang, Hong-Xun; Chen, Lei

    2017-02-01

    Two new coordination polymers generally formulated as [Ni3(Hchda)2(chda)2(bpy)2(H2O)2]n (1) and [Ni3(Hchda)2(chda)2(bpp)2(H2O)2]n (2) [H2chda = 1,1'-cyclohexanediacetic acid, bpy = 4,4'-bipyridine and bpp = 1,3-bis(4-pyridyl)propane], have been successfully assembled through mixed-ligands synthetic strategy with flexible alicyclic carboxylate and bipyridyl ligands. There structures feature trinuclear nickel secondary building units connected via the bridging bipyridyl spacers to form two-dimensional (4,4) grid layer. The nature of the different N-donor auxiliary ligands leads to the discrepancy in supramolecular structure of the two compounds. Magnetic studies indicate the ferromagnetic intra-complex magnetic interaction in the molecule for 1 and 2.

  20. Solvothermal synthesis and structure of coordination polymers of Nd(III) and Dy(III) with rigid isophthalic acid derivatives and flexible adipic acid

    Science.gov (United States)

    Kariem, Mukaddus; Kumar, Manesh; Yawer, Mohd; Sheikh, Haq Nawaz

    2017-12-01

    Two new coordination polymers (CPs) with the formula [Nd(hip)(adip) 0.5(H2O)2]n.nH2O (1) and [Dy(aip)(adip)0.5(H2O)2]n.nH2O (2) were synthesized by self-assembly of lanthanide salts with rigid [5-hydroxyisophthalic acid (H2hip)], [5-aminoisophthalic acid (H2aip)] and flexible [adipic acid (H2adip)] linkers under solvothermal conditions. The CPs 1 &2 crystallize in monoclinic C2/c space group. Both the CPs have 1D linear ladder shaped extension with the linkages having the backbone of hip2-, aip2- and adip2- ligands. The 1D linear ladder chains generate three dimensional (3D) supramolecular frameworks via significant π-π and hydrogen bonding interactions. The CP 2 (Dy) emit strong ligand sensitized characteristic f-f luminescence emission. The CP 2 also exhibit weak ferromagnetic interactions at low temperatures.

  1. Synthesis and characterization of a multifunctional inorganic-organic hybrid mixed-valence copper(I/II) coordination polymer: {[CuCN][Cu(isonic)2]}n

    Science.gov (United States)

    Liu, Dong-Sheng; Chen, Wen-Tong; Ye, Guang-Ming; Zhang, Jing; Sui, Yan

    2017-12-01

    A new multifunctional mixed-valence copper(I/II) coordination polymer, {[CuCN][Cu(isonic)2]}n(1) (Hisonic = isonicotinic acid), was synthesized by treating isonicotinic acid and 5-amino-tetrazolate (Hatz = 5-amino-tetrazolate) with copper(II) salts under hydrothermal conditions, and characterized by elemental analysis, infrared spectroscopy, and single crystal X-ray diffraction, respectively. The X-ray diffraction analysis reveals that compound exhibit noncentrosymmetric polar packing arrangement. It is three-dimensional (3D) framework with (3,5)-connected 'seh-3' topological network constructed from metal organic framework {[Cu(isonic)2]}n and the inorganic linear chain{Cu(CN)}n subunits. A remarkable feature of 1 is the rhombic open channels that are occupied by a linear chain of {Cu(CN)}n. Impressively compound 1 displays not only a second harmonic generation (SHG) response, but also a ferroelectric behavior and magnetic properties.

  2. A multifunctional three-fold interpenetrated coordination polymer showing excellent luminescent sensing for Cr(VI)/ Fe(III) and photocatalytic properties

    Science.gov (United States)

    Zhu, Zheng; Wang, Mei; Xu, Cun-gang; Zong, Zi-ao; Zhang, Dong-mei; Bi, Shuang-yu; Fan, Yu-hua

    2017-12-01

    A three-fold interpenetrated coordination polymer [Cd2(L)(bibp)3]n (1) (H4L = 5,5‧-(1,4-phenylenebis(methoxy))diisophthalic acid, bibp = 4,4'-bis(imidazolyl)biphenyl) has been rationally constructed, successfully solvothermally synthesized and fully characterized. Complex 1 shows a 3D three-fold interpenetrated novel topological framework with the point symbol (4. 69)2(42. 62. 7. 8), and represents a variety of potential applications. Luminescence studies demonstrate that 1 has high selectivity and sensitivity for pollutant Cr(VI) (CrO42- and Cr2O72-) anion and Fe(III) cation; Photocatalytic studies show that 1 exhibits great degradation activity of three organic dyes (methylene blue (MB), Rhodamine B (RhB) and MalachiteGreen oxalate (MGO)). Furthermore, the possible mechanisms of the luminescent quench and photocatalytic properties have been deduced.

  3. Synthesis, crystal structures and properties of three coordination polymers based on semi-rigid bis(benzimidazole-1-ylmethyl)biphenyl ligand

    Science.gov (United States)

    Liang, Lili; Xue, Hongbao; Chen, Feijian; Zhang, Manli; Zhang, Bingyuan; Tao, Zhaolin

    2017-11-01

    Solvothermal reactions of three metal salts with a linear semi-rigid ligand 4,4‧-bis(benzimidazol-1-ylmethy1)biphenyl) (bbmb) and terephthalic acid (H2TA), lead to three metal-organic coordination polymers, namely, {[Co(bbmb)(TA)] 4H2O} 1, [Zn2(bbmb)2(TA)(NO2)2] 2 and [Cd(bbmb)(TA)(H2O)] 3. Single-crystal X-ray diffraction analyses reveal that compound 1 exhibits a zigzag-shaped 1-D chain, which extended into a three-dimensional supermolecular framework through π-π interactions, compound 2 exhibits a thick two-dimensional sheet, while compound 3 exhibits a unique 3D two-fold interpenetrated network of irl topology. Moreover, IR spectroscopy, powder X-ray diffraction, thermogravimetric analyses, and the properties of the three compounds were studied.

  4. Two novel penetrating coordination polymers based on flexible S-containing dicarboxylate acid with sensing properties towards Fe3+ and Cr2O72- ions

    Science.gov (United States)

    Chen, Zhiwei; Mi, Xiuna; Wang, Suna; Lu, Jing; Li, Yunwu; Li, Dacheng; Dou, Jianmin

    2018-05-01

    Two new coordination polymers (CPs), namely, {[Zn(L)(bpp)]·DMF}n (1) and {[Zn(L)(bpe)]·DMF}n (2) (L = 2,2'-[benzene-1,3-diylbis(methanediylsulfanediyl)]dibenzoic acid, bpp= 1,3-bis(4-pyridyl)propane, bpe = 1,2-Bis(4-pyridyl)ethylene, DMF = N,N-Dimethylformamide), have been solvothermally synthesized and fully characterized. Complex 1 displays a 2D→2D three-fold"false" interpenetrating structure while complex 2 possesses a novel 3-D 4-connected structure with fascinating self-penetrating moieties. The luminescence studies reveal that these complexes exhibited excellent selectivity for Fe3+ and Cr2O72- ions in DMF. The sensing mechanism was investigated through PXRD, XPS , EDS mapping measurements, and discussed in details.

  5. Mixed-valence copper(I,II) complexes with 4-(1H-pyrazol-1-yl)-6-R-pyrimidines: from ionic structures to coordination polymers.

    Science.gov (United States)

    Vinogradova, Katerina A; Krivopalov, Viktor P; Nikolaenkova, Elena B; Pervukhina, Natalia V; Naumov, Dmitrii Yu; Boguslavsky, Evgenii G; Bushuev, Mark B

    2016-01-14

    Two pyrimidine-based ligands, 4-(3,5-diphenyl-1H-pyrazol-1-yl)-6-(morpholino)pyrimidine () and 4-(3,5-diphenyl-1H-pyrazol-1-yl)-6-phenoxypyrimidine (), and a series of mixed-valence copper(i,ii) halide complexes, [Cu(L(2))2Br]2[Cu2Br4] (), [Cu(L(2))2Cl][CuCl2] (), and [Cu2L(3)Br3]n (), have been synthesized. The complex [Cu(L(2))2Br]2[Cu2Br4] was prepared by the reaction of with CuBr2 in a 1 : 1 molar ratio in MeCN. Its chlorido-analogue, the complex [Cu(L(2))2Cl][CuCl2], was synthesized by the reaction between , CuCl2 and CuCl in a 2 : 1 : 1 molar ratio in MeCN. The ligand acts as a chelating one. In the structures of the complexes [Cu(L(2))2Br]2[Cu2Br4] and [Cu(L(2))2Cl][CuCl2] the Cu(2+) ion is in the cationic part of the complex whereas the Cu(+) ion is located in the anionic part. The best way to synthesize the mixed-valence 1D coordination polymer [Cu2L(3)Br3]n is to react CuBr2 with in a 2 : 1 molar ratio in the MeCN/CHCl3 mixture on heating. In the structure of [Cu2L(3)Br3]n the ligand shows chelating/bridging tridentate coordination. This is the first example of the tridentate coordination of 4-(1H-pyrazol-1-yl)-6-R-pyrimidines. The striking difference between the coordination behavior of and (chelating bidentate vs. chelating/bridging coordination) is related with the possibility of rotation of the 6-phenoxy group around the C-O bond which makes the N(1) pyrimidine atom less sterically hindered, enabling it to participate in metal ion binding. Importantly, all copper ions in [Cu2L(3)Br3]n show similar tetrahedral environments, CuNBr3 and CuN2Br2, which is extremely rare for mixed-valence copper(i,ii) compounds. The ligands and show blue emission which is quenched upon their coordination to copper ions. The 1D coordination polymer [Cu2L(3)Br3]n shows high thermal stability and unusual solvent-occlusion properties. The role of the substituents favoring the formation of the mixed-valence copper(i,ii) complexes with 4-(1H-pyrazol-1-yl)-6-R

  6. Incorporation of multilayered silver nanoparticles into polymer brushes as 3-dimensional SERS substrates and their application for bacteria detection

    Energy Technology Data Exchange (ETDEWEB)

    Zhang, Qian; Wang, Xiang-Dong; Tian, Ting; Chu, Li-Qiang, E-mail: chuliqiang@tust.edu.cn

    2017-06-15

    Highlights: • POEGMA/AgNPs composite film prepared via the in-stacking method is employed as 3D SERS substrate. • Control over POEGMA chain length is achieved via SI-ATRP method. • Influence of POEGMA chain length and in-stacking process on SERS performance is investigated. • The 3D SERS substrate is used for the ultrasensitive detection of ATP and S. aureus. - Abstract: Surface-enhanced Raman scattering (SERS) sensors have been extensively studied for ultrasensitive detection of diverse chemical or biological analytes. Facile fabrication of highly sensitive SERS substrates is believed to be of crucial importance in these analytical applications. In this regard, the preparation of 3-dimensional (3D) SERS substrates are explored via the incorporation of multilayered silver nanoparticles (AgNPs) into poly (oligo(ethylene glycol) methacrylate) (POEGMA) brushes by repeating the immersion-rinsing-drying steps for different lengths of time (i.e., the so-called in-stacking method). The POEGMA brushes of different chain lengths are synthesized by surface-initiated atom transfer radical polymerization (ATRP) with various reaction time. The resulting POEGMA/AgNP nanocomposites are characterized by FE-SEM, UV–vis and Raman spectroscopy. FE-SEM and UV–vis results indicate that the AgNPs are successfully incorporated into the POEGMA brushes with a 3D configuration. The nanocomposite films are employed as SERS substrates for the detection of a Raman reporter molecule (i.e., 4-aminothiophenol), giving rise to an enhancement factor of up to 1.29 × 10{sup 7} and also having relatively good uniformity and reproducibility. The obtained 3D SERS substrates are also used for the detection of a typical gram-positive bacterium, Staphylococcus aureus. The limit of detection is found to be as low as ca. 8 CFU/mL.

  7. Proton conducting membranes prepared by incorporation of organophosphorus acids into alcohol barrier polymers for direct methanol fuel cells

    Science.gov (United States)

    Jiang, Zhongyi; Zheng, Xiaohong; Wu, Hong; Pan, Fusheng

    A novel type of DMFC membrane was developed via incorporation of organophosphorus acids (OPAs) into alcohol barrier materials (polyvinyl alcohol/chitosan, PVA/CS) to simultaneously acquire high proton conductivity and low methanol permeability. Three kinds of OPAs including amino trimethylene phosphonic acid (ATMP), ethylene diamine tetra(methylene phosphonic acid) (EDTMP) and hexamethylene diamine tetra(methylene phosphonic acid) (HDTMP), with different molecular structure and phosphonic acid groups content were added into PVA/CS blends and served the dual functions as proton conductor as well as crosslinker. The as-prepared OPA-doped PVA/CS membranes exhibited remarkably enhanced proton conducting ability, 2-4 times higher than that of the pristine PVA/CS membrane, comparable with that for Nafion ®117 membrane (5.04 × 10 -2 S cm -1). The highest proton conductivities 3.58 × 10 -2, 3.51 × 10 -2 and 2.61 × 10 -2 S cm -1 for ATMP-, EDTMP- and HDTMP-doped membranes, respectively were all achieved at highest initial OPA doping content (23.1 wt.%) at room temperature. The EDTMP-doped PVA/CS membrane with an acid content of 13.9 wt.% showed the lowest methanol permeability of 2.32 × 10 -7 cm 2 s -1 which was 16 times lower than that of Nafion ®117 membrane. In addition, the thermal stability and oxidative durability were both significantly improved by the incorporation of OPAs in comparison with pristine PVA/CS membranes.

  8. Proton conducting membranes prepared by incorporation of organophosphorus acids into alcohol barrier polymers for direct methanol fuel cells

    Energy Technology Data Exchange (ETDEWEB)

    Jiang, Zhongyi; Zheng, Xiaohong; Wu, Hong; Pan, Fusheng [Key Laboratory for Green Chemical Technology, School of Chemical Engineering and Technology, Tianjin University, Tianjin 300072 (China)

    2008-10-15

    A novel type of DMFC membrane was developed via incorporation of organophosphorus acids (OPAs) into alcohol barrier materials (polyvinyl alcohol/chitosan, PVA/CS) to simultaneously acquire high proton conductivity and low methanol permeability. Three kinds of OPAs including amino trimethylene phosphonic acid (ATMP), ethylene diamine tetra(methylene phosphonic acid) (EDTMP) and hexamethylene diamine tetra(methylene phosphonic acid) (HDTMP), with different molecular structure and phosphonic acid groups content were added into PVA/CS blends and served the dual functions as proton conductor as well as crosslinker. The as-prepared OPA-doped PVA/CS membranes exhibited remarkably enhanced proton conducting ability, 2-4 times higher than that of the pristine PVA/CS membrane, comparable with that for Nafion {sup registered} 117 membrane (5.04 x 10{sup -2} S cm{sup -1}). The highest proton conductivities 3.58 x 10{sup -2}, 3.51 x 10{sup -2} and 2.61 x 10{sup -2} S cm{sup -1} for ATMP-, EDTMP- and HDTMP-doped membranes, respectively were all achieved at highest initial OPA doping content (23.1 wt.%) at room temperature. The EDTMP-doped PVA/CS membrane with an acid content of 13.9 wt.% showed the lowest methanol permeability of 2.32 x 10{sup -7} cm{sup 2} s{sup -1} which was 16 times lower than that of Nafion {sup registered} 117 membrane. In addition, the thermal stability and oxidative durability were both significantly improved by the incorporation of OPAs in comparison with pristine PVA/CS membranes. (author)

  9. Synthesis, structural analyses and antimicrobial activity of the water soluble 1D coordination polymer [Ag(3-aminopyridine)]ClO4

    Science.gov (United States)

    Soliman, Saied M.; Elsilk, Sobhy E.

    2017-12-01

    The synthesis, characterization and molecular structure aspects of the [Ag(3-aminopyridine)]ClO4 coordination polymer have been presented. Single crystal X-ray diffraction (SC-XRD) analysis showed that the asymmetric unit consists of two Ag, one 3-aminopyridine (3APy) and one ionic perchlorate anion. The 3-aminpyridine (3APy) acts as a bridged ligand connecting the Ag-atoms via the amine and pyridine ring N-atoms leading to the formation of 1D coordination polymer. The perchlorate anion connects the 1D chains via a complicated set of Nsbnd H⋯O and Csbnd H⋯O hydrogen bonding interactions. Strong FTIR spectral bands at 1143.1, 1116.7 and 1085.6 cm-1 and a weak band at 932.9 cm-1 revealed the ionic character of the complex. Single point DFT calculations combined with atoms in molecules (AIM) and natural bond orbital (NBO) analyses indicated stronger Agsbnd N(py) than Agsbnd N(NH2) interaction. The former has more covalent character according to the AIM topological parameters. The Ag⋯O interactions are weak and are mainly affected by dispersion interactions. Of the six DFT methods used for geometry optimizations, the TPSSTPSS then PBEPBE are the most powerful DFT methods to predict the Agsbnd N distances. Effect of methods on the frontier molecular orbitals energies and shapes are also presented. Preliminary antimicrobial studies showed that the [Ag(3APy)]ClO4 complex has more activity against all the studied microorganisms than the free 3APy.

  10. Heteronuclear, mixed-metal Ag(I)-Mn(II) coordination polymers with bridging N-pyridinylisonicotinohydrazide ligands: synthesis, crystal structures, magnetic and photoluminescence properties.

    Science.gov (United States)

    Bikas, Rahman; Hosseini-Monfared, Hassan; Vasylyeva, Vera; Sanchiz, Joaquín; Alonso, Javier; Barandiaran, Jose Manuel; Janiak, Christoph

    2014-08-21

    Mixed-metal dicyanoargentate-bridged coordination polymers of Ag(i)-Mn(ii) have been prepared and their structure and magnetic properties were determined. Reaction of manganese(ii) chloride and potassium dicyanoargentate(i) with (X)(pyridin-2-ylmethylene)isonicotinohydrazide ligands (HL(1) X = Ph, HL(2) X = Me, HL(3) X = H) produced the coordination polymer 2D-[Mn(μ-L(1))(Cl)(μ-NCAgCN)Mn0.5(CH3OH)]n (), 1D-{[Mn(L(2))(Cl)(μ-NCAgCN)Mn0.5(CH3OH)]CH3OH}n () and [Mn(L(3))(Cl)(μ-NCAgCN)Mn0.5(CH3OH)]n () in good yields. Trinuclear {Mn(μ-L(1))Mn(μ-L(1))Mn} and [Ag(CN)2](-) building units form a two-dimensional slab in and 1D strands in . Variable temperature magnetic susceptibility measurements showed that despite the long distance among the high spin Mn(ii) ions [10.4676(12) Å and 10.522(1) Å, for and , respectively], weak antiferromagnetic coupling takes place through the long NC-Ag-CN bridge. The best fit parameters to the model led to the magnetic coupling constant of J = -0.1 and J = -0.47 cm(-1) for and , respectively. The photoluminescence behaviour of compounds and was studied. The spectrum of compound shows a broad emission centered at about 450 nm and two excitation maxima at 270 and 310 nm.

  11. Synthesis, structure and characterization of two copper(II) supramolecular coordination polymers based on a multifunctional ligand 2-amino-4-sulfobenzoic acid.

    Science.gov (United States)

    Wei, Yan; Zhang, Lei; Wang, Meng-Jie; Chen, Si-Chun; Wang, Zi-Hao; Zhang, Kou-Lin

    2015-07-01

    Copper(II) coordination polymers have attracted considerable interest due to their catalytic, adsorption, luminescence and magnetic properties. The reactions of copper(II) with 2-amino-4-sulfobenzoic acid (H(2)asba) in the presence/absence of the auxiliary chelating ligand 1,10-phenanthroline (phen) under ambient conditions yielded two supramolecular coordination polymers, namely (3-amino-4-carboxybenzene-1-sulfonato-κO(1))bis(1,10-phenanthroline-κ(2)N,N')copper(II) 3-amino-4-carboxybenzene-1-sulfonate monohydrate, [Cu(C7H6N2O5S)(C12H8N2)2](C7H6N2O5S)·H2O, (1), and catena-poly[[diaquacopper(II)]-μ-3-amino-4-carboxylatobenzene-1-sulfonato-κ(2)O(4):O(4')], [Cu(C7H6N2O5S)(H2O)2]n, (2). The products were characterized by FT-IR spectroscopy, thermogravimetric analysis (TGA), solid-state UV-Vis spectroscopy and single-crystal X-ray diffraction analysis, as well as by variable-temperature powder X-ray diffraction analysis (VT-PXRD). Intermolecular π-π stacking interactions in (1) link the mononuclear copper(II) cation units into a supramolecular polymeric chain, which is further extended into a supramolecular double chain through interchain hydrogen bonds. Supramolecular double chains are then extended into a two-dimensional supramolecular double layer through hydrogen bonds between the lattice Hasba(-) anions, H2O molecules and double chains. Left- and right-handed 21 helices formed by the Hasba(-) anions are arranged alternately within the two-dimensional supramolecular double layers. Complex (2) exhibits a polymeric chain which is further extended into a three-dimensional supramolecular network through interchain hydrogen bonds. Complex (1) shows a reversible dehydration-rehydration behaviour, while complex (2) shows an irreversible dehydration-rehydration behaviour.

  12. Syntheses, crystal structures and properties of series of 4d–4f ln(III)–Ag(I) heterometallic coordination polymers

    Energy Technology Data Exchange (ETDEWEB)

    Ran, Xing-Rui [School of Chemistry and Environment, South China Normal University, Guangzhou 510006 (China); Wang, Ning [School of Materials Science and Engineering, Nanyang Technological University, 50 Nanyang Avenue, Singapore 639798 (Singapore); Xie, Wei-Ping; Xiong, Yan-Ju; Cheng, Qian [School of Chemistry and Environment, South China Normal University, Guangzhou 510006 (China); Long, Yi [School of Materials Science and Engineering, Nanyang Technological University, 50 Nanyang Avenue, Singapore 639798 (Singapore); Yue, Shan-Tang, E-mail: yuesht@scnu.edu.cn [School of Chemistry and Environment, South China Normal University, Guangzhou 510006 (China); Guangzhou Key Laboratory of Materials for Energy Conversion and Storage, Guangzhou (China); Liu, Ying-Liang [College of Science, South China Agricultural University, Guangzhou 510642 (China)

    2015-05-15

    By control of the experimental parameters such as ligands, pH value and reacting temperature, series of three-dimensional (3D) 4d–4f Ln(III)–Ag(I) porous coordination polymers (PCPs) with interesting chain-layer construction, namely, ([Ln{sup III}Ag{sup I}(na)(ina)(ox)]·2(H{sub 2}O)){sub n} [Ln=Sm(1), Eu(2), Gd(3), Tb(4), Dy(5), Ho(6), Y(7), Yb(8)], have been successfully synthesized under hydrothermal conditions and structurally characterized. All the complexes are characterized by elemental analyses, FT-IR spectroscopy, Powder X-ray diffraction (PXRD) and thermogravimetric analyses (TGA). Furthermore, the luminescence properties of compounds 2 and 4 and the magsnetic properties of complexes 3 and 5 were also investigated in detail. - Graphical abstract: Series of three-dimensional (3D) 4d–4f Ln(III)–Ag(I) porous coordination polymers (PCPs) with interesting chain-layer construction which are featured by tetranuclear Ln{sub 2}Ag{sub 2} and ‘non-linear’ N–Ag–N linkages. - Highlights: • Complexes 1–8 are first built by three kinds of organic ligands based on nicotinic acid and isonicotinic acid. • PCPs 1–8 are featured by tetranuclear Ln{sub 2}Ag{sub 2} and ‘non-linear’ N–Ag–N linkages. • The total solvent-accessible volume of PCP 2 comprises 11.6% of the crystal volume after dislodging the free water molecules. • Complexes 2 and 4 exhibit characteristic lanthanide-centered luminescence, while compounds 3 and 5 show antiferromagnetic behaviors.

  13. Synthesis, vibrational spectrometry and thermal characterizations of coordination polymers derived from divalent metal ions and hydroxyl terminated polyurethane as ligand

    Science.gov (United States)

    Laxmi; Khan, Shabnam; Kareem, Abdul; Zafar, Fahmina; Nishat, Nahid

    2018-01-01

    A series of novel coordination polyurethanes [HTPU-M, where M = Mn(II) 'd5', Ni(II) 'd8', and Zn(II) 'd10'] have been synthesized to investigate the effect of divalent metal ions coordination on structure, thermal and adsorption properties of low molecular weight hydroxyl terminated polyurethane (HTPU). HTPU-M have been synthesized in situ where, sbnd OH group of HTPU (synthesized by the condensation polymerization reaction of ethylene glycol (EG) and toluene diisocyanate (TDI) in presence of catalyst) on condensation polymerization with metal acetate in presence of acid catalyst synthesized HTPU-M followed by coordination of metal ions with hetero atoms. The structure, composition and geometry of HTPU-M have been confirmed by vibrational spectrometry (FTIR), 1H NMR, elemental analysis and UV-Visible spectroscopy. Morphological structures of HTPU-M were analyzed by X-Ray Diffraction analysis (XRD), Field Emission Scanning Electron Microscope (FE-SEM) with Energy Dispersive X-ray spectroscopy (EDX) and High Resolution Transmission Electron Microscope (HR-TEM) techniques. The thermal degradation pattern and thermal stability of HTPU-M in comparison to HTPU was investigated by thermal-gravimetric (TG)/differential thermal (DT), analyses along with Integral procedure decomposition temperature (IPDT) by Doyle method. The molecular weight of HTPU was determined by gel permeation chromatography (GPC). The preliminary adsorption/desorption studies of HTPU-M for Congo red (CR) was studied by batch adsorption techniques. The results indicated that HTPU-M have amorphous, layered morphology with higher number of nano-sized grooves in comparison to HTPU. Coordination of metal to HTPU plays a key role in enhancing the thermal stability [HTPU-Ni(II) > HTPU-Mn(II) > HTPU-Zn(II) > HTPU]. The HTPU-M can be utilized for industrial waste water treatment by removing environmental pollutants.

  14. Synthesis, vibrational spectrometry and thermal characterizations of coordination polymers derived from divalent metal ions and hydroxyl terminated polyurethane as ligand.

    Science.gov (United States)

    Laxmi; Khan, Shabnam; Kareem, Abdul; Zafar, Fahmina; Nishat, Nahid

    2018-01-05

    A series of novel coordination polyurethanes [HTPU-M, where M=Mn(II) 'd 5 ', Ni(II) 'd 8 ', and Zn(II) 'd 10 '] have been synthesized to investigate the effect of divalent metal ions coordination on structure, thermal and adsorption properties of low molecular weight hydroxyl terminated polyurethane (HTPU). HTPU-M have been synthesized in situ where, OH group of HTPU (synthesized by the condensation polymerization reaction of ethylene glycol (EG) and toluene diisocyanate (TDI) in presence of catalyst) on condensation polymerization with metal acetate in presence of acid catalyst synthesized HTPU-M followed by coordination of metal ions with hetero atoms. The structure, composition and geometry of HTPU-M have been confirmed by vibrational spectrometry (FTIR), 1 H NMR, elemental analysis and UV-Visible spectroscopy. Morphological structures of HTPU-M were analyzed by X-Ray Diffraction analysis (XRD), Field Emission Scanning Electron Microscope (FE-SEM) with Energy Dispersive X-ray spectroscopy (EDX) and High Resolution Transmission Electron Microscope (HR-TEM) techniques. The thermal degradation pattern and thermal stability of HTPU-M in comparison to HTPU was investigated by thermal-gravimetric (TG)/differential thermal (DT), analyses along with Integral procedure decomposition temperature (IPDT) by Doyle method. The molecular weight of HTPU was determined by gel permeation chromatography (GPC). The preliminary adsorption/desorption studies of HTPU-M for Congo red (CR) was studied by batch adsorption techniques. The results indicated that HTPU-M have amorphous, layered morphology with higher number of nano-sized grooves in comparison to HTPU. Coordination of metal to HTPU plays a key role in enhancing the thermal stability [HTPU-Ni(II)>HTPU-Mn(II)>HTPU-Zn(II)>HTPU]. The HTPU-M can be utilized for industrial waste water treatment by removing environmental pollutants. Copyright © 2017 Elsevier B.V. All rights reserved.

  15. Crystal structure of the coordination polymer [FeIII2{PtII(CN4}3

    Directory of Open Access Journals (Sweden)

    Maksym Seredyuk

    2015-01-01

    Full Text Available The title complex, poly[dodeca-μ-cyanido-diiron(IIItriplatinum(II], [FeIII2{PtII(CN4}3], has a three-dimensional polymeric structure. It is built-up from square-planar [PtII(CN4]2− anions (point group symmetry 2/m bridging cationic [FeIIIPtII(CN4]+∞ layers extending in the bc plane. The FeII atoms of the layers are located on inversion centres and exhibit an octahedral coordination sphere defined by six N atoms of cyanide ligands, while the PtII atoms are located on twofold rotation axes and are surrounded by four C atoms of the cyanide ligands in a square-planar coordination. The geometrical preferences of the two cations for octahedral and square-planar coordination, respectively, lead to a corrugated organisation of the layers. The distance between neighbouring [FeIIIPtII(CN4]+∞ layers corresponds to the length a/2 = 8.0070 (3 Å, and the separation between two neighbouring PtII atoms of the bridging [PtII(CN4]2− groups corresponds to the length of the c axis [7.5720 (2 Å]. The structure is porous with accessible voids of 390 Å3 per unit cell.

  16. Radiation synthesis and modification of polymers for biomedical applications. Final results of a co-ordinated research project. 1996-2000

    International Nuclear Information System (INIS)

    2002-12-01

    Radiation techniques are being used for synthesis of hydrogels, functional polymers, interpenetrating systems, chemical modification of surfaces, immobilization of bioactive materials, synthesis of functional micro- and nanospheres and processing of naturally derived biomaterials. Potential medical applications of these biomaterials include implants, topical dressings, treatment devices and drug delivery systems. Biotechnological applications include diagnostic assays, separation and purification systems, immobilized enzyme and cell bioprocesses and cell culture surfaces. The main objective of the CRP on The use of Radiation Processing to Prepare Biomaterials for Application in Medicine was to co-ordinate the research carried out in the participating countries, to ensure that different research programmes complement each other and the information exchange is available to all. Furthermore, the objective was to expand the use of ionizing radiation in two major areas: synthesis of polymers and gels for medical and biotechnological applications, and modification of surfaces to achieve a specific functionality and/or to immobilize bioactive materials. This publication contains 10 reports of participants; each of the reports has been indexed separately

  17. Synthesis of non-toxic As and Cr nanoparticles through redox activity of highly flexible layered coordination polymer of Ni(II)

    Science.gov (United States)

    Agarwal, Rashmi A.

    2018-03-01

    A simple method for the sequestration of As(III) and Cr(VI) from water has been demonstrated by utilizing a highly flexible porous coordination polymer (PCP) of Ni(II) in its as synthesized form or without solvent removal. This PCP reduces the high toxicity of As(III) and Cr(VI) ions into non-toxic As(0) and Cr/Cr2O3/CrO2 (zero, tri and tetravalent) nanoparticles (NPs) within its pores, and this is characterized by powder x-ray diffraction, x-ray photoelectron spectroscopy and high-resolution transmission electron microscopy analysis. The high functionality of this polymer is due to the presence of monodentate carboxylate groups of a benzenetricarboxylate linker, which provide anchoring sites to the metal ions of the metal precursors. Due to the highly oxidising nature of these toxic ions, a redox reaction takes place between the framework metal ions and toxic metal ions, which is explained by an electron paramagnetic resonance study. This is the first report to synthesize non-toxic, as well as useful, NPs of As and Cr from their highly toxic ions within the cavities of a PCP for remediation of the toxic waste stream and contaminated waste water.

  18. Coordination Polymers Containing 1,3-Phenylenebis-((1H-1,2,4-triazol-1-yl)methanone) Ligand: Synthesis and ε-Caprolactone Polymerization Behavior.

    Science.gov (United States)

    Bello-Vieda, Nestor J; Murcia, Ricardo A; Muñoz-Castro, Alvaro; Macías, Mario A; Hurtado, John J

    2017-11-10

    The reaction of isophthaloyl dichloride with 1 H -1,2,4-triazole afforded the new ligand 1,3-phenylenebis(1,2,4-triazole-1-yl)methanone ( 1 ). A series of Co(II), Cu(II), Zn(II) and Ni(II) complexes were synthesized using 1 and then characterized by melting point analysis, elemental analysis, theoretical calculations, thermogravimetric analysis, X-ray powder diffraction, nuclear magnetic resonance, infrared and Raman spectroscopy. Experimental and computational studies predict the formation of coordination polymers (CPs). The cobalt and copper CPs and zinc(II) complex were found to be good initiators for the ring-opening polymerization of ε-caprolactone (CL) under solvent-free conditions. ¹H-NMR analysis showed that the obtained polymers of CL were mainly linear and had terminal hydroxymethylene groups. Differential scanning calorimetry showed that the obtained polycaprolactones had high crystallinity, and TGA showed that they had decomposition temperatures above 400 °C. These results provide insight and guidance for the design of metal complexes with potential applications in the polymerization of CL.

  19. Construction of a 2D Co(II) Coordination Polymer with (4,4)-Connected Topology: Synthesis, Crystal Structure, and Surface Photo-electric Property

    Energy Technology Data Exchange (ETDEWEB)

    Li, Jiaming [Qinzhou Univ., Qinzhou (China)

    2014-04-15

    A 2D grid-like (4, 4)-connected topology coordination polymer, [Co(BTA){sub 2}(H{sub 2}O){sub 2}]{sub n}, where HBTA = 2-(1H-benzotriazol-1-yl)acetic acid, has been synthesized by hydrothermal method and characterized by single crystal X-ray diffraction, IR spectroscopy, elemental analysis and surface photovoltage spectroscopy (SPS). X-ray diffraction analyses indicated that displays octahedral metal centers with secondary building units (SBUs) [Co(BTA){sub 2}(H{sub 2}O){sub 2}] bridged by the BTA. ligands. In the crystal, the 2D supramolecular architecture is further supported by O-H···O, O-H···N, C-H···O hydrogen bonds and π··π stacking interactions. The SPS of polymer 1 indicates that there are positive response bands in the range of 300.600 nm showing photo-electric conversion properties. There are good relationships between SPS and UV-Vis spectra.

  20. Coordination Polymers Containing 1,3-Phenylenebis-((1H-1,2,4-triazol-1-ylmethanone Ligand: Synthesis and ε-Caprolactone Polymerization Behavior

    Directory of Open Access Journals (Sweden)

    Nestor J. Bello-Vieda

    2017-11-01

    Full Text Available The reaction of isophthaloyl dichloride with 1H-1,2,4-triazole afforded the new ligand 1,3-phenylenebis(1,2,4-triazole-1-ylmethanone (1. A series of Co(II, Cu(II, Zn(II and Ni(II complexes were synthesized using 1 and then characterized by melting point analysis, elemental analysis, theoretical calculations, thermogravimetric analysis, X-ray powder diffraction, nuclear magnetic resonance, infrared and Raman spectroscopy. Experimental and computational studies predict the formation of coordination polymers (CPs. The cobalt and copper CPs and zinc(II complex were found to be good initiators for the ring-opening polymerization of ε-caprolactone (CL under solvent-free conditions. 1H-NMR analysis showed that the obtained polymers of CL were mainly linear and had terminal hydroxymethylene groups. Differential scanning calorimetry showed that the obtained polycaprolactones had high crystallinity, and TGA showed that they had decomposition temperatures above 400 °C. These results provide insight and guidance for the design of metal complexes with potential applications in the polymerization of CL.

  1. Luminescent coordination polymers for the VIS and NIR range constituting LnCl₃ and 1,2-bis(4-pyridyl)ethane.

    Science.gov (United States)

    Dannenbauer, N; Matthes, P R; Müller-Buschbaum, K

    2016-04-21

    A series of 14 lanthanide containing coordination polymers LnCl3 with 1,2-bis(4-pyridyl)ethane (bpe) was synthesized from either thiazole or pyridine. Depending on the ligand content, a structural diversity from 3D-frameworks [LnCl3(bpe)2]·thz, Ln = Ce-Lu, to 1D-strands [La2Cl6(bpe)2(thz)6] and [LnCl3(bpe)(py)2]·(bpe/py), Ln = Gd, Er, was obtained and characterized by X-ray single crystal diffraction, powder diffraction, differential thermal analysis and thermogravimetry (DTA/TG), IR-spectroscopy and photoluminescence spectroscopy. The compounds exhibit a variety of luminescence properties and different phenomena. This includes ligand centred fluorescence, metal-centred 5d-4f/4f-4f emission in the visible and the NIR range, antenna effects via Dexter and Förster energy transfer mechanisms, excitation dependent emission with a correlating shift of the chromaticity coordinates and inner filter effects by combined re-absorption/emission.

  2. Synthesis, structure, and electrochemistry and magnetic properties of a novel 1D homochiral MnIII(5-Brsalen) coordination polymer with left-handed helical character

    Science.gov (United States)

    Dong, Dapeng; Yu, Naisen; Zhao, Haiyan; Liu, Dedi; Liu, Jia; Li, Zhenghua; Liu, Dongping

    2016-01-01

    A novel homochiral manganese (III) Mn(5-Brsalen) coordination polymer with left-handed helical character by spontaneous resolution on crystallization by using Mn(5-Brsalen) and 4,4-bipyridine, [MnIII(5-Brsalen)(4,4-bipy)]·ClO4·CH3OH (1) (4,4-bipy = 4,4-bipyridine) has been synthesized and structurally characterized by X-ray single-crystal diffraction, elemental analysis and infrared spectroscopy. In compound 1, each manganese(III) anion is six-coordinate octahedral being bonded to four atoms of 5-Brsalen ligand in an equatorial plane and two nitrogen atoms from a 4,4-bipyridine ligand in axial positions. The structure of compound 1 can be described a supramolecular 2D-like structure which was formed by the intermolecular π-stacking interactions between the neighboring chains of the aromatic rings of 4,4-bipyridine and 5-Brsalen molecules. UV-vis absorption spectrum, electrochemistry and magnetic properties of the compound 1 have also been studied.

  3. Anhydrous thallium hydrogen L-glutamate: polymer networks formed by sandwich layers of oxygen-coordinated thallium ions cores shielded by hydrogen L-glutamate counterions.

    Science.gov (United States)

    Bodner, Thomas; Wirnsberger, Bianca; Albering, Jörg; Wiesbrock, Frank

    2011-11-07

    Anhydrous thallium hydrogen L-glutamate [Tl(L-GluH)] crystallizes from water (space group P2(1)) with a layer structure in which the thallium ions are penta- and hexacoordinated exclusively by the oxygen atoms of the γ-carboxylate group of the hydrogen L-glutamate anions to form a two-dimensional coordination polymer. The thallium-oxygen layer is composed of Tl(2)O(2) and TlCO(2) quadrangles and is only 3 Å high. Only one hemisphere of the thallium ions participates in coordination, indicative of the presence of the 6s(2) lone pair of electrons. The thallium-oxygen assemblies are shielded by the hydrogen l-glutamate anions. Only the carbon atom of the α-carboxylate group deviates from the plane spanned by the thallium ions, the γ-carboxylate groups and the proton bearing carbon atoms, which are in trans conformation. Given the abundance of L-glutamic and L-aspartic acid in biological systems on the one hand and the high toxicity of thallium on the other hand, it is worth mentioning that the dominant structural motifs in the crystal structure of [Tl(L-GluH)] strongly resemble their corresponding analogues in the crystalline phase of [K(L-AspH)(H(2)O)(2)].

  4. Mössbauer spectroscopic study on spin crossover coordination polymer Fe(3-Clpy){sub 2}[Pd(CN){sub 4}

    Energy Technology Data Exchange (ETDEWEB)

    Kitazawa, Takafumi, E-mail: kitazawa@chem.sci.toho-u.ac.jp; Sekiya, Madoka; Kawasaki, Takeshi; Takahashi, Masashi [Toho University, Department of Chemistry, Faculty of Science (Japan)

    2016-12-15

    {sup 57}Fe Mössbauer spectroscopic results on the alternatively prepared spin crossover coordination polymer Fe(3-Clpy){sub 2}Pd(CN){sub 4} sample I agree with those of SQUID data. Mössbauer specrum at RT shows two diffrent doublets which correspond to the HS1(inner doublet) and HS2(outer doublet). The intensity of the HS1 doublet decreases on cooling to 78 K at the expense of a new one featuring the LS singlet. Almost 100 % of HS1 change to LS singlet due to iron(II) ions coordinated by four N atoms of cyano groups and two N atoms of 3-Clpy ligand in the sample I. The SQUID data of the sample I prepared by a new direct contact method are different from those of the already reported Fe(3-Clpy){sub 2}Pd(CN){sub 4} sample. The differences of the SQUID data are associated with particle size effects in molecule spin crossover samples.

  5. 2D l-Di-toluoyl-tartaric acid Lanthanide Coordination Polymers: Toward Single-component White-Light and NIR Luminescent Materials.

    Science.gov (United States)

    Niu, Wan-Ying; Sun, Jing-Wen; Yan, Peng-Fei; Li, Yu-Xin; An, Guang-Hui; Li, Guang-Ming

    2016-02-18

    A series of five l-di-p-toluoyl-tartaric acid (l-DTTA) lanthanide coordination polymers, namely {[Ln4 K(4)  L6 (H2O)x ]⋅yH2 O}n , [Ln=Dy (1), x=24, y=12; Ln=Ho (2), x=23, y=12; Ln=Er (3), x=24, y=12; Ln=Yb (4), x=24, y=11; Ln=Lu (5), x=24, y=12] have been isolated by simple reactions of H2L (H2 L= L-DTTA) with LnCl3 ⋅6 H2O at ambient temperature. X-ray crystallographic analysis reveals that complexes 1-5 feature two-dimensional (2D) network structures in which the Ln(3+) ions are bridged by carboxylate groups of ligands in two unique coordinated modes. Luminescent spectra demonstrate that complex 1 realizes single-component white-light emission, while complexes 2-4 exhibit a characteristic near-infrared (NIR) luminescence in the solid state at room temperature. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  6. Synthesis and Characterization of Novel Copper(II 2D Coordination Polymers from a Fluorinated Flexible Ligand with Remarkable Clathration Ability

    Directory of Open Access Journals (Sweden)

    Kayoko Kasai

    2011-11-01

    Full Text Available Two-dimensional (2D grid coordination polymers were prepared by the reaction of 1,4-bis(4-pyridylmethyltetrafluorobenzene (bpf with Cu(NO32 in the presence of aromatic compounds. Crystal structures of {[Cu(bpf2(NO32]·(biphenyl2}n (1, {[Cu(bpf2(NO32]·(m-C6H4(OMe22}n (2, {[Cu(bpf2(NO32]·PhtBu}n (3 and {[Cu(bpf2(NO3(H2O]NO3·(bpf0.5}n (4 were determined. The grid networks were held together by C–H···O and C–H···F hydrogen bonds via the NO3− anions and the tetrafluorophenylene rings of bpf, respectively. Biphenyl, m-dimethoxybenzene, t-butylbenzene, and bpf molecules were clathrated in cyclic cavities of the grid networks through arene-perfluoroarene interactions. These coordination networks have remarkable clathration ability for aromatic compounds.

  7. Biocompatible nanocomposite of TiO2 incorporated bi-polymer for articular cartilage tissue regeneration: A facile material.

    Science.gov (United States)

    Cao, Lei; Wu, Xiaofeng; Wang, Qiugen; Wang, Jiandong

    2018-01-01

    The development and design of polymeric hydrogels for articular cartilage tissue engineering have been a vital biomedical research for recent days. Organic/inorganic combined hydrogels with improved surface activity have shown potential for the repair and regeneration of hard tissues, but have not been broadly studied for articular cartilage tissue engineering applications. In this work, bi-polymeric hydrogel composite was designed with the incorporation some quantities of stick-like TiO 2 nanostructures for favorable surface behavior and enhancement of osteoblast adhesions. The microscopic investigations clearly exhibited that the stick-like TiO 2 nanostructured materials are highly inserted into the PVA/PVP bi-polymeric matrix, due to the long-chain PVA molecules are promoted to physical crosslinking density in hydrogel network. The results of improved surface topography of hydrogel matrixes show that more flatted cell morphologies and enhanced osteoblast attachment on the synthesized nanocomposites. The crystalline bone and stick-like TiO 2 nanocomposites significantly improved the bioactivity via lamellipodia and filopodia extension of osteoblast cells, due to its excellent intercellular connection and regulated cell responses. Consequently, these hydrogel has been enhanced the antibacterial activity against Staphylococcus aureus and Escherichia coli bacterial pathogens. Hence it is concluded that these hydrogel nanocomposite with improved morphology, osteoblast behavior and bactericidal activity have highly potential candidates for articular cartilage tissue regeneration applications. Copyright © 2017 Elsevier B.V. All rights reserved.

  8. Effect of three bis-pyridyl-bis-amide ligands with various spacers on the structural diversity of new multifunctional cobalt(II) coordination polymers

    Energy Technology Data Exchange (ETDEWEB)

    Lin, Hong-Yan [Department of Chemistry, Bohai University, Jinzhou 121000 (China); Lu, Huizhe [Department of Applied Chemistry, China Agricultural University, Beijing, 100193 (China); Le, Mao; Luan, Jian [Department of Chemistry, Bohai University, Jinzhou 121000 (China); Wang, Xiu-Li, E-mail: wangxiuli@bhu.edu.cn [Department of Chemistry, Bohai University, Jinzhou 121000 (China); Liu, Guocheng; Zhang, Juwen [Department of Chemistry, Bohai University, Jinzhou 121000 (China)

    2015-03-15

    Three new cobalt(II) coordination polymers [Co{sub 2}(1,4-NDC){sub 2}(3-bpye)(H{sub 2}O)] (1), [Co(1,4-NDC)(3-bpfp)(H{sub 2}O)] (2) and [Co(1,4-NDC)(3-bpcb)] (3) [3-bpye=N,N′-bis(3-pyridinecarboxamide)-1,2-ethane, 3-bpfp=bis(3-pyridylformyl)piperazine, 3-bpcb=N,N′-bis(3-pyridinecarboxamide)-1,4-benzene, and 1,4-H{sub 2}NDC=1,4-naphthalenedicarboxylic acid] have been hydrothermally synthesized. The structures of complexes 1–3 have been determined by X-ray single crystal diffraction analyses and further characterized by infrared spectroscopy (IR), powder X-ray diffraction (PXRD) and thermogravimetric analyses (TGA). Complex 1 is a 3D coordination structure with 8-connected (4{sup 20}.6{sup 8}) topology constructed from 3D [Co{sub 2}(1,4-NDC){sub 2}(H{sub 2}O)]{sub n} framework and bidentate 3-bpye ligands. Complex 2 shows 1D “cage+cage”-like chain formed by 1D [Co{sub 2}(1,4-NDC){sub 2}]{sub n} ribbon chains and [Co{sub 2}(3-bpfp){sub 2}] loops, which are further linked by hydrogen bonding interactions to form a 3D supramolecular network. Complex 3 displays a 3D coordination network with a 6-connected (4{sup 12}.6{sup 3}) topology based on 2D [Co{sub 2}(1,4-NDC){sub 2}]{sub n} layers and bidentate 3-bpcb bridging ligands. The influences of different bis-pyridyl-bis-amide ligands with various spacers on the structures of title complexes are studied. Moreover, the fluorescent properties, electrochemical behaviors and magnetic properties of complexes 1–3 have been investigated. - Graphical abstract: Three multifunctional cobalt(II) complexes constructed from three bis-pyridyl-bis-amide and 1,4-naphthalenedicarboxylic acid have been hydrothermally synthesized and characterized. The fluorescent, electrochemical and magnetic properties of 1–3 have been investigated. - Highlights: • Three multifunctional cobalt(II) complexes based on various bis-pyridyl-bis-amide ligands. • Complex 1 is a 3D coordination structure with 8-connected (4{sup 20}.6{sup 8

  9. One-dimensional mercury(II) coordination polymers with a flexible bidentate schiff base ligand (Me.sub.2./sub.N-Ba).sub.2./sub.Bn: Synthesis, characterization, and crystal structures

    Czech Academy of Sciences Publication Activity Database

    Khalaji, A.D.; Bahramian, B.; Jafari, K.; Fejfarová, Karla; Dušek, Michal

    2013-01-01

    Roč. 39, č. 12 (2013), s. 877-884 ISSN 1070-3284 R&D Projects: GA ČR(CZ) GAP204/11/0809 Institutional support: RVO:68378271 Keywords : mercury * structure analysis * coordination polymers Subject RIV: BM - Solid Matter Physics ; Magnetism Impact factor: 0.629, year: 2013

  10. Synthesis and characterization of new coordination polymer with l-proline amino acid ligand, new precursor for preparation of pure phase lead(II) oxide nanoparticles via thermal decomposition

    Czech Academy of Sciences Publication Activity Database

    Varzdar, S.; Hashemi, L.; Morsali, A.; Dušek, Michal

    2017-01-01

    Roč. 14, č. 11 (2017), s. 2255-2261 ISSN 1735-207X Institutional support: RVO:68378271 Keywords : coordination polymer * nanoparticle * lead(II) oxide * proline amino acid Subject RIV: BM - Solid Matter Physics ; Magnetism OBOR OECD: Condensed matter physics (including formerly solid state physics, supercond.) Impact factor: 1.407, year: 2016

  11. Colorimetric assay for on-the-spot alcoholic strength sensing in spirit samples based on dual-responsive lanthanide coordination polymer particles with ratiometric fluorescence

    Energy Technology Data Exchange (ETDEWEB)

    Deng, Jingjing, E-mail: jjdeng@des.ecnu.edu.cn [School of Ecological and Environmental Sciences, East China Normal University, 500 Dongchuan Road, Shanghai 200241 (China); Shi, Guoyue [Department of Chemistry, East China Normal University, 500 Dongchuan Road, Shanghai 200241 (China); Zhou, Tianshu, E-mail: tszhou@des.ecnu.edu.cn [School of Ecological and Environmental Sciences, East China Normal University, 500 Dongchuan Road, Shanghai 200241 (China)

    2016-10-26

    This study demonstrates a new strategy for colorimetric detection of alcoholic strength (AS) in spirit samples based on dual-responsive lanthanide infinite coordination polymer (Ln-ICP) particles with ratiometric fluorescence. The ICP used in this study are composed of two components: one is the supramolecular Ln-ICP network formed by the coordination between the ligand 2,2’-thiodiacetic acid (TDA) and central metal ion Eu{sup 3+}; and the other is a fluorescent dye, i.e., coumarin 343 (C343), both as the cofactor ligand and as the sensitizer, doped into the Ln-ICP network through self-adaptive chemistry. Upon being excited at 300 nm, the red fluorescence of Ln-ICP network itself at 617 nm is highly enhanced due to the concomitant energy transfer from C343 to Eu{sup 3+}, while the fluorescence of C343 at 495 nm is supressed. In pure ethanol solvent, the as-formed C343@Eu-TDA is well dispersed and quite stable. However, the addition of water into ethanolic dispersion of C343@Eu-TDA destructs Eu-TDA network structure, resulting in the release of C343 from ICP network into the solvent. Consequently, the fluorescence of Eu-TDA turns off and the fluorescence of C343 turns on, leading to the fluorescent color change of the dispersion from red to blue, which constitutes a new mechanism for colorimetric sensing of AS in commercial spirit samples. With the method developed here, we could clearly distinguish the AS of different spirit samples within a wide linear range from 10% vol to 100% vol directly by “naked eye” with the help of UV-lamp (365 nm). This study not only offers a new method for on-the-spot visible detection of AS, but also provides a strategy for dual-responsive sensing mode by rational designing the optical properties of the Ln-ICP network and the guest, respectively. - Highlights: • Dual responsive lanthanide coordination polymer particles C343@Eu-TDA were synthesized. • The guest molecular coumarin 343 sensitized the luminescence of Eu

  12. Coordination Chemistry inside Polymeric Nanoreactors: Metal Migration and Cross-Exchange in Amphiphilic Core-Shell Polymer Latexes

    Directory of Open Access Journals (Sweden)

    Si Chen

    2016-01-01

    Full Text Available A well-defined amphiphilic core-shell polymer functionalized with bis(p-methoxy-phenylphosphinophenylphosphine (BMOPPP in the nanogel (NG core has been obtained by a convergent RAFT polymerization in emulsion. This BMOPPP@NG and the previously-reported TPP@NG (TPP = triphenylphosphine and core cross-linked micelles (L@CCM; L = TPP, BMOPPP having a slightly different architecture were loaded with [Rh(acac(CO2] or [RhCl(COD]2 to yield [Rh(acac(CO(L@Pol] or [RhCl(COD(L@Pol] (Pol = CCM, NG. The interparticle metal migration from [Rh(acac(CO(TPP@NG] to TPP@NG is fast at natural pH and much slower at high pH, the rate not depending significantly on the polymer architecture (CCM vs. NG. The cross-exchange using [Rh(acac(CO(BMOPPP@Pol] and [RhCl(COD(TPP@Pol] (Pol = CCM or NG as reagents at natural pH is also rapid (ca. 1 h, although slower than the equivalent homogeneous reaction on the molecular species (<5 min. On the other hand, the subsequent rearrangement of [Rh(acac(CO(TPP@Pol] and [RhCl(COD(TPP@Pol] within the TPP@Pol core and of [Rh(acac(CO(BMOPPP@Pol] and [RhCl(COD(BMOPPP@Pol] within the BMOPPP@Pol core, leading respectively to [RhCl(CO(TPP@Pol2] and [RhCl(CO(BMOPPP@Pol2], is much more rapid (<30 min than on the corresponding homogeneous process with the molecular species (>24 h.

  13. Hydrothermal synthesis, crystal structure and properties of a novel chain coordination polymer constructed by tetrafunctional phosphonate anions and cobalt ions

    International Nuclear Information System (INIS)

    Guan, Lei; Wang, Ying

    2015-01-01

    A novel cobalt phosphonate, [Co(HL)(H 2 O) 3 ] n (1) (L=N(CH 2 PO 3 H) 3 3− ) has been synthesized by hydrothermal reaction at 150 °C and structurally characterized by X-ray diffraction, infrared spectroscopy, elemental and thermogravimetric analysis. Complex 1 features a 1D chain structure with double-channel built from CoO 6 octahedra bridged together by the phosphonate groups. Each cobalt ion is octahedrally coordinated by three phosphonate oxygen atoms and three water molecules. The coordinated water molecules can form the hydrogen bonds with the phosphonate oxygen atoms to link the 1D chains, building a 2D layered structure, further resulting in a 3D network. The luminescence spectrum indicates an emission maximum at 435 nm. The magnetic susceptibility curve exhibits a dominant antiferromagnetic behavior with a weakly ferromagnetic component at low temperatures. - Graphical abstract: The connectivity between cobalt ions and the ligands results in a chain structure with a 1D double-channel structure, which is constructed by A-type subrings and B-type subrings. - Highlights: • The tetrafunctional phosphonate ligand was used as the ligand. • A novel chain structure can be formed by A-type rings and B-type rings. • Two types of rings can form a 1D double-channel structure, along the c-axis

  14. Mechanochemical Synthesis of 3d Transition-Metal-1,2,4-Triazole Complexes as Precursors for Microwave-Assisted and Thermal Conversion to Coordination Polymers with a High Influence on the Dielectric Properties.

    Science.gov (United States)

    Brede, Franziska A; Heine, Johanna; Sextl, Gerhard; Müller-Buschbaum, Klaus

    2016-02-18

    The complexes [MCl2 (TzH)4] (M=Mn (1), Fe (2); TzH=1,2,4-1H-triazole) and [ZnCl2 (TzH)2] (3) have been obtained by mechanochemical reactions of the corresponding divalent metal chloride and 1,2,4-1H-triazole. They were successfully used as precursors for the formation of coordination polymers either by a microwave-assisted reaction or by thermal conversion. For manganese, the conversion directly yielded 1∞ [MnCl2 TzH] (4), whereas for the iron-containing precursor, 1∞ [FeCl2 TzH] (6), was formed via the intermediate coordination polymer 1∞ [FeCl(TzH)2]Cl (5). For cobalt, the isotypic polymer 1∞ [CoCl(TzH)2]Cl (7) was obtained, but exclusively by a microwave-induced reaction directly from CoCl2 . The crystal structures were resolved from single crystals and powders. The dielectric properties were determined and revealed large differences in permittivity between the precursor complexes and the rigid chain-like coordination polymers. Whereas the monomeric complexes exhibit very different dielectric behaviour, depending on the transition metal, from "low-k" to "high-k" with the permittivity ranging from 4.3 to >100 for frequencies of up to 1000 Hz, the coordination polymers and complexes with strong intermolecular interactions are all close to "low-k" materials with very low dielectric constants up to 50 °C. Therefore, the conversion procedures can be used to deliberately influence the dielectric properties from complex to polymer and for different 3d transition-metal ions. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  15. Hybrid materials based on novel 2D lanthanide coordination polymers covalently bonded to amine-modified SBA-15 and MCM-41: assembly, characterization, structural features, thermal and luminescence properties.

    Science.gov (United States)

    Wang, Jun; Dou, Wei; Kirillov, Alexander M; Liu, Weisheng; Xu, Cailing; Fang, Ran; Yang, Lizi

    2016-11-22

    Three novel 2D coordination polymers [Tb 2 (μ 4 -L) 2 (μ-HL)(μ-HCOO)(DEF)] n (Tb-L), [Eu(μ 4 -L)(L)(H 2 O) 2 ] n (Eu-L), and [Nd(μ 4 -L)(L)(H 2 O) 2 ] n (Nd-L) were assembled from the corresponding lanthanide(iii) nitrates and 5 methoxy-(4-benzaldehyde)-1,3-benzenedicarboxylic acid (H 2 L) as a main multifunctional building block bearing carboxylate and aldehyde functional groups, using H 2 O/DEF {DEF = N,N-diethylformamide} as a reaction medium. The obtained coordination polymers were isolated as stable microcrystalline solids and fully characterized by elemental analysis, FT-IR spectroscopy, TGA, BET, PXRD, and single-crystal X-ray diffraction methods. Their structures feature intricate 2D metal-organic networks, which were topologically classified as underlying layers with the 4,6L26 (for Tb-L) or sql (for Eu-L and Nd-L) topologies. Besides, a novel series of mesoporous hybrid materials wherein the Tb-L, Eu-L, or Nd-L coordination polymers are covalently grafted into the amine-functionalized SBA-15-NH 2 or MCM-41-NH 2 matrices (via the formation of Schiff-base groups) was also synthesized and fully characterized. These hybrid materials show high thermal and photoluminescence stability, as well as remarkable chemical resistance to boiling water, and acidic or alkaline medium. Luminescent properties of the parent coordination polymers and derived hybrid materials are investigated in detail, showing that the latter combine the luminescent characteristics (intense green or red emissions and excellent stability) of lanthanide coordination polymers and structural features of ordered mesoporous silica molecular sieves. Moreover, light emitting devices were assembled, by coating the hybrid materials onto the surface of UV-LED bulbs, and showed excellent light emitting properties.

  16. Designing Multifunctional 5-Cyanoisophthalate-Based Coordination Polymers as Single-Molecule Magnets, Adsorbents, and Luminescent Materials.

    Science.gov (United States)

    Seco, Jose M; Oyarzabal, Itziar; Pérez-Yáñez, Sonia; Cepeda, Javier; Rodríguez-Diéguez, Antonio

    2016-11-07

    Detailed structural, magnetic, and photoluminescence characterization of a family of new compounds based on 5-cyanoisophthalate (CNip) ligand and several transition metal or lanthanide ions, namely, [Cu 3 (μ 3 -CNip) 2 (μ-H 2 O) 2 (μ 3 -OH) 2 ] n (1), {[Co 3 (μ 4 -CNip) 3 (DMF) 4 ]·∼2DMF} n (2), [Cd(μ 4 -CNip) (DMF)] n (3), {[Ln 2 (μ 4 -CNip)(μ 3 -CNip) 2 (DMF) 4 ]·∼DMF·H 2 O} n (4-Ln) (with Ln III = Tb, Dy, and Er), {[Gd 6 (μ 3 -CNip) 5 (μ 4 -CNip) 3 (μ-form) 2 (H 2 O) (DMF) 10 ]·∼3DMF·3H 2 O} n (5), {[Zn 32 (μ 4 -CNip) 12 (μ-CNip) 12 (μ 4 -O) 8 (H 2 O) 24 ]·∼12DMF} n (6) (where DMF = dimethylformamide, form = formate), is reported. The large structural diversity found in the system may be explained mainly in terms of the coordination characteristics that are inherent to the employed metal ions, the coordination versatility of the dicarboxylic ligand and the synthetic conditions. Interestingly, some crystal structures (three-dimensional (3D) frameworks of 4-Ln and 5 and 3D network of 6) exhibit open architectures containing large solvent-occupied void systems, among which 5 reveals permanent porosity as confirmed by N 2 adsorption measurements at 77 K. Magnetic direct current (dc) susceptibility data on compounds 1, 2, and 5 were measured. Moreover, compounds 2, 4-Dy, 4-Er, and 5 show slow magnetic relaxation, from which it is worth highlighting the effective energy barrier of 44 K at zero dc field for the dysprosium counterpart. Compound 5 also deserves to be mentioned given the few 3D Gd-organic frameworks reported examples. Photophysical properties were also accomplished at different temperatures, confirming both the fluorescent emission of 5-cyanoisophthalate ligands when coordinated to cadmium ions in 3 and their capacity to sensitize the long-lived fluorescence of the selected lanthanide ions in 4-Ln. Broken symmetry and time-dependent density functional theory computational calculations support the experimental luminescence and

  17. Synthesis, structure and magnetic properties of cobalt(II) and copper(II) coordination polymers assembled by phthalate and 4-methylimidazole

    International Nuclear Information System (INIS)

    Baca, S.G.; Malinovskii, S.T.; Franz, Patrick; Ambrus, Christina; Stoeckli-Evans, Helen; Gerbeleu, Nicolae; Decurtins, Silvio

    2004-01-01

    New coordination polymers [M(Pht)(4-MeIm) 2 (H 2 O)] n (M=Co (1), Cu (2); Pht 2- =dianion of o-phthalic acid; 4-MeIm=4-methylimidazole) have been synthesized and characterized by IR spectroscopy, X-ray crystallography, thermogravimetric analysis and magnetic measurements. The crystal structures of 1 and 2 are isostructural and consist of [M(4-MeIm) 2 (H 2 O)] building units linked in infinite 1D helical chains by 1,6-bridging phthalate ions which also act as chelating ligands through two O atoms from one carboxylate group in the case of 1. In complex 1, each Co(II) atom adopts a distorted octahedral N 2 O 4 geometry being coordinated by two N atoms from two 4-MeIm, three O atoms of two phthalate residues and one O atom of a water molecule, whereas the square-pyramidal N 2 O 3 coordination of the Cu(II) atom in 2 includes two N atoms of N-containing ligands, two O atoms of two carboxylate groups from different Pht, and a water molecule. An additional strong O-H↑··O hydrogen bond between a carboxylate group of the phthalate ligand and a coordinated water molecule join the 1D helical chains to form a 2D network in both compounds. The thermal dependences of the magnetic susceptibilities of the polymeric helical Co(II) chain compound 1 were simulated within the temperature range 20-300 K as a single ion case, whereas for the Cu(II) compound 2, the simulations between 25 and 300 K, were made for a linear chain using the Bonner-Fisher approximation. Modelling the experimental data of compound 1 with MAGPACK resulted in: g=2.6, vertical bar D vertical bar=62 cm -1 . Calculations using the Bonner-Fisher approximation gave the following result for compound 2: g=2.18, J=-0.4 cm -1

  18. Two novel alkaline earth coordination polymers constructed from cinnamic acid and 1,10-phenanthroline: synthesis and structural and thermal properties.

    Science.gov (United States)

    Bendjellal, Nassima; Trifa, Chahrazed; Bouacida, Sofiane; Boudaren, Chaouki; Boudraa, Mhamed; Merazig, Hocine

    2018-02-01

    In coordination chemistry and crystal engineering, many factors influence the construction of coordination polymers and the final frameworks depend greatly on the organic ligands used. The diverse coordination modes of N-donor ligands have been employed to assemble metal-organic frameworks. Carboxylic acid ligands can deprotonate completely or partially when bonding to metal ions and can also act as donors or acceptors of hydrogen bonds; they are thus good candidates for the construction of supramolecular architectures. We synthesized under reflux or hydrothermal conditions two new alkaline earth(II) complexes, namely poly[(1,10-phenanthroline-κ 2 N,N')bis(μ-3-phenylprop-2-enoato-κ 3 O,O':O)calcium(II)], [Ca(C 10 H 7 O 2 ) 2 (C 10 H 8 N 2 )] n , (1), and poly[(1,10-phenanthroline-κ 2 N,N')(μ 3 -3-phenylprop-2-enoato-κ 4 O:O,O':O')(μ-3-phenylprop-2-enoato-κ 3 O,O':O)barium(II)], [Ba(C 10 H 7 O 2 ) 2 (C 10 H 8 N 2 )] n , (2), and characterized them by FT-IR and UV-Vis spectroscopies, thermogravimetric analysis (TGA) and single-crystal X-ray diffraction analysis, as well as by powder X-ray diffraction (PXRD) analysis. Complex (1) features a chain topology of type 2,4 C4, where the Ca atoms are connected by O and N atoms, forming a distorted bicapped trigonal prismatic geometry. Complex (2) displays chains of topology type 2,3,5 C4, where the Ba atom is nine-coordinated by seven O atoms of bridging/chelating carboxylate groups from two cinnamate ligands and by two N atoms from one phenanthroline ligand, forming a distorted tricapped prismatic arrangement. Weak C-H...O hydrogen bonds and π-π stacking interactions between phenanthroline ligands are responsible to the formation of a supramolecular three-dimensional network. The thermal decompositions of (1) and (2) in the temperature range 297-1173 K revealed that they both decompose in three steps and transform to the corresponding metal oxide.

  19. Cd(II)-coordination polymers based on tetracarboxylic acid and diverse bis(imidazole) ligands: Synthesis, structural diversity and photoluminescence properties

    Energy Technology Data Exchange (ETDEWEB)

    Arıcı, Mürsel, E-mail: marici@ogu.edu.tr [Department of Chemistry, Faculty of Arts and Sciences, Eskişehir Osmangazi University, 26480 Eskişehir (Turkey); Yeşilel, Okan Zafer [Department of Chemistry, Faculty of Arts and Sciences, Eskişehir Osmangazi University, 26480 Eskişehir (Turkey); Taş, Murat [Department of Science Education, Education Faculty, Ondokuz Mayıs University, 55139 Samsun (Turkey)

    2017-01-15

    Three new Cd(II)-coordination polymers, namely, ([Cd{sub 2}(μ{sub 6}-ao{sub 2}btc)(μ-1,5-bipe){sub 2}]·2H{sub 2}O){sub n} (1), ([Cd{sub 2}(μ{sub 6}-ao{sub 2}btc)(μ-1,4-bix){sub 2}]{sub n}·2DMF) (2) and ([Cd{sub 2}(μ{sub 8}-abtc)(μ-1,4-betix)]·DMF·H{sub 2}O){sub n} (3) (ao{sub 2}btc=di-oxygenated form of 3,3′,5,5′-azobenzenetetracarboxylate, 1,5-bipe: 1,5-bis(imidazol-1yl)pentane, 1,4-bix=1,4-bis(imidazol-1ylmethyl)benzene, 1,4-betix=1,4-bis(2-ethylimidazol-1ylmethyl)benzene) were synthesized with 3,3′,5,5′-azobenzenetetracarboxylic acid and flexible, semi-flexible and semi-flexible substituted bis(imidazole) linkers. They were characterized by IR spectroscopy, elemental analysis, single-crystal X-ray diffraction, powder X-ray diffractions (PXRD) and thermal analyses (TG/DTA). Complexes 1–3 exhibited structural diversities depending on flexible, semi-flexible and semi-flexible substituted bis(imidazole) ligands. Complex 1 was 2D structure with 3,6L18 topology. Complex 2 had a 3D pillar-layered framework with the rare sqc27 topology. When semi-flexible substituted bis(imidazole) linker was used, 3D framework of complex 3 was obtained with the paddlewheel Cd{sub 2}(CO{sub 2}){sub 4}-type binuclear SBU. Moreover, thermal and photoluminescence properties of the complexes were determined in detailed. - Graphical abstract: In this study, three novel Cd(II)-coordination polymers were synthesized with 3,3′,5,5′-azobenzenetetracarboxylic acid and flexible, semi-flexible and semi-flexible substituted bis(imidazole) linkers. They were characterized by IR spectroscopy, elemental analysis, single-crystal X-ray diffraction, powder X-ray diffractions (PXRD) and thermal analyses (TG/DTA). Complexes 1–3 exhibited structural diversities depending on flexible, semi-flexible and semi-flexible substituted bis(imidazole) ligands. Complex 1 was 2D structure with 3,6L18 topology. Complex 2 had a 3D pillar-layered framework with the rare sqc27 topology. When semi

  20. Metal and Ligand Effects on the Construction of Divalent Coordination Polymers Based on bis-Pyridyl-bis-amide and Polycarboxylate Ligands

    Directory of Open Access Journals (Sweden)

    Miao-Ning Chang

    2017-12-01

    Full Text Available Ten coordination polymers constructed from divalent metal salts, polycarboxylic acids, and bis-pyridyl-bis-amide ligands with different donor atom positions and flexibility are reported. They were structurally characterized by single-crystal X-ray diffraction. The ten coordination polymers are as follows: (1 {[Ni(L1(3,5-PDA(H2O3]·2H2O}n (L1 = N,N′-di(3-pyridylsuberoamide, 3,5-H2PDA = 3,5-pyridinedicarboxylic acid; (2 {[Ni2(L12(1,3,5-HBTC2(H2O4]·H2O}n (1,3,5-H3BTC = 1,3,5-benzenetricarboxylic acid; (3 {[Ni(L2(5-tert-IPA(H2O2]·2H2O}n (L2 = N,N′-di(3-pyridyladipoamide, 5-tert-H2IPA = 5-tert-butylisophthalic acid; (4 [Ni(L31.5(5-tert-IPA]n (L3 = N,N′-di(4-pyridyladipoamide; (5 [Co(L1(1,3,5-HBTC(H2O]n; (6 {[Co3(L13(1,3,5-BTC2(H2O2]·6H2O}n; (7 [Cu(L4(AIPA]n (L4 = N,N′-bis(3-pyridinylterephthalamide, H2AIPA = 5-acetamido isophthalic acid; (8 {[Cu(L20.5(AIPA]·MeOH}n; (9 {[Zn(L4(AIPA]·2H2O}n; and (10 {[Zn(L2(AIPA]·2H2O}n. Complex 1 forms a 1D chain and 2 is a two-fold interpenetrated 2D layer with the sql topology, while 3 is a 2D layer with the hcp topology and 4 shows a self-catenated 3D framework with the rare (42·67·8-hxg-d-5-C2/c topology. Different Co/1,3,5-H3BTC ratios were used to prepare 5 and 6, affording a 2D layer with the sql topology and a 2D layer with the (4·852(42(832(8 topology that can be further simplified to an hcp topology. While complex 7 is a 2D layer with the (42·67·8(42·6-3,5L2 topology and 8 is a 2-fold interpenetrated 3D framework with the pcu topology, complexes 9 and 10 are self-catenated 3D frameworks with the (424·64-8T2 and the (44·610·8-mab topologies, respectively. The effects of the identity of the metal center, the ligand isomerism, and the flexibility of the spacer ligands on the structural diversity of these divalent coordination polymers are discussed. The luminescent properties of 9 and 10 and their photocatalytic effects on the degradation of dyes are also investigated.

  1. Thermal conductivity and stability of a three-phase blend of carbon nanotubes, conductive polymer, and silver nanoparticles incorporated into polycarbonate nanocomposites

    KAUST Repository

    Patole, Archana

    2015-04-16

    Metallic and non-metallic nanofillers can be used together in the design of polycarbonate (PC) nanocomposites with improved electrical properties. Here, the preparation of three-phase blend (carbon nanotubes (CNT), silver nanoparticles, and conductive polymer) in a two-step process before incorporation in the PC is reported. First, ethylene diamine functionalized multiwall carbon nanotubes (MWCNT-EDA) were decorated with Ag nanoparticles. Next, the Ag-decorated CNTs were coated with poly(3,4-ethylenedioxythiophene) polystyrene sulfonate (PEDOT:PSS). Due to the high thermal conductivity instrinsic to both metallic and non-metallic phases, it is expected that the thermal properties of the resulting nanocomposite would largely differ from those of pristine PC. We thus investigated in detail how this hybrid conductive blend affected properties such as the glass transition temperature, the thermal stability, and the thermal conductivity of the nanocomposite. It was found that this strategy results in improved thermal conductivity and thermal stability of the material. © 2015 Wiley Periodicals, Inc.

  2. The potential of incorporation of binary salts and ionic liquid in P(VP-co-VAc) gel polymer electrolyte in electrochemical and photovoltaic performances.

    Science.gov (United States)

    Ming, Ng Hon; Ramesh, S; Ramesh, K

    2016-06-08

    In this study, dye-sensitized solar cells (DSSCs) has been assembled with poly(1-vinylpyrrolidone-co-vinyl acetate) (P(VP-co-VAc)) gel polymer electrolytes (GPEs) which have been incorporated with binary salt and an ionic liquid. The potential of this combination was studied and reported. The binary salt system GPEs was having ionic conductivity and power conversion efficiency (PCE) that could reach up to 1.90 × 10(-3) S cm(-1) and 5.53%, respectively. Interestingly, upon the addition of the ionic liquid, MPII into the binary salt system the ionic conductivity and PCE had risen steadily up to 4.09 × 10(-3) S cm(-1) and 5.94%, respectively. In order to know more about this phenomenon, the electrochemical impedance studies (EIS) of the GPE samples have been done and reported. Fourier transform infrared studies (FTIR) and thermogravimetric analysis (TGA) have also been studied to understand more on the structural and thermal properties of the GPEs. The Nyquist plot and Bodes plot studies have been done in order to understand the electrochemical properties of the GPE based DSSCs and Tafel polarization studies were done to determine the electrocatalytic activity of the GPE samples.

  3. Coordination polymers with the chiral ligand N-p-tolylsulfonyl-L-glutamic acid: Influence of metal ions and different bipyridine ligands on structural chirality

    International Nuclear Information System (INIS)

    He Rong; Song Huihua; Wei Zhen; Zhang Jianjun; Gao Yuanzhe

    2010-01-01

    Four new polymers, namely [Ni(-tsgluO)(2,4'-bipy) 2 (H 2 O) 2 ] n .5nH 2 O (1), [Co(-tsgluO)(2,4'-bipy) 2 (H 2 O) 2 ] n .5nH 2 O (2), [Ni(-tsgluO)(4,4'-bipy)] n .0.5nH 2 O (3), and [Co(-tsgluO)(4,4'-bipy)] n .0.5nH 2 O (4), where tsgluO 2- =(+)-N-p-tolylsulfonyl-L-glutamate dianion, 2,4'-bipy=2,4'-bipyridine, and 4,4'-bipy=4,4'-bipyridine, have been prepared and structurally characterized. Compounds 1 and 2 are isostructural and mononuclear, and crystallize in the acentric monoclinic space group Cc, forming 1D chain structures. Compound 3 is also mononuclear, but crystallizes in the chiral space group P2 1 , forming a homochiral 2D architecture. In contrast to the other complexes, compound 4 crystallizes in the space group P-1 and is composed of binuclear [Co 2 O 6 N 2 ] n 4- units, which give rise to a 2D bilayer framework. Moreover, compounds 1, 2, and 4 self-assemble to form 3D supramolecular structures through π-π stacking and hydrogen-bonding interactions, while compound 3 is further hydrogen-bonded to form 3D frameworks. We have demonstrated the influence of the central metal and bipyridine ligands on the framework chirality of the coordination complexes. - Graphical abstract: Four novel polymers based on a chiral ligand were prepared and structurally characterized; it represents the first series of investigations about the effect of central metals and bipyridine ligands on framework chirality.

  4. Synthesis, structural characterization and photoluminescent properties of 2D multilayer Cu+ coordination polymers via Csbnd H⋯π and π⋯π interactions

    Science.gov (United States)

    Huang, Ting-Hong; Zhu, Sheng-Lan; Xiong, Xian-Lian; Li, Jia-Dong; Yang, Hu; Huang, Xin; Huang, Xue-Ren; Zhang, Kunming

    2017-09-01

    Two Cu(I) coordination polymers, {[Cu(pmbb)0.5(4,4'-bipy)0.5(PPh3)](BF4) (H2O)2}n (1) and {[Cu(pmbb)0.5(bpe)0.5(PPh3)](BF4)(DMF)}n (2) (pmbb = N, N'-bis(pyridin-2-ylmethylene)biphenyl -4,4'-diamine, 4,4'-bipy = 4,4'-bipyridine, bpe = 1,2-bis(4-pyridyl)ethylene), PPh3 = triphenyl phosphine), have been synthesized and characterized by IR, 1H NMR, 13C NMR, 31P NMR, 19F NMR, 11B-NMR, TG and X-ray crystal structure analysis. The structural analysis shows that complexes 1 and 2 contain diverse and interesting 2D supramolecular networks based on inter-chain interactions. Complex 1 displays a 1D zig-zag chain and a 1D+1D→2D supramolecular network formed by intermolecular Csbnd H···π interaction. For 2, each 1D zig-zag chain interacts with neighboring ones via intermolecular Csbnd H···π and π···π stacking interactions, leading to the formation of a 2D-stacking network. Furthermore, solid-state UV-Vis absorption spectra of complexes 1 and 2 indicate the existence of MLCT absorption. Complexes 1 and 2 show efficient luminescent emission peaks at 435 and 452 nm assigned to MLCT excited states, and the emission decay lifetimes are 20.82 μs for 1 and 20.72 μs for 2, displaying strong room-temperature solid-state photoluminescence. Moreover, thermogravimetric analysis shows that the heat stability of polymers is 1>2.

  5. Mechanochemical and thermal formation of 1H-benzotriazole coordination polymers and complexes of 3d-transition metals with intriguing dielectric properties.

    Science.gov (United States)

    Brede, Franziska A; Mühlbach, Friedrich; Sextl, Gerhard; Müller-Buschbaum, Klaus

    2016-07-14

    Liquid-assisted grinding (LAG) reactions have been successfully applied to achieve a series of complexes and coordination polymers based on divalent 3d-transition metal chlorides (TM chlorides) and the aromatic ligand 1H-benzotriazole (BtzH). The obtained substances were investigated via single crystal X-ray, powder X-ray determination and simultaneous DTA/TG analysis as model compounds for structural and chemical influences on their dielectric properties. Depending on the synthesis method, different constitutions and structures are observed. Two polymorphous forms of the 1D polymer [MnCl2(BtzH)2] (1 and 2) as well as the complexes [ZnCl2(BtzH)2]·BtzH (3) and [CoCl2(BtzH)2]·BtzH (4) have been obtained as phase-pure bulk substances via the mechanochemical LAG route, and even single crystals are available. For comparison, thermal reactions were also carried out and have led to the formation of the neutral complexes: [CoCl2(BtzH)2] (5) and [CoCl2(BtzH)4]·4BtzH (6), [ZnCl2(BtzH)2] (7) and the anionic complex BtzH2[CoCl3BtzH] (8). In addition, thermal treatment of 3 yields the benzotriazolium salt {(BtzH)2H}Cl (9). The transition metal compounds were additionally analysed regarding their dielectric properties by frequency-dependent as well as temperature-dependent permittivity investigations. It is intriguing that compounds 1 and 3 show remarkably low dielectric constants and loss factors up to 50 °C highlighting them as potential "low-k materials".

  6. Syntheses, structures and selective dye adsorption of five formic-based coordination polymers prepared by in-situ hydrolysis of N, N‧-dimethylformamide

    Science.gov (United States)

    Zhu, Zheng; Meng, Xiang-min; Zhang, Dong-mei; Zhang, Xia; Wang, Mei; Jin, Fan; Fan, Yu-hua

    2017-04-01

    Five functional coordination polymers (formic-based CPs) namely: {[Cu2(CHOO)3(bibp)2]·CHOO}n (1), {[Co2(CHOO)3(bibp)2]·NO3·H2O}n (2), {[Ni2(CHOO)3(bibp)2]·NO3·H2O}n (3) [Co(CHOO)2(bbibp)]n (4) and [Zn(CHOO)2(bbibp)]n (5) (bibp=4,4‧-bis(imidazolyl)biphenyl, bbibp=4,4‧-bis(benzoimidazo-1-yl)biphenyl) have been successfully hydrothermally synthesized using the in-situ hydrolysis of N, N‧-dimethylformamide (DMF) as the source of formate. All of these five polymers were characterized by single-crystal X-ray diffraction, elemental analysis, IR spectra, powder X-ray diffraction (PXRD), and thermogravimetric (TG) analysis. Complexes 1-3 have the similar three-dimensional 3D kag topological framework built from the bibp ligand as the support member between the neighboring formic planes. Both complexes 4 and 5 have the similar one-dimensional 1D linear chain which is further assembled into 3D supermolecular structure by C-H…O hydrogen bonds. The dyes adsorption experiments have also been investigated systematically. The results show that complexes 2 and 3 exhibit high selective adsorption ability towards anionic dyes in their aqueous solution. Moreover, complex 2 displays good reversibility in the process of the dyes adsorption-release. Meanwhile, the unusual blocking phenomenon was firstly observed when complex 2 was in MO/OIV aqueous solutions with different concentration.

  7. Syntheses, structures and selective dye adsorption of five formic-based coordination polymers prepared by in-situ hydrolysis of N, N′-dimethylformamide

    Energy Technology Data Exchange (ETDEWEB)

    Zhu, Zheng; Meng, Xiang-min; Zhang, Dong-mei; Zhang, Xia; Wang, Mei [Key Laboratory of Marine Chemistry Theory and Technology, Ministry of Education, College of Chemistry and Chemical Engineering, Ocean University of China, Qingdao, Shandong 266100 (China); Jin, Fan [Max Planck Institute for Terrestrial Microbiology & LOEWE Center for Synthetic Microbiology (SYNMIKRO), Marburg 35043 (Germany); Fan, Yu-hua [Key Laboratory of Marine Chemistry Theory and Technology, Ministry of Education, College of Chemistry and Chemical Engineering, Ocean University of China, Qingdao, Shandong 266100 (China)

    2017-04-15

    Five functional coordination polymers (formic-based CPs) namely: ([Cu{sub 2}(CHOO){sub 3}(bibp){sub 2}]·CHOO){sub n} (1), ([Co{sub 2}(CHOO){sub 3}(bibp){sub 2}]·NO{sub 3}·H{sub 2}O)n (2), ([Ni{sub 2}(CHOO){sub 3}(bibp){sub 2}]·NO{sub 3}·H{sub 2}O){sub n} (3) [Co(CHOO){sub 2}(bbibp)]{sub n} (4) and [Zn(CHOO){sub 2}(bbibp)]{sub n} (5) (bibp=4,4′-bis(imidazolyl)biphenyl, bbibp=4,4′-bis(benzoimidazo-1-yl)biphenyl) have been successfully hydrothermally synthesized using the in-situ hydrolysis of N, N′-dimethylformamide (DMF) as the source of formate. All of these five polymers were characterized by single-crystal X-ray diffraction, elemental analysis, IR spectra, powder X-ray diffraction (PXRD), and thermogravimetric (TG) analysis. Complexes 1–3 have the similar three-dimensional 3D kag topological framework built from the bibp ligand as the support member between the neighboring formic planes. Both complexes 4 and 5 have the similar one-dimensional 1D linear chain which is further assembled into 3D supermolecular structure by C–H…O hydrogen bonds. The dyes adsorption experiments have also been investigated systematically. The results show that complexes 2 and 3 exhibit high selective adsorption ability towards anionic dyes in their aqueous solution. Moreover, complex 2 displays good reversibility in the process of the dyes adsorption-release. Meanwhile, the unusual blocking phenomenon was firstly observed when complex 2 was in MO/OIV aqueous solutions with different concentration.

  8. Seven new Zn(II)/Cd(II) coordination polymers with 2-(hydroxymethyl)-1H-benzo[d]imidazole-5-carboxylic acid: Synthesis, structures and properties

    Science.gov (United States)

    Wang, Xin-Fang; Zhou, Sheng-Bin; Du, Ceng-Ceng; Wang, Duo-Zhi; Jia, Dianzeng

    2017-08-01

    Using a new simi-rigid multitopic ligand 2-(hydroxymethyl)-1H-benzo[d]imidazole-5-carboxylic acid (H2L), seven new coordination polymers [Zn3(L)2(μ2-OH)2]n (1), {[Zn2(HL)2(H2O)2]·SiF6}n (2), [Zn(HL)(SCN)]n (3), {[Zn2(HL)2(SO4)]·(4,4‧-bpy)}n (4) [4,4‧-bpy =4,4‧-bipyridine], {[Zn(HL)2]·2H2O}n (5), {[Cd(HL)2]·2H2O}n (6) and [Cd2(HL)2(H2O)2(SO4)]n (7) have been successfully obtained from H2L ligand under solvothermal conditions and structurally characterized by single-crystal X-ray diffraction, elemental analysis, thermogravimetric analysis, powder X-ray diffraction and IR spectroscopy. In addition, UV-vis diffuse-reflectance spectra demonstrate wide band gaps. Complex 1 features a 3D topological net of {412·63} with the stoichiometry (6-c), contains 1D channels with the accessible solvent volume of 42.1%. 3, 4, 5 and 6 have a 1D chain structure, 5 and 6 further assemble to form 2D sheet and 3D supramolecular frameworks by hydrogen-bonding interactions, respectively. Complexes 2 and 7 possess a 2D layered structure, and the 2D supramolecular network of 2 can be rationalized to be four-connected {44·62} topological sql network with the dinuclear units, while 7 shows a 3-nodal 2D net with a point symbol of {63}. Moreover, the fluorescent emission, fluorescence lifetimes of 1-7 have been investigated and discussed. Interesting enough, complex 1 showed high efficiency for catalyzing the Knoevenagel condensation reaction between 4-substituted aromatic aldehydes and malononitrile as selective heterogeneous catalyst. The CPs combining catalytic and fluorescent properties could further meet the requirement as a multifunctional material. Seven new Zn(II)/Cd(II) coordination polymers with simi-rigid multitopic ligand, [(2-(hydroxymethyl)-1H-benzo[d]imidazole-5-carboxylic acid) (H2L)] have been successfully obtained and structurally characterized by single-crystal X-ray diffraction, elemental analysis, thermogravimetric analysis, powder X-ray diffraction and IR

  9. Two-step adsorption on jungle-gym-type porous coordination polymers: dependence on hydrogen-bonding capability of adsorbates, ligand-substituent effect, and temperature.

    Science.gov (United States)

    Uemura, Kazuhiro; Yamasaki, Yukari; Onishi, Fumiaki; Kita, Hidetoshi; Ebihara, Masahiro

    2010-11-01

    A preliminary study of isopropanol (IPA) adsorption/desorption isotherms on a jungle-gym-type porous coordination polymer, [Zn(2)(bdc)(2)(dabco)](n) (1, H(2)bdc = 1,4-benzenedicarboxylic acid, dabco =1,4-diazabicyclo[2.2.2]octane), showed unambiguous two-step profiles via a highly shrunk intermediate framework. The results of adsorption measurements on 1, using probing gas molecules of alcohol (MeOH and EtOH) for the size effect and Me(2)CO for the influence of hydrogen bonding, show that alcohol adsorption isotherms are gradual two-step profiles, whereas the Me(2)CO isotherm is a typical type-I isotherm, indicating that a two-step adsorption/desorption is involved with hydrogen bonds. To further clarify these characteristic adsorption/desorption behaviors, selecting nitroterephthalate (bdc-NO(2)), bromoterephthalate (bdc-Br), and 2,5-dichloroterephthalate (bdc-Cl(2)) as substituted dicarboxylate ligands, isomorphous jungle-gym-type porous coordination polymers, {[Zn(2)(bdc-NO(2))(2)(dabco)]·solvents}(n) (2 ⊃ solvents), {[Zn(2)(bdc-Br)(2)(dabco)]·solvents}(n) (3 ⊃ solvents), and {[Zn(2)(bdc-Cl(2))(2)(dabco)]·solvents}(n) (4 ⊃ solvents), were synthesized and characterized by single-crystal X-ray analyses. Thermal gravimetry, X-ray powder diffraction, and N(2) adsorption at 77 K measurements reveal that [Zn(2)(bdc-NO(2))(2)(dabco)](n) (2), [Zn(2)(bdc-Br)(2)(dabco)](n) (3), and [Zn(2)(bdc-Cl(2))(2)(dabco)](n) (4) maintain their frameworks without guest molecules with Brunauer-Emmett-Teller (BET) surface areas of 1568 (2), 1292 (3), and 1216 (4) m(2) g(-1). As found in results of MeOH, EtOH, IPA, and Me(2)CO adsorption/desorption on 2-4, only MeOH adsorption on 2 shows an obvious two-step profile. Considering the substituent effects and adsorbate sizes, the hydrogen bonds, which are triggers for two-step adsorption, are formed between adsorbates and carboxylate groups at the corners in the pores, inducing wide pores to become narrow pores. Interestingly, such

  10. Carboxylate ligands induced structural diversity of zinc(II) coordination polymers based on 3,6-bis(imidazol-1-yl)carbazole: Syntheses, structures and photocatalytic properties

    Energy Technology Data Exchange (ETDEWEB)

    Cheng, Hong-Jian, E-mail: hjcheng@cslg.cn; Tang, Hui-Xiang; Shen, Ya-Li; Xia, Nan-Nan; Yin, Wen-Yu; Zhu, Wei; Tang, Xiao-Yan; Ma, Yun-Sheng; Yuan, Rong-Xin, E-mail: yuanrx@cslg.edu.cn

    2015-12-15

    Solvothermal reactions of Zn(NO{sub 3}){sub 2}·6H{sub 2}O with 3,6-bis(1-imidazolyl)carbazole (3,6-bmcz) and 1,4-benzenedicarboxylic acid (1,4-H{sub 2}bdc), p-phenylenediacetic acid (p-H{sub 2}pda), benzophenone-4,4-dicarboxylic acid (H{sub 2}bpda) afforded three coordination polymers [Zn(1,4-bdc)(3,6-bmcz)]{sub n} (1), {[Zn(p-pda)(3,6-bmcz)]·1.5H_2O}{sub n} (2) and {[Zn(bpda)(3,6-bmcz)]·0.25H_2O}{sub n} (3). Complexes 1–3 were characterized by elemental analysis, IR, powder X-ray diffraction, and single-crystal X-ray diffraction. Complex 1 shows 3D structure with 2D nets inclined polycatenation. Complexes 2 and 3 possess an extended 3D supramolecular architecture based on their respective 2D layers through hydrogen-bonding interactions and the π···π stacking interactions. The solid state luminescent and optical properties of 1–3 at ambient temperature were also investigated. A comparative study on their photocatalytic activity toward the degradation of methylene blue in polluted water was explored. - Graphical abstract: Reactions of Zn(NO{sub 3}){sub 2} and 3,6-(1-imidazolyl)carbazole with 1,4-benzenedicarboxylic acid, p-phenylenediacetic acid or benzophenone-4,4-dicarboxylic acid afforded three coordination polymers with different topologies and photocatalytic activity. - Highlights: • Reactions of 1,4-H{sub 2}bdc, p-H{sub 2}pda or H{sub 2}bpda with 3,6-bmcz and Zn(II) gave three CPs. • Complex 1 is a 3D entanglement. • Complex 2 or 3 is a 3D supramolecular structure based on different 2D layers. • Complex 2 exhibited good catalytic activity of methylene blue photodegradation.

  11. Polymer Solar Cells – Non Toxic Processing and Stable Polymer Photovoltaic Materials

    DEFF Research Database (Denmark)

    Søndergaard, Roar

    The field of polymer solar cell has experienced enormous progress in the previous years, with efficiencies of small scale devices (~1 mm2) now exceeding 8%. However, if the polymer solar cell is to achieve success as a renewable energy resource, mass production of sufficiently stable and efficient...... and development of more stable materials. The field of polymer solar cells has evolved around the use of toxic and carcinogenic solvents like chloroform, benzene, toluene, chlorobenzene, dichlorobenzene and xylene. As large scale production of organic solar cells is envisaged to production volumes corresponding...... synthesis of polymers carrying water coordinating side chains which allow for processing from semi-aqueous solution. A series of different side chains were synthesized and incorporated into the final polymers as thermocleavable tertiary esters. Using a cleavable side chain induces stability to solar cells...

  12. Hydrothermal synthesis and crystal Structure of a new coordination polymer: [Zn1(deta(btec(H2O2]n

    Directory of Open Access Journals (Sweden)

    Manel Halouani

    2013-05-01

    Full Text Available A new metal–organic compound [Zn1(deta(btec(H2O2]n where (deta= Diethylenetriamine and (btec= benzenetetracarboxylic acid (I was hydrothermally synthesized from an aqueous solution of Zn(NO32 6H2O, (deta and (btec. Compound I crystallizes in the monoclinic system with the P21/c space group. The unit cell parameters are a= 9.6716(5Å, b= 14.3776(8Å, c= 13.5306(8Å, β= 105.311(3°, Z= 4, V= 1814.71(18 Å3 and Dx= 1.657 g/cm3. The refinement converged into R= 0.045, Rw= 0.048. The structure, determined by single crystal X-ray diffraction, consists of a network of ZnO4 centers, tetrahedrally coordinated by pyromellitate anions giving rise to a two-dimensional sheet structure. The connectivity resembles a 4-connected network in which each Zn atom is connected to four btec anions and each btec anion is linked to four Zn2+ ions.

  13. Coordination polymer nanocapsules prepared using metal-organic framework templates for pH-responsive drug delivery

    Science.gov (United States)

    Tang, Lei; Shi, Jiafu; Wang, Xiaoli; Zhang, Shaohua; Wu, Hong; Sun, Hongfan; Jiang, Zhongyi

    2017-07-01

    A facile, efficient, and versatile approach is presented to synthesize pH-responsive nanocapsules (˜120 nm) by combining the advantages of metal-organic frameworks (MOFs) and metal-organic thin films. ZIF-8 nanoparticles are used as templates on which a thin film coating of iron(III)-catechol complexes is derived from the coordination between dopamine-modified alginate (AlgDA) and iron(III) ions. After the template removal, nanocapsules with a pH-responsive wall are obtained. Doxorubicin (Dox), a typical anticancer drug, is first immobilized in ZIF-8 frameworks through coprecipitation and then encapsulated in nanocapsules after the removal of ZIF-8. The structure of the iron(III)-catechol complex varies with pH value, thus conferring the Dox@Nanocapsules with tailored release behavior in vitro. Cytotoxicity tests illustrate the highly effective cytotoxicity of Dox@Nanocapsules towards cancer cells. This study provides a new method for preparing smart nanocapsules and offers more opportunities for the controlled delivery of drugs.

  14. New one-dimensional azido-bridged manganese(II) coordination polymers exhibiting alternating ferromagnetic-antiferromagnetic interactions: structural and magnetic studies.

    Science.gov (United States)

    Gao, En-Qing; Bai, Shi-Qiang; Yue, Yan-Feng; Wang, Zhe-Ming; Yan, Chun-Hua

    2003-06-02

    Five Mn(II)[bond]azido coordination polymers of formula [Mn(L)(N(3))(2)](n) have been synthesized and crystallographically characterized, and their magnetic properties studied, where L's are the bidentate Schiff bases obtained from the condensation of pyridine-2-carbaldehyde with aniline (1) and its derivatives p-toluidine (2), m-toluidine (3), p-chloroaniline (4), and m-chloroaniline (5). All the complexes consist of the zigzag Mn(II)[bond]azido chains in which the Mn(II) ions are alternately bridged by two end-to-end (EE) and two end-on (EO) azido ligands, the cis-octahedral coordination being completed by the two nitrogen atoms of the Schiff base ligands. Compound 2 is unique in that the Mn[bond](EE-N(3))(2)[bond]Mn ring adopts an unusual twist conformation with the two linear azido bridges crossing each other. By contrast, the rings in the other compounds take the usual chair conformation with the two azido bridges parallel. The double EO bridging fragments in the complexes are similar with the bridging angles (Mn[bond]N[bond]Mn) ranging from 99.6 degrees to 104.0 degrees. Magnetic analyses reveal that alternating ferro- and antiferromagnetic interactions are mediated through the alternating EO and EE azido bridges with the J(F) and J(AF) parameters in the ranges of 4.1-8.0 and -11.8 to -15.4 cm(-1), respectively. Finally, the magnetostructural correlations are investigated. The present complexes follow the general trend that the ferromagnetic interaction through the double EO bridge increases with the Mn[bond]N[bond]Mn bridging angle, while the antiferromagnetic interaction through the double EE bridge is dependent on the distortion of the Mn[bond](N(3))(2)[bond]Mn ring from planarity toward the chair conformation and the Mn[bond]N[bond]N angle.

  15. Solvent-induced synthesis of cobalt(II) coordination polymers based on a rigid ligand and flexible carboxylic acid ligands: syntheses, structures and magnetic properties.

    Science.gov (United States)

    Wang, Ting; Zhang, Chuanlei; Ju, Zemin; Zheng, Hegen

    2015-04-21

    Five new cobalt(ii) coordination architectures, {[Co(L)2(H2O)2]·2H2O·2NO3}n (), {[Co(L)(ppda)]·2H2O}n (), {[Co2(L)(ppda)2]2·H2O}n (), {[Co(L)(nba)]·5H2O}n (), and {[Co(L)(oba)]2·3H2O}n (), have been constructed from the rigid ligand L [L = 2,8-di(1H-imidazol-1-yl)dibenzofuran] and different flexible carboxylic acid ligands [H2ppda = 4,4'-(perfluoropropane-2,2-diyl)dibenzoic acid, H2nba = 4,4'-azanediyldibenzoic acid, and H2oba = 4,4'-oxydibenzoic acid]. Depending on the nature of the solvent systems, these five different coordination polymers were synthesized and characterized by single-crystal X-ray diffraction, IR, PXRD and elemental analysis. Compounds , and were obtained by a one-pot method, and then we utilized the solvent-induced effect to obtain almost pure crystals of , respectively. Compound is an infinite 1D chain which is formed by L ligands and Co atoms. Compound contains a [Co2(CO2)4] secondary building unit (SBU), and can be topologically represented as a 6-connected 2-fold interpenetrating pcu net with the point symbol of {4(12)·6(3)}. Compound can be characterized as a 4-connected sql tetragonal planar network with the point symbol of {4(4)·6(2)}. In compounds and , there is a 1D chain which is formed by flexible carboxylic acid ligands and Co atoms; then the 1D chain is linked by L ligands in the tilting direction, leading to the formation of a 2D layer. Furthermore, UV-vis, TGA and magnetic properties have been investigated in detail.

  16. Position Accuracy of Implant Analogs on 3D Printed Polymer versus Conventional Dental Stone Casts Measured Using a Coordinate Measuring Machine.

    Science.gov (United States)

    Revilla-León, Marta; Gonzalez-Martín, Óscar; Pérez López, Javier; Sánchez-Rubio, José Luis; Özcan, Mutlu

    2017-11-17

    To compare the accuracy of implant analog positions on complete edentulous maxillary casts made of either dental stone or additive manufactured polymers using a coordinate measuring machine (CMM). A completely edentulous maxillary model of a patient with 7 implant analogs was obtained. From this model, two types of casts were duplicated, namely conventional dental stone (CDS) using a custom tray impression technique after splinting (N = 5) and polymer cast using additive manufacturing based on the STL file generated. Polymer casts (N = 20; n = 5 per group) were fabricated using 4 different additive manufacturing technologies (multijet printing-MJP1, direct light processing-DLP, stereolithography-SLA, multijet printing-MJP2). CMM was used to measure the correct position of each implant, and distortion was calculated for each system at x-, y-, and z-axes. Measurements were repeated 3 times per specimen in each axis yielding a total of 546 measurements. Data were analyzed using ANOVA, Sheffé tests, and Bonferroni correction (α = 0.05). Compared to CMM, the mean distortion (μm) ranged from 22.7 to 74.9, 23.4 to 49.1, and 11.0 to 85.8 in the x-, y-, and z-axes, respectively. CDS method (x-axis: 37.1; z-axis: 27.62) showed a significant difference compared to DLP on the x-axis (22.7) (p = 0.037) and to MJP1 on the z-axis (11.0) (p = 0.003). Regardless of the cast system, x-axes showed more distortion (42.6) compared to y- (34.6) and z-axes (35.97). Among additive manufacturing technologies, MJP2 presented the highest (64.3 ± 83.6), and MJP1 (21.57 ± 16.3) and DLP (27.07 ± 20.23) the lowest distortion, which was not significantly different from CDS (32.3 ± 22.73) (p > 0.05). For the fabrication of the definitive casts for implant prostheses, one of the multijet printing systems and direct light processing additive manufacturing technologies showed similar results to conventional dental stone. Conventional dental stone casts could be accurately duplicated using some

  17. A two-dimensional CdII coordination polymer: poly[diaqua[μ3-5,6-bis(pyridin-2-ylpyrazine-2,3-dicarboxylato-κ5O2:O3:O3,N4,N5]cadmium

    Directory of Open Access Journals (Sweden)

    Monserrat Alfonso

    2016-09-01

    Full Text Available The reaction of 5,6-bis(pyridin-2-ylpyrazine-2,3-dicarboxylic acid with cadmium dichloride leads to the formation of the title two-dimensional coordination polymer, [Cd(C16H8N4O4(H2O2]n. The metal atom is sevenfold coordinated by one pyrazine and one pyridine N atom, two water O atoms, and by two carboxylate O atoms, one of which bridges two CdII atoms to form a Cd2O2 unit situated about a centre of inversion. Hence, the ligand coordinates to the cadmium atom in an N,N′,O-tridentate and an O-monodentate manner. Within the polymer network, there are a number of O—H...O hydrogen bonds present, involving the water molecules and the carboxylate O atoms. There are also C—H...N and C—H...O hydrogen bonds present. In the crystal, the polymer networks lie parallel to the bc plane. They are aligned back-to-back along the a axis with the non-coordinating pyridine rings directed into the space between the networks.

  18. Syntheses and Characterization of New Nickel Coordination Polymers with 4,4’-Dipyridylsulfide. Dynamic Rearrangements of One-Dimensional Chains Responding to External Stimuli: Temperature Variation and Guest Releases/Re-Inclusions

    Directory of Open Access Journals (Sweden)

    Hiroyuki Kawaguchi

    2010-08-01

    Full Text Available Crystal structures and dynamic rearrangements of one-dimensional coordination polymers with 4,4'-dipyridylsulfide (dps have been studied. Reaction of Ni(NO32·6H2O with dps in EtOH yielded [Ni(dps2(NO32]·EtOH (1, which had channels filled with guest EtOH molecules among the four Ni(dps2 chains. This coordination polymer reversibly transformed the channel structure responding to temperature variations. Immersion of 1 in m-xylene released guest EtOH molecules to yield a guest-free coordination polymer [Ni(dps2(NO32] (2a, which was also obtained by treatment of Ni(NO32·6H2O with dps in MeOH. On the other hand, removal of the guest molecules from 1 upon heating at 130 °C under reduced pressure produced a guest-free coordination polymer [Ni(dps2(NO32] (2b. Although the 2a and 2b guest-free coordination polymers have the same formula, they showed differences in the assembled structures of the one-dimensional chains. Exposure of 2b to EtOH vapor reproduced 1, while 2a did not convert to 1 in a similar reaction. Reaction of Ni(NO32·6H2O with dps in acetone provided [Ni(dps(NO32(H2O]·Me2CO (4 with no channel structure. When MeOH or acetone was used as a reaction solvent, the [Ni(dps2(NO32]·(guest molecule type coordination polymer ,which was observed in 1, was not formed. Nevertheless, the reaction of Ni(NO32·6H2O with dps in MeOH/acetone mixed solution produced [Ni(dps2(NO32]·0.5(MeOH·acetone (5, which has an isostructural Ni-dps framework to 1.

  19. Synthesis, structure and characterization of two new metal-organic coordination polymers based on the ligand 5-iodobenzene-1,3-dicarboxylate.

    Science.gov (United States)

    Zhang, Xu; Zhang, Lei; Wang, Meng-Jie; Zhang, Kou-Lin

    2015-09-01

    Two new coordination polymers (CPs) formed from 5-iodobenzene-1,3-dicarboxylic acid (H2iip) in the presence of the flexible 1,4-bis(1H-imidazol-1-yl)butane (bimb) auxiliary ligand, namely poly[[μ2-1,4-bis(1H-imidazol-1-yl)butane-κ(2)N(3):N(3')](μ3-5-iodobenzene-1,3-dicarboxylato-κ(4)O(1),O(1'):O(3):O(3'))cobalt(II)], [Co(C8H3IO4)(C10H14N4)]n or [Co(iip)(bimb)]n, (1), and poly[[[μ2-1,4-bis(1H-imidazol-1-yl)butane-κ(2)N(3):N(3')](μ2-5-iodobenzene-1,3-dicarboxylato-κ(2)O(1):O(3))zinc(II)] trihydrate], {[Zn(C8H3IO4)(C10H14N4)]·3H2O}n or {[Zn(iip)(bimb)]·3H2O}n, (2), were synthesized and characterized by FT-IR spectroscopy, thermogravimetric analysis (TGA), solid-state UV-Vis spectroscopy, single-crystal X-ray diffraction analysis and powder X-ray diffraction analysis (PXRD). The iip(2-) ligand in (1) adopts the (κ(1),κ(1)-μ2)(κ(1), κ(1)-μ1)-μ3 coordination mode, linking adjacent secondary building units into a ladder-like chain. These chains are further connected by the flexible bimb ligand in a trans-trans-trans conformation. As a result, a twofold three-dimensional interpenetrating α-Po network is formed. Complex (2) exhibits a two-dimensional (4,4) topological network architecture in which the iip(2-) ligand shows the (κ(1))(κ(1))-μ2 coordination mode. The solid-state UV-Vis spectra of (1) and (2) were investigated, together with the fluorescence properties of (2) in the solid state.

  20. A simple but efficient strategy to enhance hydrostability of intensely fluorescent Mg-based coordination polymer (CP) via forming a composite of CP with hydrophobic PVDF.

    Science.gov (United States)

    Zhai, Lu; Zhang, Wen-Wei; Zuo, Jing-Lin; Ren, Xiao-Ming

    2016-02-28

    A coordination polymer (CP) of Mg(2+) with 1,3,5-benzenetricarboxylate (BTC(3-)) was synthesized using a solvothermal method. The Mg-CP, with a formula of Mg3(BTC)(HCOO)3(DMF)3, crystallizes in the trigonal space group P3[combining macron], with cell parameters of a = b = 13.972(5) Å, c = 8.090(5) Å and V = 1367.6(11) Å(3), and shows a lamella structure built from planar rosette-type hexanuclear architectures. The Mg-CP emits intense blue fluorescence arising from π* → π transition of intra-ligand of BTC(3-) with 21.69% quantum yield, yet it exhibits poor stability to water. The composites of Mg-CP with hydrophobic polyvinylidene fluoride (PVDF) were sequentially prepared by mechanically mixed, tableted and annealed processes, which showed good compatibility between Mg-CP and PVDF, high hydrostability, and intense blue emission. This study suggests a simple but efficient method to solve the drawbacks of some functional CPs unstable to water and to promote them as practical applications in the field of functional materials.

  1. Two intriguing hydroxy-copper(II) coordination polymers with bis(triazole) and bicarboxylate ligands: Syntheses, structures and photocatalytic degradation of organic dyes

    Science.gov (United States)

    Zhao, Shan; Zheng, Tian-Rui; Shi, Lu-Lu; Li, Ke; Li, Bao-Long; Li, Hai-Yan

    2017-09-01

    Two intriguing coordination polymers [Cu2(OH)(mbtx)(sip)(H2O)2]n (1) and {[Cu3(OH)2(mbtx)(nip)2]·H2O}n (2) were synthesized by the hydrothermal method and characterized by elementary analysis, IR, PXRD, diffuse reflectance spectra and single-crystal X-ray diffraction (mbtx = 1,3-bis(1,2,4-triazol-4-yl)benzene, sip = sulfoisophthalate, nip = 5-nitroisophthalate). 1 shows an unusual 3-connected 2D network based on the dimeric hydroxy-copper(II) cluster [Cu2(μ-OH)] with the point symbol of 63. 2 exhibits an unusual 3D network based on 1D hydroxyl-copper(II) chains [Cu3(OH)2]n. 1 and 2 are highly efficient and universal photocatalysts for the degradation of the organic dyes such as methyl orange (MO), methylene blue (MB) and rhodamine B (RhB) under UV irradiation. The photocatalytic mechanism was supposed.

  2. Two novel 2D coordination polymers constructed from 5-aminoisophthalic acid and 4,4‧-bipyridyl ligands: Syntheses, crystal structure, and photocatalytic performance

    Science.gov (United States)

    Xu, Dao-Xin; Wang, Chong-Chen; Wang, Peng; Li, Jin; Guo, Xin-Xing; Gao, Shi-Jie

    2017-05-01

    Two coordination polymers, [Zn(5-aip)(bpy)0.5]·H2O (1), and [Ni(5-aip)(bpy)0.5(H2O)]·2H2O (2), constructed by 5-aminoisophthalic acid (5-H2aip), 4,4'-bipyridine (bpy), and corresponding ions, have been synthesized under hydrothermal conditions, and characterized by single crystal X-ray diffraction, Fourier transform infrared spectroscopy (FTIR), CHN elemental analysis and UV-Visible diffuse reflectance spectra (UV-Vis DRS). Both 1 and 2 were built up of two-dimensional [Zn(5-aip)(bpy)0.5] and [Ni(5-aip)(bpy)0.5(H2O)] sheets, respectively. The UV-Vis DRS results revealed that the Eg values of 1 and 2 are 3.4 and 2.4 eV, respectively. The photocatalytic activities of degradation of methyl orange (MO), methylene blue (MB) and MO&MB mixture over 1 and degradation of MB over 2 under UV light irradiation were investigated. The results revealed that 1 exhibited good performance to photocatalytically decompose MB, MO and MB&MO mixture, while 2 can only degrade MB efficiently.

  3. Four thiophene-pyridyl-amide-based ZnII/CdII coordination polymers: Assembly, structures, photocatalytic properties and fluorescent recognition for Fe3+

    Science.gov (United States)

    Wang, Xiu-Li; Wu, Xiao-Mei; Liu, Guo-Cheng; Li, Qiao-Min; Lin, Hong-Yan; Wang, Xiang

    2017-05-01

    By tuning metal ions and combining with different dicarboxylates, four new semi-rigid thiophene-bis-pyridyl-bis-amide-based coordination polymers, namely, [Zn(3-bptpa)(1,3-BDC)]·DMA·2H2O (1), [Zn(3-bptpa)(5-MIP)] (2), [Cd(3-bptpa)(1,3-BDC)]·2H2O (3) and [Cd(3-bptpa)(5-MIP)]·4H2O (4) (3-bptpa=N,N‧-bis(pyridine-3-yl)thiophene-2,5-dicarboxamide, 1,3-H2BDC=1,3-benzenedicarboxylic acid, 5-H2MIP=5-methylisophthalic acid, DMA=N,N-dimethylacetamide), were solvothermally/hydrothermally synthesized and structurally characterized by single-crystal X-ray diffraction analyses, IR spectra, UV-vis diffuse-reflectance spectra (DRS), powder X-ray diffraction (PXRD) and thermal gravimetric analyses (TG). The structural analysis reveals that Zn-complexes 1 and 2 are similar 2D networks. While Cd-complexes 3 and 4 exhibit similar 2-fold interpenetrating 3D α-Po frameworks with the (412·63) topology. The photocatalytic properties for the degradation of methylene blue (MB) under ultraviolet light irradiation of the title complexes have been investigated in detail. Furthermore, the luminescent sensing behaviors for metal cations of 1-4 have been studied, the results indicate that 3 is an excellent fluorescent probe, with high sensitivity, selectivity, and simple regeneration, for environmentally relevant Fe3+ ions.

  4. Three coordination polymers based on a star-like geometry 4, 4', 4'' -nitrilotribenzoic acid ligand and their framework dependent luminescent properties

    Science.gov (United States)

    Hu, Zhiyong; Zhao, Meng; Su, Jian; Xu, Shasha; Hu, Lei; Liu, Hui; Zhang, Qiong; Zhang, Jun; Wu, Jieying; Tian, Yupeng

    2018-02-01

    Three novel coordination polymers, [Zn(μ2-HTCA)(Phen)]n (1), {[Cd(μ3-HTCA)(Phen)]·2H2O}n (2), [Mn(μ2-HTCA)(Phen)(H2O)]n (3) were prepared by hydrothermal synthesis from the 4, 4', 4''-nitrilotribenzoicacid (H3TCA) and 1, 10-phenanthroline monohydrate (Phen) with different transition metal salts, which were characterized by elemental analysis, IR spectra, powder and single-crystal X-ray diffraction and thermogravimetric analysis. The photophysical properties of the complexes were investigated by solid-state diffuse reflectance spectra, photoluminescent properties, lifetime and quantum yield. For these complexes, it was found that the band gaps follow the order: 3 < 2 < 1 < 2.80 eV, fluorescence intensity order: 1 > H3TCA > 2 > 3; quantum yield order: H3TCA > 1 > 2 > 3; while the lifetime order: 1 > 2 > H3TCA > 3.

  5. Carboxylate ligands induced structural diversity of zinc(II) coordination polymers based on 3,6-bis(imidazol-1-yl)carbazole: Syntheses, structures and photocatalytic properties

    Science.gov (United States)

    Cheng, Hong-Jian; Tang, Hui-Xiang; Shen, Ya-Li; Xia, Nan-Nan; Yin, Wen-Yu; Zhu, Wei; Tang, Xiao-Yan; Ma, Yun-Sheng; Yuan, Rong-Xin

    2015-12-01

    Solvothermal reactions of Zn(NO3)2·6H2O with 3,6-bis(1-imidazolyl)carbazole (3,6-bmcz) and 1,4-benzenedicarboxylic acid (1,4-H2bdc), p-phenylenediacetic acid (p-H2pda), benzophenone-4,4-dicarboxylic acid (H2bpda) afforded three coordination polymers [Zn(1,4-bdc)(3,6-bmcz)]n (1), {[Zn(p-pda)(3,6-bmcz)]·1.5H2O}n (2) and {[Zn(bpda)(3,6-bmcz)]·0.25H2O}n (3). Complexes 1-3 were characterized by elemental analysis, IR, powder X-ray diffraction, and single-crystal X-ray diffraction. Complex 1 shows 3D structure with 2D nets inclined polycatenation. Complexes 2 and 3 possess an extended 3D supramolecular architecture based on their respective 2D layers through hydrogen-bonding interactions and the π···π stacking interactions. The solid state luminescent and optical properties of 1-3 at ambient temperature were also investigated. A comparative study on their photocatalytic activity toward the degradation of methylene blue in polluted water was explored.

  6. Highly efficient electrochemiluminescence based on 4-amino-1,2,4-triazole Schiff base two-dimensional Zn/Cd coordination polymers.

    Science.gov (United States)

    Zhang, Shu-Hua; Wang, Ji-Ming; Zhang, Hai-Yang; Fan, Yi-Peng; Xiao, Yu

    2017-01-03

    Four coordination polymers, formulated as [Zn(L 1 ) 2 ] n (1), [Cd(L 1 ) 2 ] n (2), [Zn(L 2 ) 2 ] n (3) and [Cd(L 2 ) 2 ] n (4) (HL1 is (E)-2-(((4H-1,2,4-triazol-4-yl)imino)methyl)-4,6-dibromophenol; HL2 is (E)-2-(((4H-1,2,4-triazol-4-yl)imino)methyl)-4,6-dichlorophenol) have been synthesized through vial reactions. The four compounds were structurally characterized by single crystal X-ray diffraction, elemental analysis, PXRD, and fluorescence spectroscopy. For 1-4, a detailed analysis of Hirshfeld surfaces and fingerprint plots facilitates a comparison of intermolecular interactions, which are crucial in building different supramolecular architectures. C-HX (X = Br, Cl) interactions play a crucial role in stabilizing the self-assembly process among adjacent 2-D networks for both complexes. Above all, complexes 1-4 showed highly intense electrochemical luminescence (ECL) in DMF solution and high thermal stability.

  7. Formation of Rosette-Shaped Cd(II) Thiolate Coordination Polymer in Aqueous Solution and Conversion to CdS by Calcination

    International Nuclear Information System (INIS)

    Han, Sung June; Lee, Myung Han; Jeon, Young Jin

    2010-01-01

    We have synthesized rosette-shaped Cd-MSA CPs by a reaction between Cd(II) ions and MSA in aqueous solution and calcined the obtained CPs to obtain CdS microstructures. Upon calcination, the morphology of the CPs does not undergo any significant change, but the particle diameter decreases by 74%. This indicates that our strategy can be used for the synthesis of CPs from other metal thiolates as well. We expect this strategy to be suitable for the preparation of important metal chalcogenide nanostructures and microstructures that can be used in future applications. Coordination polymers (CPs) have attracted considerable attention because of their potential applications in gas storage, catalysis, ion exchange, separation, biomedicine, etc. For use in the above mentioned applications, the structure and morphology of these CPs have been controlled by judicious choice of metals, ligands, and reaction conditions. Recently, Oh and coworkers have reported that CPs can be successfully converted into metal oxides by calcination without causing any significant change in their morphology

  8. Selective sensing of two novel coordination polymers based on tris(4-carboxylphenyl)phosphine oxide for organic molecules and Fe3+ and Hg2+ ions

    Science.gov (United States)

    Huo, Liangqin; Zhang, Jie; Gao, Lingling; Wang, Xiaoqing; Fan, Liming; Fang, Kegong; Hu, Tuoping

    2017-12-01

    Two novel coordination polymers, formulated as {[Zn(HTPO)(bib)]·4H2O}n (1), {[Cu3(TPO)2 (bib)3]·2DMF·0.5EtOH·0.5H2O}n (2) (H3TPO = tris(4-carboxylphenyl)phosphine oxide; bib = 1,4-bis(1H-imidazol-4-yl) benzene), have been synthesized under solvothermal method and characterized by single-crystal X-ray diffraction, elemental analysis (EA), IR spectra, thermogravimetric (TG) analysis, powder X-ray diffraction (PXRD). Structural analysis reveals that complex 1 is a 2D 4-connected sheet with an intriguing 2D + 2D→2D network. Complex 2 displays a 3D 3,4-connected net with the point symbol of {103}2{106}3. Furthermore, the photoluminescence properties of 1 and 2 were investigated in the solid state and various solvent emulsions, the results show that 1 and 2 have better fluorescent recognition for organic molecules, Fe3+ and Hg2+ ions.

  9. Tetracarboxylate-based Co(II), Ni(II) and Cu(II) three-dimensional coordination polymers: syntheses, structures and magnetic properties.

    Science.gov (United States)

    Su, Shengqun; Guo, Zhiyong; Li, Guanghua; Deng, Ruiping; Song, Shuyan; Qin, Chao; Pan, Chengling; Guo, Huadong; Cao, Feng; Wang, Song; Zhang, Hongjie

    2010-10-14

    Methylenediisophthalic acid (H(4)MDIP), as semi-rigid 'V'-shaped carboxylate ligands, react with CoO, NiO and Cu(NO(3))(2)·3H(2)O to give three novel coordination polymers [H(3)O](2)[Co(3)(MDIP)(2)]·2DMF (1), [Ni(2)(HMDIP)(μ(2)-OH)(H(2)O)(3)(DMF)]·4H(2)O·DMF (2) and [Cu(3)(MDIP)(μ(2)-OH)(2)(H(2)O)(4)]·6.5H(2)O (3) (DMF = N,N'-dimethylformamide). All compounds have been characterized by thermogravimetric analysis, IR spectroscopy, elemental and single-crystal X-ray diffraction analyses. Complex 1 is an unusual open anionic framework that is defined as the metal-organic replica of fluorite. Both 2 and 3 features a 3D open framework with one-dimensional elliptical channels and R- and L-helical chains, and their resulting frameworks can be rationalized as crb and pts topology respectively. An interesting feature of complex 3 is the presence of the linear Cu(3) units that is formed by carboxylate and μ(2)-hydroxyl groups linking three Cu(II) metal centers. Magnetic investigations indicate that ferromagnetic couplings are dominant in the three compounds.

  10. A family of entangled coordination polymers constructed from a flexible V-shaped long bicarboxylic acid and auxiliary N-donor ligands: Luminescent sensing

    Energy Technology Data Exchange (ETDEWEB)

    Wang, Jun [Key Laboratory of Synthetic and Natural Functional Molecule Chemistry of Ministry of Education, College of Chemistry and Materials Science, Northwest University, Xi' an 710127 (China); College of Chemistry and Environmental Engineering, Sichuan University of Science & Engineering, Zigong 643000 (China); Bai, Chao [Key Laboratory of Synthetic and Natural Functional Molecule Chemistry of Ministry of Education, College of Chemistry and Materials Science, Northwest University, Xi' an 710127 (China); Hu, Huai-Ming, E-mail: ChemHu1@NWU.EDU.CN [Key Laboratory of Synthetic and Natural Functional Molecule Chemistry of Ministry of Education, College of Chemistry and Materials Science, Northwest University, Xi' an 710127 (China); Yuan, Fei; Xue, Gang-Lin [Key Laboratory of Synthetic and Natural Functional Molecule Chemistry of Ministry of Education, College of Chemistry and Materials Science, Northwest University, Xi' an 710127 (China)

    2017-05-15

    Eight Zn(II)-based coordination polymers, namely, [Zn{sub 2}L{sub 2}(2,2’-bipy)]{sub n}·nH{sub 2}O (1), [Zn{sub 2}L{sub 2}(phen)]{sub n}·nH{sub 2}O (2), [ZnL(phen)(H{sub 2}O)]{sub n} (3), [Zn{sub 3}L{sub 3}(4,4’-bipy)]{sub n} (4), [Zn{sub 2}L{sub 2}(4,4’-bipy){sub 2}]{sub n} [Zn{sub 2}L{sub 2}(H{sub 2}O){sub 2}]{sub n}·2nH{sub 2}O (5), [Zn{sub 4}L{sub 4}(bpp){sub 2}]{sub n} (6), [ZnL(bbi){sub 0.5}]{sub n} (7), [ZnL(bpz)]{sub n} (8) (H{sub 2}L=4,4’-([1,2-phenylenebis-(methylene)]bis(oxy))dibenzoic acid, 2,2’-bipy =2,2’-bipyridine, phen =1,10-phenanthroline, 4,4’-bpy=4,4’-bipyridine, bpp =1,3-bis(4-pyridyl)propane, bbi=1,4-bis(imidazol-1-yl)butane, bpz=3,3′,5,5′-tetramethyl-4,4′-bipyrazole), have been hydrothermally synthesized and structurally characterized. 1–8 display various coordination motifs with different entangled forms and conformations due to the effect of the assistant N-donor ligands. The photoluminescent properties of compounds 1–8 in solid state were studied. Interestingly, 3 exhibits highly efficient luminescent sensing for Cu{sup 2+} cations and CrO{sub 4}{sup 2-} anions, as well as detection ability for the different organic solvents and nitro explosives. These results indicated that it could be utilized as a multi-responsive luminescent sensor. Furthermore, compound 3 also shows good chemical resistance to both acidity and alkalinity solutions with pH ranging from 2 to 13. Thus, multi-photofunctionality and fluorescent response to pH have been combined in the 3, which is the first example in the Zn-based hybrid materials. - Graphical abstract: Eight new Zn(II)-based coordination polymers constructed from a flexible V-shaped long bicarboxylic acid and different N-donor ligands have been hydrothermally synthesized through fixing the metal salts and the solvent systems. The photoluminescent properties of complexes 1−8 in solid state were studied. Interestingly, 3 exhibits highly efficient luminescent sensing for Cu{sup 2

  11. Hydrothermal assembly, structures, topologies, luminescence, and magnetism of a novel series of coordination polymers driven by a trifunctional nicotinic acid building block.

    Science.gov (United States)

    Gu, Jin-Zhong; Liang, Xiao-Xiao; Cai, Yan; Wu, Jiang; Shi, Zi-Fa; Kirillov, Alexander M

    2017-08-22

    In this work, a trifunctional N,O-building block, 5-(4-carboxyphenoxy)nicotinic acid (H 2 cpna), that combines three distinct types of functional groups (COOH, N-pyridyl, and O-ether) was used for the hydrothermal assembly of thirteen new coordination compounds: [Co(μ 3 -Hcpna) 2 ] n (1), [Mn(μ 4 -cpna)(H 2 O)] n (2), [Mn(μ 4 -cpna)(H 2 O) 2 ] n (3), [Mn(μ-cpna)(2,2'-bipy)(H 2 O) 2 ] n (4), {[Ni(μ 3 -cpna)(2,2'-bipy)(H 2 O)] 2 ·H 2 O} n (5), {[Cd(μ 3 -cpna)(2,2'-bipy)]·2H 2 O} n (6), [Zn 2 (μ-cpna) 2 (2,2'-bipy) 2 ] (7), [Cu(μ-cpna)(2,2'-bipy)(H 2 O)] n (8), {[Mn(μ-cpna)(phen) 2 ]·6H 2 O} n (9), {[Ni(μ 3 -cpna)(phen)(H 2 O)]·H 2 O} n (10), [Zn 2 (μ-cpna) 2 (phen) 2 ] (11), {[Pb(μ 3 -cpna)(phen)]·H 2 O} n (12), and [Ni(μ 3 -cpna)(4,4'-bipy) 0.5 (H 2 O)] n (13). These products were synthesized from the corresponding metal(ii) chlorides, H 2 cpna, NaOH, and optional N-donor supporting ligands or templates {bis(4-pyridyl)amine (bpa), 2,2'-bipyridine (2,2'-bipy), 4,4'-bipyridine (4,4'-bipy), or 1,10-phenanthroline (phen)}. Products 1-13 were characterized in the solid state by standard methods, including elemental and thermogravimetric analysis (TGA), IR spectroscopy, and powder (PXRD) and single-crystal X-ray diffraction. The structures of 1-13 feature distinct structural types, namely the 3D metal-organic frameworks (MOFs 1-3), the 2D coordination polymers (5, 6, 10, 12, and 13), the 1D coordination polymers (4, 8, and 9), and the 0D discrete cyclic dimers (7 and 11). Such a wide structural diversity of 1-13 is driven by various factors, including the type of the metal(ii) node, the deprotonation degree of H 2 cpna, and/or the type of supporting ligand or template. Notably, an addition of bpa can tune the structure of MOF 3 by the template effect. Topological classification of underlying metal-organic networks was performed, leading to several distinct topological nets: rtl (in 1), hxg-d-4-C2/m (in 2), sra (in 3), 2C1 (in 4, 8 and 9), fes (in 5, 10

  12. Four coordination polymers based on 5-tert-butyl isophthalic acid and rigid bis(imidazol-1yl)benzene linkers: Synthesis, luminescence detection of acetone and optical properties

    Energy Technology Data Exchange (ETDEWEB)

    Arıcı, Mürsel, E-mail: marici@ogu.edu.tr [Department of Chemistry, Faculty of Arts and Sciences, Eskişehir Osmangazi University, 26480 Eskişehir (Turkey); Zafer Yeşilel, Okan [Department of Chemistry, Faculty of Arts and Sciences, Eskişehir Osmangazi University, 26480 Eskişehir (Turkey); Büyükgüngör, Orhan [Department of Physics, Faculty of Arts and Sciences, Ondokuz Mayıs University, 55139 Samsun (Turkey)

    2017-05-15

    Four coordination polymers including, [Co(µ-Htbip){sub 2}(µ-dib)]{sub n} (1), [Co(µ-tbip)(µ-dmib){sub 0.5}]{sub n} (2), [Zn{sub 2}(µ-tbip)(µ{sub 3}-tbip)(µ-dmib){sub 1.5}]{sub n} (3) and [Cd(µ{sub 3}-tbip)(µ-dib){sub 0.5} (H{sub 2}O)]{sub n} (4) (tbip: 5-tert-butylisophthalate, dib: 1,4-bis(imidazol-1yl)benzene, dmib: 1,4-bis(imidazol-1yl)-2,5-dimethylbenzene), were hydrothermally synthesized and characterized by elemental analysis, IR spectra, single crystal and powder X-ray diffraction and thermal analysis (TG/DTA). The structural diversity is observed depending on ligands and coordination number of metal centers in the synthesized complexes. The tbip ligand displayed five different coordination modes in its complexes. In 1 and 2, complex 1 is 3D framework with the dia topology while complex 2 has 2D structure with the sql topology depending on coordination geometries of Co ions. Complex 3 is 3D framework with the fsh 4,6-conn topology and complex 4 has 2D 4-connected sql topology. Photoluminescent properties of complex 3 dispersed in various organic solvents were investigated and the results showed that 3 dispersed in methanol could be used as a fluorescent sensor for the detection of acetone. Moreover, thermal and optical properties of the complexes were also studied. - Graphical abstract: Four coordination polymers were hydrothermally synthesized and characterized by various techniques. The complexes showed the structural diversity depending on ligands and coordination number of metal centers. The tbip ligand displayed four different coordination modes in its complexes. In 1 and 2, complexes 1 and 2 are 3D and 2D structures with the dia and sql topologies depending on coordination geometries of Co ions, respectively. Complexes 3 and 4 are 3D and 2D structures with the fsh 4,6-conn and sql topology, respectively. Photoluminescent properties of complex 3 dispersed in various organic solvents were investigated and the results showed that 3 dispersed in

  13. Incorporating Embedded Microporous Layers into Topologically Equivalent Pore Network Models for Oxygen Diffusivity Calculations in Polymer Electrolyte Membrane Fuel Cell Gas Diffusion Layers

    International Nuclear Information System (INIS)

    Fazeli, Mohammadreza; Hinebaugh, James; Bazylak, Aimy

    2016-01-01

    Highlights: • Pore network model for modeling PEMFC MPL-coated GDL effective diffusivity. • Bilayered GDL (substrate and MPL) is modeled with a hybrid network of block MPL elements combined with discrete substrate pores. • Diffusivities of MPL-coated GDLs agree with analytical solutions. - Abstract: In this work, a voxel-based methodology is introduced for the hybridization of a pore network with interspersed nano-porous material elements allowing pore network based oxygen diffusivity calculations in a 3D image of a polymer electrolyte membrane (PEM) fuel cell gas diffusion layer (GDL) with an embedded microporous layer (MPL). The composite GDL is modeled by combining a hybrid network of block MPL elements with prescribed bulk material properties and a topologically equivalent network of larger discrete pores and throats that are directly derived from the 3D image of the GDL substrate. This hybrid network was incorporated into a pore network model, and effective diffusivity predictions of GDL materials with MPL coatings were obtained. Stochastically generated numerical models of carbon paper substrates with and without MPLs were used, and the pore space was directly extracted from this realistic geometry as the input for the pore network model. The effective diffusion coefficient of MPL-coated GDL materials was predicted from 3D images in a pore network modeling environment without resolving the nano-scale structure of the MPL. This method is particularly useful due to the disparate length scales that are involved when attempting to capture pore-scale transport in the GDL. Validation was performed by comparing our predicted diffusivity values to analytical predictions, and excellent agreement was observed. Upon conducting a mesh sensitivity study, it was determined that an MPL element size of 7 μm provided sufficiently high resolution for accurately describing the MPL nano-structure.

  14. Sonochemical synthesis of nano-scale mixed-ligands lead(II) coordination polymers as precursors for preparation of PbO and PbBr(OH) nano-structures; thermal, structural and X-ray powder diffraction studies.

    Science.gov (United States)

    Sadeghzadeh, Homa; Morsali, Ali; Yilmaz, Veysel T; Büyükgüngör, Orhan

    2010-03-01

    Nano-structures of two new lead(II) two-dimensional coordination polymers, [Pb(2)(2-pyc)(2)(I)(2)](n) (1) and [Pb(2)(2-pyc)(2)(Br)(2)](n) (2), {2-Hpyc=2-pyridinecarboxilic acid } were synthesized by a sonochemical method that produce the coordination polymers at nano-size. The new nano-structures were characterized by scanning electron microscopy, X-ray powder diffraction, IR spectroscopy and elemental analyses. Compounds 1 and 2 were structurally characterized by single crystal X-ray diffraction and consist of two-dimensional polymeric units. The thermal stability of compounds 1 and 2 were studied by thermal gravimetric and differential thermal analyses. PbO and PbBr(OH) nano-structures were obtained by calcination of the nano-structures of compounds 1 and 2 at 400 degrees C, respectively. Copyright 2009 Elsevier B.V. All rights reserved.

  15. One-dimensional coordination polymers of [Co3(dpa)4]2+ and [MF6]2- (M = ReIV, ZrIV and SnIV)

    DEFF Research Database (Denmark)

    Bulicanu, Vladimir; Pedersen, Kasper Steen; Rouzières, Mathieu

    2015-01-01

    One-dimensional coordination polymers of alternating metal-metal bonded trinuclear [Co3(dpa)4]2+ (dpa = the anion of 2,2'-dipyridylamine) building blocks and [ReF6]2- (1), [ZrF6]2- (2) or [SnF6]2- (3) linkers have been self-assembled and crystallographically characterized. Magnetic measurements...

  16. [Cu.sub.2./sub.(μ-Me.sub.2./sub.N-ba).sub.2./sub.bn)I].sub.n./sub., 1D coordination polymer of copper(I) iodide: synthesis, characterization, and crystal structure

    Czech Academy of Sciences Publication Activity Database

    Khalaji, A.D.; Jafari, K.; Bahramian, B.; Fejfarová, Karla; Dušek, Michal

    2013-01-01

    Roč. 144, č. 11 (2013), s. 1621-1626 ISSN 0026-9247 Grant - others:AV ČR(CZ) AP0701 Program:Akademická prémie - Praemium Academiae Institutional research plan: CEZ:AV0Z10100521 Keywords : coordination polymer * Schiff base * copper * x-ray diffraction * structure analysis Subject RIV: BM - Solid Matter Physics ; Magnetism Impact factor: 1.347, year: 2013

  17. Effects of π-conjugation attenuation on the photophysics and exciton dynamics of poly(p-phenylenevinylene) polymers incorporating 2,2'-bipyridines

    International Nuclear Information System (INIS)

    Chen, L. X.; Jager, W. J.; Niemczyk, M. P.; Wasielewski, M. R.

    1999-01-01

    The effect of π-conjugation attenuation on the photophysics and exciton dynamics of two conjugated polymers 1 and 2 are examined in solution. The structures of polymers 1 and 2 have 2,2'-bipyridyl-5-vinylene units that alternate with one and three 2,5-bis(n-decyloxy)-1,4-phenylenevinylene monomer units, respectively. The photophysics and exciton dynamics of polymers 1 and 2 were compared to those of the homopolymer, poly(2,5-bis(2'-ethylhexyloxy)-1,4-phenylenevinylene) (BEH-PPV). A series of changes in the photophysics of polymers 1 and 2 were found as a result of π-conjugation attenuation. These changes include blue shifts in absorption and emission spectra, spectral diffusion in stimulated emission, enhancement in photoluminescence quantum yields and lifetimes, and increases in photoinduced absorption intensities and lifetimes. These changes are systematically more pronounced in polymer 1 than in polymer 2 and are correlated with π-conjugation attenuation in the polymers due to twisting of the 2,2'-bipyridine groups about the 2,2' single bond. An exciton dynamics model involving an ensemble of initial exciton states localized on oligomeric segments within the polymer with different conjugation lengths is proposed to describe the observed differences between polymers 1 and 2 and BEH-PPV. When the electronic coupling between these segments is strong, the polymer displays characteristics that are close to those of a one-dimensional semiconductor. However, when these couplings are weakened by groups, such as the 2,2'-bipyridine that attenuate π-conjugation, the polymer displays properties of an ensemble of oligomers

  18. Balancing the stability and drug release of polymer micelles by the coordination of dual-sensitive cleavable bonds in cross-linked core.

    Science.gov (United States)

    Deng, Hongzhang; Zhang, Yumin; Wang, Xue; Jianhuazhang; Cao, Yan; Liu, Jinjian; Liu, Jianfeng; Deng, Liandong; Dong, Anjie

    2015-01-01

    The optimal structure design of nanocarriers to inhibit premature release of anticancer drugs from nanocarriers during blood circulation and improve drug release inside tumor cells is still a significant issue for polymer micelles applied to antitumor drug delivery. Herein, in order to balance the contradiction between polymer micellar stability and drug release, dual-sensitive cleavable cross-linkages of benzoic imine conjugated disulfide bonds were introduced into the core of the amphiphilic copolymer micelles to form core-cross-linked micelles. First, biodegradable poly(ethylene glycol)-b-(polycaprolactone-g-poly(methacrylic acid-p-hydroxy benzaldehyde-cystamine)), i.e. mPEG-b-(PCL-g-P(MAA-Hy-Cys)) (PECMHC) copolymers were synthesized and assembled into PECMHC micelles (PECMHC Ms). Then, simply by introducing H2O2 to the PECMHC Ms dispersions to oxidate the thiol groups of cystamine moieties in the core, core-cross-linked PECMHC micelles (cc-PECMHC Ms) ∼100 nm in size were readily obtained in water. In vitro studies of doxorubicin (DOX)-loaded cc-PECMHC Ms show that the cross-linked core impeded the drug release in the physical conditions, owing to the high stability of the micelles against both extensive dilution and salt concentration, while it greatly accelerated DOX release in mildly acidic (pH ∼5.0-6.0) medium with glutathione, owing to the coordination of the pH-sensitive cleaving of benzoic imine bonds and the reduction-sensitive cleaving of disulfide bonds. The in vivo tissue distribution and tumor accumulation of the DOX-loaded cc-PECMHC Ms were monitored via fluorescence images of DOX. DOX-loaded cc-PECMHC Ms exhibited enhanced tumor accumulation because of their high stability in blood circulation and less DOX premature release. Therefore, the cc-PECMHC Ms with dual-sensitive cleavable bonds in the cross-linked core were of excellent biocompatibility, high extracellular stability and had intelligent intracellular drug release properties

  19. Three two-dimensional coordination polymers constructed from transition metals and 2,3-norbornanedicarboxylic acid: Hydrothermal synthesis, crystal structures and photocatalytic properties

    Science.gov (United States)

    Zhang, Jia; Wang, Chong-Chen

    2017-02-01

    Three novel coordination polymers based on transition metals like Co(II), Cu(II) and Mn(II), namely [Co2(bpy)2(nbda)2(H2O)2]·2H2O (denoted as BUC-1), [Cu2(bpy)2(nbda)2(H2O)2]·2H2O (BUC-2), [Mn2(bpy)2(nbda)2(H2O)2]·2H2O (BUC-3), (where bpy = 4,4‧-bipyridine, H2nbda = 2,3-norbornanedicarboxylic acid, BUC = Beijing University of Civil Engineering and Architecture), were synthesized under hydrothermal conditions, and characterized by CNH elemental analyses (EA), Fourier Transform infrared spectroscopy (FTIR), and single crystal X-ray diffraction (SCXRD). BUC 1-3 were isostructural and crystallized in the monoclinic space group C2/c, in which the corresponding metal atoms were linked by typical bidentate bpy ligands into two adjacent 1D [M1(bpy)]n2n+ and [M2(bpy)]n2n+ (M = Co(II), Cu(II), Mn(II)), further joined by versatile nbda2- ligands into 2D [M2(bpy)2(nbda)2]n sheets. Finally, three-dimensional supramolecular frameworks were constructed with the aid of the intermolecular hydrogen bonding interactions. BUC 1-3 exhibited different photocatalytic degradation ability to decompose methylene blue (MB) and methyl orange (MO) under UV light irradiation. Additionally, a possible photocatalytic mechanism HOMO-LUMO was proposed and discussed, which was further confirmed by radicals trapping experiments using isopropanol as radical scavenger.

  20. Self-assembled 3D heterometallic Cu(II)/Fe(II) coordination polymers with octahedral net skeletons: structural features, molecular magnetism, thermal and oxidation catalytic properties.

    Science.gov (United States)

    Karabach, Yauhen Y; Guedes da Silva, M Fátima C; Kopylovich, Maximilian N; Gil-Hernández, Beatriz; Sanchiz, Joaquin; Kirillov, Alexander M; Pombeiro, Armando J L

    2010-12-06

    The new three-dimensional (3D) heterometallic Cu(II)/Fe(II) coordination polymers [Cu(6)(H(2)tea)(6)Fe(CN)(6)](n)(NO(3))(2n)·6nH(2)O (1) and [Cu(6)(Hmdea)(6)Fe(CN)(6)](n)(NO(3))(2n)·7nH(2)O (2) have been easily generated by aqueous-medium self-assembly reactions of copper(II) nitrate with triethanolamine or N-methyldiethanolamine (H(3)tea or H(2)mdea, respectively), in the presence of potassium ferricyanide and sodium hydroxide. They have been isolated as air-stable crystalline solids and fully characterized including by single-crystal X-ray diffraction analyses. The latter reveal the formation of 3D metal-organic frameworks that are constructed from the [Cu(2)(μ-H(2)tea)(2)](2+) or [Cu(2)(μ-Hmdea)(2)](2+) nodes and the octahedral [Fe(CN)(6)](4-) linkers, featuring regular (1) or distorted (2) octahedral net skeletons. Upon dehydration, both compounds show reversible escape and binding processes toward water or methanol molecules. Magnetic susceptibility measurements of 1 and 2 reveal strong antiferromagnetic [J = -199(1) cm(-1)] or strong ferromagnetic [J = +153(1) cm(-1)] couplings between the copper(II) ions through the μ-O-alkoxo atoms in 1 or 2, respectively. The differences in magnetic behavior are explained in terms of the dependence of the magnetic coupling constant on the Cu-O-Cu bridging angle. Compounds 1 and 2 also act as efficient catalyst precursors for the mild oxidation of cyclohexane by aqueous hydrogen peroxide to cyclohexanol and cyclohexanone (homogeneous catalytic system), leading to maximum total yields (based on cyclohexane) and turnover numbers (TONs) up to about 22% and 470, respectively.

  1. Design and synthesis of four coordination polymers generated from 2,2'-biquinoline-4,4'-dicarboxylate and aromatic bidentate ligands

    International Nuclear Information System (INIS)

    Ye Junwei; Zhang Ping; Ye Kaiqi; Zhang Hongyu; Jiang Shimei; Ye Ling; Yang Guangdi; Wang Yue

    2006-01-01

    Four coordination polymers [Zn(bqdc)(phen)] n (1), [Zn(bqdc)(bpy)(H 2 O)] n (2), [Mn(bqdc)(bpy)(H 2 O) 2 ] n (3) and [Mn(bqdc)(phen)(H 2 O) 2 ] n (4) (H 2 bqdc=2,2'-biquinoline-4,4'-dicarboxylic acid, phen=1,10-phenanthroline and bpy=2,2'-bipyridyl) have been synthesized under hydrothermal conditions and characterized by single-crystal X-ray diffraction. Crystal data for 1: monoclinic system, C2/c, a=14.141(3)A, b=10.021(2)A, c=18.511(4)A, β=103.78(3) o , V=2547.6(9)A 3 , Z=4. Crystal data for 2: monoclinic system, p2 1 /n, a=13.656(3)A, b=10.015(2)A, c=19.127(4)A, β=107.13(7) o , V=2500.1(9)A 3 , Z=4. Crystal data for 3: monoclinic system, C2/c, a=14.5050(8)A, b=15.1932(8)A, c=12.7549(6)A, β=116.8010(11) o , V=2508.9(2)A 3 , Z=4. Crystal data for 4: monoclinic system, C2/c, a=14.1732(17)A, b=16.115(3)A, c=12.809(3)A, β=117.04(3) o , V=2605.7(8)A 3 , Z=4. Single helix-like chains exist in 1. The supramolecular structure of 1 exhibits extended two-dimensional network while 2-4 display extended three-dimensional architectures based on interchain hydrogen bonding and π-π interactions. Compounds 1 and 2 show blue photoluminescence under UV light suggesting that they may be employed to develop luminescent materials. Compounds 3 and 4 show interesting magnetic behaviors

  2. Coligand-directed synthesis of five Co(II)/Ni(II) coordination polymers with a neutral tetradentate ligand: syntheses, crystal structures, and properties.

    Science.gov (United States)

    Qin, Ling; Wang, Zhong-Jie; Wang, Ting; Zheng, He-Gen; Chen, Jin-Xi

    2014-09-07

    The solvothermal reactions of 1,1'-oxybis[3,5-di-4-pyridine]-benzene (L) and transition metal cations (Co and Ni) afford five novel coordination polymers in the presence of flexible bridging ligands (4,4'-H2nba = 4,4'-dicarboxydiphenylamine, H2cam = d-camphoric acid, 4,4'-H2sdb = 4,4'-sulfonyldibenzoic acid, H2chdc = 1,4-trans-cyclohexanedicarboxylic acid), namely {[Co2L2(OH)2(nba)]·2DMF}n (), {[CoL(cam)(H2O)]}n (), {[Co3(L)(4,4'-sdb)3(H2O)]·1.5CH3CN·4H2O}n (), {[Ni3(L)(4,4'-sdb)3(H2O)]·1.5CH3CN·4H2O}n (), and {[Ni2L2(chdc)2(H2O)2]·(H2O)3}n () (DMF = N,N-dimethylformamide). Their structures have been determined by single-crystal X-ray diffraction analyses and further characterized by elemental analyses, IR spectroscopy, and powder X-ray diffraction. Complex reveals a 2-fold interpenetrating three-dimensional (3D) framework with the Schläfli symbol {4·8·10(4)}{4·8·10} topology. Compound crystallizes in the achiral space group with the d-camphorate ligand racemized. Compounds and reveal similar structure with the {3·4(4)·6}{3(2)·4(8)·5(9)·6(9)} topology based on a linear trinuclear building block M3(OOCR)6 (M = Co(ii) or Ni(ii)). Compound is a wavy sheet, where both carboxylate and L ligands act as bidentate ligands. Moreover, UV-Visible absorption spectra of complexes , and the magnetic properties of have been investigated.

  3. Lead(II) coordination polymers based on rigid-flexible 3,5-bis-oxyacetate-benzoic acid: Structural transition driven by temperature control

    Energy Technology Data Exchange (ETDEWEB)

    Chen, Yong-Qiang, E-mail: chenjzxy@126.com; Tian, Yuan

    2017-03-15

    Three Pb(II) complexes ([Pb{sub 3}(BOABA){sub 2}(H{sub 2}O)]·H{sub 2}O){sub n} (1), ([Pb{sub 4}(BOABA){sub 2}(µ{sub 4}-O)(H{sub 2}O){sub 2}]·H{sub 2}O){sub n} (2), and [Pb{sub 3}(BOABA){sub 2}(H{sub 2}O)]{sub n} (3) (H{sub 3}BOABA=3,5-bis-oxyacetate-benzoic acid) were obtained under the same reaction systems with different temperatures. Complexes 1 and 2 are two dimensional (2D) networks based on Pb-BOABA chains and Pb{sub 4}(µ{sub 4}-O)(COO){sub 6} SBUs, respectively. Complex 3 presents an interesting three dimensional (3D) framework, was obtained by increasing the reaction temperature. Structural transition of the crystallization products is largely dependent on the reaction temperature. Moreover, the fluorescence properties of complexes 1–3 have been investigated. - Graphical abstract: Three Pb(II) coordination polymers were obtained under the same reaction systems with different temperatures. Both of complexes 1 and 2 are 2D network. 3 presents a 3D framework based on Pb–O–C rods SBUs. The 2D to 3D structures transition between three complexes was achieved successfully by temperature control. - Highlights: • Three Pb(II) complexes were obtained under the same reaction systems with different temperatures. • Structural transition of the crystallization products is largely dependent on the reaction temperature. • The luminescence properties studies reveal that three complexes exhibit yellow fluorescence emission behavior, which might be good candidates for obtaining photoluminescent materials.

  4. Sonochemical synthesis of two novel Pb(II) 2D metal coordination polymer complexes: New precursor for facile fabrication of lead(II) oxide/bromide micro-nanostructures.

    Science.gov (United States)

    Hayati, Payam; Suárez-García, Salvio; Gutierrez, Angel; Şahin, Ertan; Molina, Daniel Ruiz; Morsali, Ali; Rezvani, Ali Reza

    2018-04-01

    Two new lead(II) coordination polymer complexes (CSCs) (2D), [Pb 2 (L) 2 (Br) 2 ] n ·H 2 O (1), [Pb 2 (HL / )(L / )(H 2 O) 2 ] n ·H 2 O (2), where L = C 6 H 5 NO 2 (2-pyridinecarboxylic acid) and L /  = C 9 H 6 O 6 (1,3,5-tricarboxylic acid), have been synthesized under different experimental conditions. Micrometric crystals (bulk) or microsized materials have been obtained depending on using the branch tube method or sonochemical irradiation. All materials have been characterized by scanning electron microscopy (SEM), powder X-ray diffraction (PXRD) and FT-IR spectroscopy. Single crystal X-ray analyses on complexes 1 and 2 shows that Pb 2+ ions are 8-coordinated, 7 and 9-coordinated, respectively. Topological analysis shows that the compound 1 and 2 are 4,6L26 and bnn net, respectively. However, neither the shape nor the morphology is maintained, showing the role of sonochemistry to modulate both morphology and dimensions of the resulting crystalline material, independently of whether we have a 2D coordination polymer (CP). Finally, micro structuration of lead(II) bromide oxide and lead(II) oxide have been prepared by calcination of two different lead (II) CPs at 700 °C that were characterized by SEM and XRD. Copyright © 2017 Elsevier B.V. All rights reserved.

  5. Utilization of mixed ligands to construct diverse Ni(II)-coordination polymers based on terphenyl-2,2′,4,4′-tetracarboxylic acid and varied N-donor co-ligands

    International Nuclear Information System (INIS)

    Wang, Chao; Zhao, Jun; Xia, Liang; Wu, Xue-Qian; Wang, Jian-Fang; Dong, Wen-Wen; Wu, Ya-Pan

    2016-01-01

    Three new coordination polymers, namely, {[Ni(H 2 L)(bix)(H 2 O) 2 ]·2h 2 O} n (1), {[Ni(HL)(Hdpa)(H 2 O) 2 ]·H 2 O} n (2), {[Ni(L) 0.5 (bpp)(H 2 O)]·H 2 O} n (3) (H 4 L=terphenyl-2,2′,4,4′-tetracarboxylic acid; bix=1,4-bis(imidazol-1-ylmethyl)benzene; dpa =4,4′-dipyridylamine; bpp=1,3-bis(4-pyridyl)propane), based on rigid H 4 L ligand and different N-donor co-ligands, have been synthesized under hydrothermal conditions. Compound 1 features a 3D 4-connected 6 6 -dia-type framework with H 4 L ligand adopts a μ 2 -bridging mode with two symmetry-related carboxylate groups in μ 1 -η 1 :η 0 monodentate mode. Compound 2 displays a 1D [Ni(HL)(Hdpa)] n ribbon chains motif, in which the H 4 L ligand adopts a μ 2 -bridging mode with two carboxylate groups in μ 1 -η 1 :η 1 and μ 1 -η 1 :η 0 monodentate modes, while 3 possesses a (4,4)-connected 3D frameworks with bbf topology, with H 4 L ligand displays a μ 4 -bridging coordination mode. The H 4 L ligand displays not only different deprotonated forms but also diverse coordination modes and conformations. The structural diversities among 1–3 have been carefully discussed, and the roles of N-donor co-ligands in the self-assembly of coordination polymers have been well documented. - Graphical abstract: Three nickel coordination polymers with different architectures based on mixed ligand system were synthesized and structurally characterized. Topology analyses indicate that 1 shows the 4-connected 6 6 -dia net, 1D ribbon chains for 2 and 3D (4,4)-connected bbf network for 3. Display Omitted - Highlights: • Three Ni-based coordination polymers with distinct features have been prepared. • Compound 1 features a 3D 4-connected 66-dia-type framework, 2 displays a 1D [Ni(HL)(Hdpa)] n ribbon chains motif, while 3 possesses a (4,4)-connected 3D frameworks with bbf topology. • The “mixed ligand assembled” strategy is significant potential for network design.

  6. Biomimetic coating of organic polymers with a protein-functionalized layer of calcium phosphate: the surface properties of the carrier influence neither the coating characteristics nor the incorporation mechanism or release kinetics of the protein.

    Science.gov (United States)

    Wu, Gang; Liu, Yuelian; Iizuka, Tateyuki; Hunziker, Ernst B

    2010-12-01

    Polymers that are used in clinical practice as bone-defect-filling materials possess many essential qualities, such as moldability, mechanical strength and biodegradability, but they are neither osteoconductive nor osteoinductive. Osteoconductivity can be conferred by coating the material with a layer of calcium phosphate, which can be rendered osteoinductive by functionalizing it with an osteogenic agent. We wished to ascertain whether the morphological and physicochemical characteristics of unfunctionalized and bovine-serum-albumin (BSA)-functionalized calcium-phosphate coatings were influenced by the surface properties of polymeric carriers. The release kinetics of the protein were also investigated. Two sponge-like materials (Helistat® and Polyactive®) and two fibrous ones (Ethisorb™ and poly[lactic-co-glycolic acid]) were tested. The coating characteristics were evaluated using state-of-the-art methodologies. The release kinetics of BSA were monitored spectrophotometrically. The characteristics of the amorphous and the crystalline phases of the coatings were not influenced by either the surface chemistry or the surface geometry of the underlying polymer. The mechanism whereby BSA was incorporated into the crystalline layer and the rate of release of the truly incorporated depot were likewise unaffected by the nature of the polymeric carrier. Our biomimetic coating technique could be applied to either spongy or fibrous bone-defect-filling organic polymers, with a view to rendering them osteoconductive and osteoinductive.

  7. Step-by-step thermal transformations of a new porous coordination polymer [(H2O)5CuBa(Me2mal)2]n (Me2mal2-=dimethylmalonate): Thermal degradation to barium cuprate

    Science.gov (United States)

    Zauzolkova, Natalya; Dobrokhotova, Zhanna; Lermontov, Anatoly; Zorina, Ekaterina; Emelina, Anna; Bukov, Mikhail; Chernyshev, Vladimir; Sidorov, Aleksey; Kiskin, Mikhail; Bogomyakov, Artem; Lytvynenko, Anton; Kolotilov, Sergey; Velikodnyi, Yuriy; Kovba, Maksim; Novotortsev, Vladimir; Eremenko, Igor

    2013-01-01

    The reactions of CuSO4·5H2O, dimethylmalonic acid and Ba(OH)2·H2O (Cu: H2Me2mal: Ba=1: 2: 2) in aqueous and aqueous-ethanol solutions (H2O: EtOH=1: 1) resulted in formation of 3D-porous coordination polymers [(H2O)3(μ-H2O)2CuBa(μ3-Me2mal)(Me2mal)]n (1) and [(μ-H2O)CuBa(μ3-Me2mal)(μ4-Me2mal)]n (2), respectively. It has been shown that compound 2 was an intermediate in the thermal degradation of compound 1. Thorough studies of solid-state thermolysis of 1 and 2 allowed to detect formation of coordination polymer [CuBa(μ4-Me2mal)(μ5-Me2mal)]n (3), structure of which was determined by X-ray powder diffraction. It has been found that the channels in polymer 3 were accessible for guest molecules (MeOH). Theoretical estimation of methanol diffusion barrier was carried out. Complete solid-phase thermolysis of 1 and 2 leads to a mixture of BaCuO2, BaCO3, and CuO. Special conditions for obtaining of a crystalline phase of pure cubic BaCuO2 were determined.

  8. Binuclear and tetranuclear Mn(II) clusters in coordination polymers derived from semirigid tetracarboxylate and N‑donor ligands: syntheses, new topology structures and magnetism

    Energy Technology Data Exchange (ETDEWEB)

    Li, Xiao-Ling [College of Chemistry and Chemical Engineering, and Henan Key Laboratory of Function-Oriented Porous Materials, Luoyang Normal University, Luoyang 471934 (China); Liu, Guang-Zhen, E-mail: gzliuly@126.com [College of Chemistry and Chemical Engineering, and Henan Key Laboratory of Function-Oriented Porous Materials, Luoyang Normal University, Luoyang 471934 (China); Xin, Ling-Yun [College of Chemistry and Chemical Engineering, and Henan Key Laboratory of Function-Oriented Porous Materials, Luoyang Normal University, Luoyang 471934 (China); Wang, Li-Ya [College of Chemistry and Chemical Engineering, and Henan Key Laboratory of Function-Oriented Porous Materials, Luoyang Normal University, Luoyang 471934 (China); College of Chemistry and Pharmacy Engineering, Nanyang Normal University, Nanyang, Henan 473061 (China)

    2017-02-15

    Two topologically new Mn(II) coordination polymers, namely ([Mn{sub 2}(H{sub 4}ipca)(4,4′-bpy){sub 1.5}(CH{sub 3}CH{sub 2}OH){sub 0.5}(H{sub 2}O){sub 1.5}]·0.5CH{sub 3}CH{sub 2}OH·2.5H{sub 2}O){sub n} (1) and (Mn{sub 4}(H{sub 4}ipca){sub 2}(bze)(H{sub 2}O){sub 4}){sub n} (2) were prepared by the solvothermal reactions of Mn(II) acetate with 5-(2’,3’-dicarboxylphenoxy)isophthalic acid (H{sub 4}ipca) in the presence of different N-donor coligands (4,4′-bpy=4,4′-bipyridyl and bze=1, 4-bis(1-imidazoly)benzene). The single crystal X-ray diffractions reveal that two complexes display 3D metal-organic frameworks with binuclear and tetranuclear Mn(II) units, respectively. Complex 1 features a (3,4,6)-connected porous framework based on dinuclear Mn(II) unit with the (4.5{sup 2}){sub 2}(4{sup 2}.6{sup 8}.8{sup 3}.9{sup 2})(5{sup 2}.8.9{sup 2}.10) new topology, and complex 2 possesses a (3,8)-connected network based on tetranuclear Mn(II) unit with the (4{sup 2}.6){sub 2}(4{sup 4}.6{sup 14}.7{sup 7}.8{sup 2}.9) new topology. Magnetic analyses indicate that both two compounds show weak antiferromagnetic interactions within binuclear and tetranuclear Mn(II) units. - Graphical abstract: Two topologically new Mn(II) metal-organic frameworks with dinuclear and tetranuclear Mn(II) units respectively were assembled by using 5-(2′,3′-Dicarboxylphenoxy)isophthalic acid and N-donor ancillary coligands. Magnetic analysis revealed the existence of dominant antiferromagnetic interactions within the polynuclear Mn(II) units. - Highlights: • Mixed ligand strategy produces two topologically new MOFs with dinuclear and tetranuclear Mn(II) respectively. • Magnetic fitting gives weak antiferromagnetic interactions within the polynuclear Mn(II) units.

  9. Thermal Expansion Behavior of MI[AuX2(CN)2]-Based Coordination Polymers (M = Ag, Cu; X = CN, Cl, Br).

    Science.gov (United States)

    Ovens, Jeffrey S; Leznoff, Daniel B

    2017-07-03

    Two sets of trans-[AuX 2 (CN) 2 ] - -based coordination polymer materials-M[AuX 2 (CN) 2 ] (M = Ag; X = Cl, Br or M = Cu; X = Br) and M[Au(CN) 4 ] (M = Ag, Cu)-were synthesized and structurally characterized and their dielectric constants and thermal expansion behavior explored. The M[AuX 2 (CN) 2 ] series crystallized in a tightly packed, mineral-like structure featuring 1-D trans-[AuX 2 (CN) 2 ] - -bridged chains interconnected via a series of intermolecular Au···X and M···X (M = Ag, Cu) interactions. The M[Au(CN) 4 ] series adopted a 2-fold interpenetrated 3-D cyano-bound framework lacking any weak intermolecular interactions. Despite the tight packing and the presence of intermolecular interactions, these materials exhibited decreased thermal stability over unbound trans-[AuX 2 (CN) 2 ] - in [ n Bu 4 N][AuX 2 (CN) 2 ]. A significant dielectric constant of up to ε r = 36 for Ag[AuCl 2 (CN) 2 ] (1 kHz) and a lower ε r = 9.6 (1 kHz) for Ag[Au(CN) 4 ] were measured and interpreted in terms of their structures and composition. A systematic analysis of the thermal expansion properties of the M[AuX 2 (CN) 2 ] series revealed a negative thermal expansion (NTE) component along the cyano-bridged chains with a thermal expansion coefficient (α CN ) of -13.7(11), -14.3(5), and -11.36(18) ppm·K -1 for Ag[AuCl 2 (CN) 2 ], Ag[AuBr 2 (CN) 2 ], and Cu[AuBr 2 (CN) 2 ], respectively. The Au···X and Ag···X interactions affect the thermal expansion similarly to metallophilic Au···Au interactions in M[Au(CN) 2 ] and AuCN; replacing X = Cl with the larger Br atoms has a less significant effect. A similar analysis for the M[Au(CN) 4 ] series (where the volume thermal expansion coefficient, α V , is 41(3) and 68.7(19) ppm·K -1 for M = Ag, Cu, respectively) underscored the significance of the effect of the atomic radius on the flexibility of the framework and, thus, the thermal expansion properties.

  10. A new 1D manganese(II) coordination polymer with end-to-end azide bridge and isonicotinoylhydrazone Schiff base ligand: Crystal structure, Hirshfeld surface, NBO and thermal analyses

    Science.gov (United States)

    Khani, S.; Montazerozohori, M.; Masoudiasl, A.; White, J. M.

    2018-02-01

    A new manganese (II) coordination polymer, [MnL2 (μ-1,3-N3)2]n, with co-ligands including azide anion and Schiff base based on isonicotinoylhydrazone has been synthesized and characterized. The crystal structure determination shows that the azide ligand acts as end-to-end (EE) bridging ligand and generates a one-dimensional coordination polymer. In this compound, each manganes (II) metal center is hexa-coordinated by four azide nitrogens and two pyridinic nitrogens for the formation of octahedral geometry. The analysis of crystal packing indicates that the 1D chain of [MnL2 (μ-1,3-N3)2]n, is stabilized as a 3D supramolecular network by intra- and inter-chain intermolecular interactions of X-H···Y (X = N and C, Y = O and N). Hirshfeld surface analysis and 2D fingerprint plots have been used for a more detailed investigation of intermolecular interactions. Also, natural bond orbital (NBO) analysis was performed to get information about atomic charge distributions, hybridizations and the strength of interactions. Finally, thermal analysis of compound showed its complete decomposition during three thermal steps.

  11. Toward a Novel Strategy for Magnetic–Resonance Molecular Imaging and Therapy of Tumor Angiogenesis: Nickel Superparamagnetic Nanoparticles Incorporated into Radiation-Functionalized Polymer Nano-Carriers

    International Nuclear Information System (INIS)

    Rizza, G.; Clochard, M.C.; Berthelot, T.

    2009-01-01

    The more recent research activity of the Irradiated Polymers team focused mainly on nanostructures membranes for nanofiltration and nanofluidic systems in biomedical and energy fields. The so called track-etched membranes were made by chemical revealing of tracks induced from swift heavy ions irradiations in collaboration with the CIRIL laboratory (GANIL, France). The background experience of the tem about electron-polymer interaction allowed us to predict the behavior of the radio-induced grafting, namely radografting, inside ion-tracks. It was the necessary to adapt our detection tools to chemical modification of picomole range and to nanometer scale architecture of these membranes. Consequently, we resorted to the use of high-cost techniques such as small angle neutron scattering to be able to characterize accurately polymer membrane nanopores. In parallel, more accessible techniques like gas permeation have been developed for a rapid evaluation of nanopore radii. The labeling of introduced chemical functionalities with fluorescent probes was a very effective mean to visualize very few amounts of molecules by confocal microscopy and to localize, for the first time, the radiografting inside theetched tracks. The study of such nanostructures has enlarged our perspectives and collaborations. Indeed, it pushed us to electrodeposite metallic nanowires and to create conductive polymer nanotubes to study the conduction in nanochannels of such systems (Biosensors and optoelectronic applications) and to study the ionic conduction in nano-channels filled of hydrogen (Polymer Electrolyte Membrane Fuel Cell application). More recently, since January 2007, we are developing a subject on another kind of polylmer device on which we are applying our known-how in radiografting. It is about the functionalized fluoropolymer nanoparticles for medical imaging. In the following, I describe in more details some of the recent works being carried out at our laboratory on the irradiated

  12. Zn(II) coordination polymer of an in situ generated 4-pyridyl (4Py) attached bis(amido)phosphate ligand, [PO2(NH4Py)2]- showing preferential water uptake over aliphatic alcohols.

    Science.gov (United States)

    Gupta, Arvind K; Nagarkar, Sanjog S; Boomishankar, Ramamoorthy

    2013-08-14

    Two polymorphic 2D-coordination polymers of composition [ZnL(HCO2)]∞ were synthesized from an in situ generated ligand [PO2(NH(4)Py)2](-) (L(-)). The ligand L(-) was generated by a facile metal-assisted P-N bond hydrolysis reaction from the corresponding phosphonium salt 1, [P(NH(4)Py)4]Cl, or from the neutral phosphoric triamide 2, [PO(NH(4)Py)3]. The de-solvated sample of the polymer [ZnL(HCO2)]∞ features polar micropores and shows a type I isotherm for CO2 sorption whereas a type II behaviour was observed for N2. The vapour sorption isotherm of the de-solvated sample of [ZnL(HCO2)]∞ shows preferential adsorption of water vapour over aliphatic alcohols.

  13. A detailed study on the interaction of a novel water-soluble glycine bridged zinc(II) Schiff base coordination polymer with BSA: synthesis, crystal structure, molecular docking and cytotoxicity effect against A549, Jurkat and Raji cell lines

    Czech Academy of Sciences Publication Activity Database

    Asadi, Z.; Golchin, M.; Eigner, Václav; Dušek, Michal; Amirghofran, Z.

    2017-01-01

    Roč. 465, Aug (2017), s. 50-60 ISSN 0020-1693 R&D Projects: GA MŠk LO1603; GA ČR(CZ) GA14-03276S EU Projects: European Commission(XE) CZ.2.16/3.1.00/24510 Institutional support: RVO:68378271 Keywords : water-soluble * coordination polymer * BSA * docking study * anticancer activity Subject RIV: BM - Solid Matter Physics ; Magnetism OBOR OECD: Condensed matter physics (including formerly solid state physics, supercond.) Impact factor: 2.002, year: 2016

  14. A new series of lanthanide coordination polymers with 2,2‧-bipyridine and glutaric acid: Synthesis, crystal structures and properties of [Ln(bipy)(glut)(NO3)

    Science.gov (United States)

    Wang, Chunguang; Xing, Yongheng; Li, Zhangpeng; Li, Jing; Zeng, Xiaoqing; Ge, Maofa; Niu, Shuyun

    2009-08-01

    A series of new lanthanide coordination polymers, with the formula [Ln(bipy)(glut)(NO 3)] (Ln = Eu ( 1), Tb ( 2), Sm ( 3), Pr ( 4); bipy = 2,2'-bipyridine; H 2glut = glutaric acid), have been synthesized under the hydrothermal condition and characterized by elemental analysis, IR spectroscopy, powder X-ray diffraction, and single-crystal X-ray diffraction. Structural analyses reveal that all four complexes are isostructural and crystallized in monoclinic system, P2 1/ c space group. For these complexes, the Ln 3+ are all linked through glutaric acid ligands to form 1D chain-like polymeric structures, and bipy and NO3- are coordinated on two sides of the chains. The thermogravimetric analysis of 1 and photoluminescent properties of 1 and 2 are discussed in detail.

  15. A three-dimensional CdII coordination polymer constructed from 1,1'-biphenyl-2,2',5,5'-tetracarboxylate and 1,4-bis(1H-imidazol-1-yl)benzene ligands.

    Science.gov (United States)

    Su, Feng; Lu, Li-Ping

    2015-07-01

    The title coordination polymer, poly[[aqua(μ5-1,1'-biphenyl-2,2',5,5'-tetracarboxylato)bis[μ2-1,4-bis(1H-imidazol-1-yl)benzene]dicadmium(II)] dihydrate], {[Cd2(C16H6O8)(C12H10N4)2(H2O)]·2H2O}n, was crystallized from a mixture of 1,1'-biphenyl-2,2',5,5'-tetracarboxylic acid (H4bpta), 1,4-bis(1H-imidazol-1-yl)benzene (1,4-bib) and cadmium nitrate in water-dimethylformamide. The crystal structure consists of two crystallographically independent Cd(II) cations, with one of the Cd(II) cations possessing a slightly distorted pentagonal bipyramidal geometry. The second Cd(II) centre is coordinated by carboxylate O atoms and imidazole N atoms from two separate 1,4-bib ligands, displaying a distorted octahedral CdN2O4 geometry. The completely deprotonated bpta(4-) ligand, exhibiting a new coordination mode, bridges five Cd(II) cations to form one-dimensional chains via μ3-η(1):η(2):η(1):η(2) and μ2-η(1):η(1):η(0):η(0) modes, and these are further linked by 1,4-bib ligands to form a three-dimensional framework with a (4(2).6(4))(4.6(2))(4(3).6(5).7(2)) topology. The structure of the coordination polymer is reinforced by intermolecular hydrogen bonding between carboxylate O atoms, aqua ligands and crystallization water molecules. The solid-state photoluminescence properties were investigated and the complex might be a candidate for a thermally stable and solvent-resistant blue fluorescent material.

  16. Polymeric coordination compounds

    Indian Academy of Sciences (India)

    Administrator

    Metal coordination polymers with one- and two-dimensional structures are of current interest due to their possible relevance to material science 1. In continuation of our previous studies 2,3, several new polymeric compounds are reported here. Among the complexes of silver with aminomethyl pyridine (amp) ...

  17. High-speed electro-optic switch based on nonlinear polymer-clad waveguide incorporated with quasi-in-plane coplanar waveguide electrodes

    Science.gov (United States)

    Jiang, Ming-Hui; Wang, Xi-Bin; Xu, Qiang; Li, Ming; Niu, Dong-Hai; Sun, Xiao-Qiang; Wang, Fei; Li, Zhi-Yong; Zhang, Da-Ming

    2018-01-01

    Nonlinear optical (NLO) polymer is a promising material for active waveguide devices that can provide large bandwidth and high-speed response time. However, the performance of the active devices is not only related to the waveguide materials, but also related to the waveguide and electrode structures. In this paper, a high-speed Mach-Zehnder interferometer (MZI) type of electro-optic (EO) switch based on NLO polymer-clad waveguide was fabricated. The quasi-in-plane coplanar waveguide electrodes were also introduced to enhance the poling and modulating efficiency. The characteristic parameters of the waveguide and electrode were carefully designed and simulated. The switches were fabricated by the conventional micro-fabrication process. Under 1550-nm operating wavelength, a typical fabricated switch showed a low insertion loss of 10.2 dB, and the switching rise time and fall time were 55.58 and 57.98 ns, respectively. The proposed waveguide and electrode structures could be developed into other active EO devices and also used as the component in the polymer-based large-scale photonic integrated circuit.

  18. Multi-scale analysis of polymer-diluted turbulent flow using a new elastic dumbbell model with incorporation of variable non-affinity

    Science.gov (United States)

    Horiuti, Kiyosi; Sayama, Shotaro

    2017-11-01

    We consider turbulent flows diluted with the polymers. The polymer chains are modeled as elastic dumbbells and represented by Brownian dynamics. The motion of solvent fluid is pursued by DNS. Affinity in the motion of the bead-spring configuration with the fluid surrounding the dumbbells is commonly assumed, but it results in emergence of Elasto-inertial turbulence (EIT) regime. When the polymers are highly stretched, molecular motions may not precisely correspond to the macroscopic deformation (de Gennes 1986). We develop a new dumbbell model in which the affine constraint is removed and non-affinity is introduced by allowing slippage of the dumbbells against the solvent. This is done by adopting the lower-convective derivative in addition to the upper-convective derivative in the governing equation for the motion of the dumbbells. We conduct its assessment in the forced homogeneous isotropic turbulence. It is shown that the dumbbells obtained from the case with complete affinity are rotated and converted to the alignment of the dumbbells in the complete non-affine case, and vice versa. This alteration of configurations is repeated quasi-periodically with the intervals comparable to the relaxation time. The largest stretching of the dumbbells and elastic energy production are achieved in the complete non-affine dumbbells. Occurrence of EIT is eliminated and de Gennes hypothesis is justified.

  19. Enhanced performance of dye-sensitized solar cells based on organic dopant incorporated PVDF-HFP/PEO polymer blend electrolyte with g-C{sub 3}N{sub 4}/TiO{sub 2} photoanode

    Energy Technology Data Exchange (ETDEWEB)

    Senthil, R.A.; Theerthagiri, J. [Solar Energy Lab, Department of Chemistry, Thiruvalluvar University, Vellore 632115 (India); Madhavan, J., E-mail: jagan.madhavan@gmail.com [Solar Energy Lab, Department of Chemistry, Thiruvalluvar University, Vellore 632115 (India); Murugan, K. [Department of Zoology, Bharathiar University, Coimbatore 641046 (India); Arunachalam, Prabhakarn [Electrochemistry Research Group, Chemistry Department, College of Science, King Saud University, Riyadh 11451 (Saudi Arabia); Arof, A.K. [Centre for Ionics University Malaya, Department of Physics, University of Malaya, Kuala Lumpur 50603 (Malaysia)

    2016-10-15

    This work describes the effect of 2-aminopyrimidine (2-APY) on poly(vinylidinefluoride-co-hexafluoropropylene) (PVDF-HFP)/polyethylene oxide (PEO) blend polymer electrolyte along with binary iodide salts (tetrabutylammonium iodide (TBAI) and potassium iodide (KI)) and iodine (I{sub 2}) were studied for enhancing the efficiency of the dye-sensitized solar cells (DSSCs) consisting of g-C{sub 3}N{sub 4}/TiO{sub 2} composite as photoanode. The g-C{sub 3}N{sub 4} was synthesized from low cost urea by thermal condensation method. It was used as a precursor to synthesize the various weight percentage ratios (5%, 10% and 15%) of g-C{sub 3}N{sub 4}/TiO{sub 2} composites by wet-impregnation method. The pure and 2-APY incorporated PVDF-HFP/PEO polymer blend electrolytes were arranged by wet chemical process (casting method) using DMF as a solvent. The synthesized g-C{sub 3}N{sub 4}/TiO{sub 2} composites and polymer blend electrolytes were studied and analyzed by Fourier transform infrared (FT-IR) spectroscopy, X-ray diffractometer (XRD) and scanning electron microscopy (SEM). The ionic conductivity values of the pure and 2-APY incorporated PVDF-HFP/PEO blend electrolytes were estimated to be 4.53×10{sup −5} and 1.87×10{sup −4} Scm{sup −1} respectively. The UV–vis absorption spectroscopy was carried out for the pure and different wt% of g-C{sub 3}N{sub 4}/TiO{sub 2} composites coated FTO films after N3 dye-sensitization. The 10 wt% g-C{sub 3}N{sub 4}/TiO{sub 2} composite film showed a maximum absorption compared to the others. The DSSC assembled with 10 wt% g-C{sub 3}N{sub 4}/TiO{sub 2} as photoanode using the pure polymer blend electrolyte exhibited a power conversion efficiency (PCE) of 3.17% , which was superior than that of DSSC based pure TiO{sub 2} (2.46%). However, the PCE was increased to 4.73% for the DSSC assembled using 10 wt% g-C{sub 3}N{sub 4}/TiO{sub 2} as photoanode with 2-APY incorporated polymer blend electrolyte. Hence, the present study is a

  20. Study of Six Green Insensitive High Energetic Coordination Polymers Based on Alkali/Alkali-Earth Metals and 4,5-Bis(tetrazol-5-yl)-2 H-1,2,3-triazole.

    Science.gov (United States)

    Chen, Dong; Jing, Dong; Zhang, Qi; Xue, Xianggui; Gou, Shaohua; Li, Hongzhen; Nie, Fude

    2017-12-14

    Constructing insensitive high-performance energetic coordination polymers (ECPs) with alkali/alkali-earth metal ions and a nitrogen-rich organic backbone has been proved to be a feasible strategy in this work. Six diverse dimensional novel ECPs (compounds 1-6) were successfully synthesized from Na I , Cs I , Ca II , Sr II , Ba II ions and a nitrogen-rich triheterocyclic 4,5-bis(tetrazol-5-yl)-2 H-1,2,3-triazole (H 3 BTT). All compounds show outstanding stability and low sensitivity, the thermal stability of these ECPs are significantly improved as the structural reinforcement increases from 1D to 3D, in which the decomposition temperature of 3D Ba II based compound 6 is as high as 397 °C. Long-term storage experiments show that compounds 5 and 6 are stable enough at high temperature. Moreover, the six compounds hold considerable detonation performances, in which Ca II based compound 5 possesses the detonation velocity of 9.12 km s -1 , along with the detonation pressure of 34.51 GPa, exceeding those of most energetic coordination polymers. Burn tests further certify that the six compounds can be versatile pyrotechnics. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  1. Self-assembly of coordination polymers of Pr(III), Nd(III), Tb(III), Dy(III) and Ho(III) with 5-hydroxyisophthalic acid and adipic acid: Syntheses, structures, porosity, luminescence and magnetic properties

    Science.gov (United States)

    Kariem, Mukaddus; Yawer, Mohd; Kumar, Manesh; Nawaz Sheikh, Haq; Sood, Puneet; Kolekar, Sanjay S.

    2017-11-01

    Five novel coordination polymers (CPs) with the formula [Ln (hip) (adip)0.5(H2O)2]n. nH2O [Ln = Pr (1), Nd (2), Tb (3), Dy (4) and Ho (5)] were synthesized by self-organization of lanthanide salts with rigid [5-hydroxyisophthalic acid (H2hip)] and flexible [adipic acid (H2adip)] linkers under solvothermal condition. X-ray diffraction revealed data that all five CPs 1-5 are isostructural and crystallizes in monoclinic C2/c space group. Coordination polymers 1-5 exhibit 1D linear ladder shaped extension with the linkage of lanthanide carboxylate chains having the backbone of H2hip and H2adip ligands. The 1D linear ladder chains get transformed into three dimensional (3D) supramolecular network via non-covalent interactions (π-π and H - bonding). The porosity study showed that 20.34 mL of N2 gets adsorbed per 1.0 g of sample at 1 atm pressure. The CP 3 (Tb) and 4 (Dy) emit strong ligand sensitized characteristic f-f luminescence emission. The CPs 3 and 4 exhibit weak ferromagnetic interactions at lower temperatures.

  2. Rethinking Sensitized Luminescence in Lanthanide Coordination Polymers and MOFs: Band Sensitization and Water Enhanced Eu Luminescence in [Ln(C15H9O5)3(H2O)3]n (Ln = Eu, Tb).

    Science.gov (United States)

    Einkauf, Jeffrey D; Kelley, Tanya T; Chan, Benny C; de Lill, Daniel T

    2016-08-15

    A coordination polymer [Ln(C15H9O9)3(H2O)3]n (1-Ln = Eu(III), Tb(III)) assembled from benzophenonedicarboxylate was synthesized and characterized. The organic component is shown to sensitize lanthanide-based emission in both compounds, with quantum yields of 36% (Eu) and 6% (Tb). Luminescence of lanthanide coordination polymers is currently described from a molecular approach. This methodology fails to explain the luminescence of this system. It was found that the band structure of the organic component rather than the molecular triplet state was able to explain the observed luminescence. Deuterated (Ln(C15H9O9)3(D2O)3) and dehydrated (Ln(C15H9O9)3) analogues were also studied. When bound H2O was replaced by D2O, lifetime and emission increased as expected. Upon dehydration, lifetimes increased again, but emission of 1-Eu unexpectedly decreased. This reduction is reasoned through an unprecedented enhancement effect of the compound's luminescence by the OH/OD oscillators in the organic-to-Eu(III) energy transfer process.

  3. A series of Zn/Cd coordination polymers constructed from 1,4-naphthalenedicarboxylate and N-donor ligands: Syntheses, structures and luminescence sensing of Cr{sup 3+} in aqueous solutions

    Energy Technology Data Exchange (ETDEWEB)

    Hu, Dong-Cheng [College of Chemistry and Chemical Engineering, Northwest Normal University, Lanzhou 730070 (China); Key Laboratory for Preparation and Application of Ordered Structural Materials of Guangdong Province, Shantou University, Shantou 515063 (China); Fan, Yan; Si, Chang-Dai; Wu, Ya-Jun; Dong, Xiu-Yan; Yang, Yun-Xia; Yao, Xiao-Qiang [College of Chemistry and Chemical Engineering, Northwest Normal University, Lanzhou 730070 (China); Liu, Jia-Cheng, E-mail: jcliu8@nwnu.edu.cn [College of Chemistry and Chemical Engineering, Northwest Normal University, Lanzhou 730070 (China)

    2016-09-15

    A novel series of Zn/Cd coordination polymers based on H{sub 3}L, namely, [Zn{sub 2}(HL){sub 2}(bipy){sub 2}(H{sub 2}O){sub 6}]{sub n} (1), [Zn(HL)(phen)]{sub n} (2), [Cd{sub 3}L{sub 2}(bbi){sub 3}]{sub n} (3), [Zn{sub 3}L{sub 2}(bbi){sub 3}]{sub n} (4) [(H{sub 3}L =4-[(1-carboxynaphthalen-2-yl)oxy]phthalic acid, bipy =4,4′-bipyridine, phen =1,10-phenanthroline, bbi =1,1′-(1,4-butanediyl)bis(imidazole] have been successfully synthesized by solvothermal reaction. Compound 1 possesses two diverse 1D chains constructed by different bipy coligands, which were further connected to form a 3D supramolecular architecture by hydrogen bonding interactions. Compound 2 possesses a complicated 1D chain based on secondary building unit (SBU) with binuclear Zn cluster. Compounds 3 and 4 exhibit similar 2D→3D framework, which can be rationalized as (3,4,4)-connected 3D net with a Schläfli symbol of (6{sup 3}.8.10{sup 2}){sub 2}(6{sup 3}){sub 2}(6{sup 4}.8.10). In particular, compound 3 exhibited a high sensitivity for Cr{sup 3+} in aqueous solutions, which suggest that compound 3 is a promising luminescent probe for selectively sensing Cr{sup 3+}. - Graphical abstract: A series of novel Zn/Cd coordination polymers have been successfully synthesized by solvothermal reaction. The unique 3D Cd{sup 2+} polymer containing bbi as second ligand demonstrates high sensitivity for detection of toxic Cr{sup 3+} in aqueous solutions. Display Omitted - Highlights: • π-conjugated semirigid tricarboxylate ligands with naphthalene rings(H{sub 3}L) were rationally designed. • Four Zn/Cd coordination polymers based on H{sub 3}L have been successfully synthesized by solvothermal reaction. • Compound 3 is a promising luminescent probe for selectively sensing Cr{sup 3+} with high sensitivity in aqueous solutions.

  4. Syntheses, structures, electrochemistry and catalytic oxidation degradation of organic dyes of two new coordination polymers derived from Cu(II) and Mn(II) and 1-(tetrazo-5-yl)-4-(triazo-1-yl)benzene

    Energy Technology Data Exchange (ETDEWEB)

    Song, Ming; Mu, Bao; Huang, Ru-Dan, E-mail: huangrd@bit.edu.cn

    2017-02-15

    Two new coordination polymers (CPs), namely, [Cu{sub 2}(ttbz)(H{sub 2}btc){sub 2}(OH)]{sub n} (1) and [Mn(ttbz){sub 2}(H{sub 2}O){sub 2}]{sub n} (2) (Httbz =1-(tetrazo-5-yl)-4-(triazo-1-yl)benzene, H{sub 3}btc =1,3,5-benzenetricarboxylic acid), have been hydrothermally synthesized and structurally characterized. Complex 1 exhibits a (3,5,5,5)-connected 2D layer with a Schläfli symbol of (3·4{sup 2})(3·4{sup 4}0.5{sup 2}0.6{sup 3})(3{sup 2}0.4{sup 4}0.5{sup 2}0.6{sup 2})(3{sup 2}0.4{sup 4}0.5{sup 3}0.6), in which the ttbz{sup -} ligand can be described as μ{sub 5}-bridge, linking Cu(II) ions into a 2D layer and H{sub 2}btc{sup -} ions play a supporting role in complex 1. The ttbz{sup -} ligand in complex 2 represents the bridging coordination mode, connecting two Mn(II) ions to form the infinite 1D zigzag chains, respectively, which are further connected by two different types of hydrogen bonds to form a 3D supramolecular. Furthermore, catalytic oxidation activities toward organic dyes and electrochemical behaviors of the title complexes have been investigated at room temperature in aqueous solutions, indicating these complexes may be applicable to color removal in a textile wastewater stream and practical applications in areas of electrocatalytic reduction toward nitrite, respectively. - Graphical abstract: Two new coordination polymers based on different structural characteristics have been hydrothermally synthesized by the mixed ligands. The catalytic oxidation activities toward organic dyes and electrochemical behaviors of the title complexes have been investigated. - Highlights: • The organic ligand containing the tetrazolyl group and triazolyl group with some advantages has been used. • Two new coordination polymers with different structural characteristics has been discussed in detail. • Catalytic oxidation activities toward organic dyes and electrochemical behaviors of the title complexes have been investigated.

  5. Nanofibers extraction from palm mesocarp fiber for biodegradable polymers incorporation; Extracao de nanofibras a partir do mesocarpo do dende para incorporacao em polimeros biodegradsveis

    Energy Technology Data Exchange (ETDEWEB)

    Kuana, Vanessa A.; Rodrigues, Vanessa B.; Takahashi, Marcio C., E-mail: ayu.kuana@gmail.com [Universidade Federal de Sao Carlos (UFSCar), Sao Carlos, SP (Brazil); Campos, Adriana de; Sena Neto, Alfredo R.; Mattoso, Luiz H.C.; Marconcini, Jose M. [Embrapa Instrumentacao (EMBRAPA/CNPDIA), Sao Carlos, SP (Brazil)

    2015-07-01

    The palm mesocarp fibers are residues produced by the palm oil industries. The objective of this paper is to determine an efficient treatment to extract crystal cellulose nanofibers from the palm mesocarp fibers to be incorporated in biodegradable polymeric composites. The fibers were saponified, bleached and analyzed with thermal gravimetric analysis, X-ray diffraction, Fourier transform infrared spectroscopy and scanning electron microscopy. (author)

  6. A set of alkali and alkaline-earth coordination polymers based on the ligand 2-(1H-benzotriazol-1-yl) acetic acid: Effects the radius of metal ions on structures and properties

    Energy Technology Data Exchange (ETDEWEB)

    Wang, Jin-Hua [Department of Chemical Engineering, Shandong Provincial Key Laboratory of Fine Chemicals, Qilu University of Technology, Jinan 250353 (China); Tang, Gui-Mei, E-mail: meiguit@163.com [Department of Chemical Engineering, Shandong Provincial Key Laboratory of Fine Chemicals, Qilu University of Technology, Jinan 250353 (China); Qin, Ting-Xiao; Yan, Shi-Chen [Department of Chemical Engineering, Shandong Provincial Key Laboratory of Fine Chemicals, Qilu University of Technology, Jinan 250353 (China); Wang, Yong-Tao, E-mail: ceswyt@sohu.com [Department of Chemical Engineering, Shandong Provincial Key Laboratory of Fine Chemicals, Qilu University of Technology, Jinan 250353 (China); Cui, Yue-Zhi [Department of Chemical Engineering, Shandong Provincial Key Laboratory of Fine Chemicals, Qilu University of Technology, Jinan 250353 (China); Weng Ng, Seik [Department of Chemistry, University of Malaya, Kuala Lumpur 50603 (Malaysia)

    2014-11-15

    Four new metal coordination complexes, namely, [Na(BTA)]{sub n} (1), [K{sub 2}(BTA){sub 2}(μ{sub 2}-H{sub 2}O)]{sub n} (2), and [M(BTA){sub 2}(H{sub 2}O){sub 2}]{sub n} (M=Ca(II) and Sr(II) for 3 and 4, respectively) [BTA=2-(1H-benzotriazol-1-yl) acetic anion], have been obtained under hydrothermal condition, by reacting the different alkali and alkaline-earth metal hydroxides with HBTA. Complexes 1–4 were structurally characterized by X-ray single-crystal diffraction, EA, IR, PXRD, and thermogravimetry analysis (TGA). These complexes display low-dimensional features displaying various two-dimensional (2D) and one-dimensional (1D) coordination motifs. Complex 1 displays a 2D layer with the thickness of 1.5 nm and possesses a topologic structure of a 11 nodal net with Schläfli symbol of (3{sup 18}). Complex 2 also shows a thick 2D sheet and its topologic structure is a 9 nodes with Schläfli symbol of (3{sup 11}×4{sup 2}). Complexes 3 and 4 possess a 1D linear chain and further stack via hydrogen bonding interactions to generate a three-dimensional supramolecular architecture. These results suggest that both the coordination preferences of the metal ions and the versatile nature of this flexible ligand play a critical role in the final structures. The luminescent spectra show strong emission intensities in complexes 1–4, which display violet photoluminescence. Additionally, ferroelectric, dielectric and nonlinear optic (NLO) second-harmonic generation (SHG) properties of 2 are discussed in detail. - Graphical abstract: A set of alkali and alkaline-earth metal coordination polymers were hydrothermally synthesized by 2-(1H-benzotriazol-1-yl)acetic acid, displaying interesting topologic motifs from two-dimension to one-dimension and specific physical properties. - Highlights: • Alkali and alkaline-earth metal coordination polymers have been obtained. • The ligand 2-(1H-benzotriazol-1-yl)acetic acid has been adopted. • The two-dimensional and one

  7. Assembly of ZnII and CdII coordination polymers with different dimensionalities based on the semi-flexible 3-(1H-benzimidazol-2-ylpropanoic acid ligand

    Directory of Open Access Journals (Sweden)

    Xiao-Yan Li

    2018-01-01

    Full Text Available Two new coordination polymers, namely, poly[[μ3-3-(1H-benzimidazol-2-ylpropionato]zinc(II], [Zn(C10H8N2O2]n, (1, and poly[bis[μ2-3-(1H-benzimidazol-2-ylpropionato]cadmium(II], [Cd(C10H8N2O22]n, (2 have been synthesized from 3-(1H-benzoimidazol-2-ylpropanoic acid ligands through a mixed-ligand synthetic strategy under a solvothermal environment, and studied by single-crystal X-ray diffraction. Complex 1 crystallizes in the orthorhombic space group Pbca and features a two-dimensional structure formed by a binuclear Zn2O4 core. Complex 2, however, crystallizes in the monoclinic space group P21/c and forms a one-dimensional chain structure. The ZnII and CdII ions have different coordination numbers and the 3-(1H-benzoimidazol-2-ylpropanoate ligands display different coordination modes. The structures reported here show the importance of the selection of metal ions and suitable ligands.

  8. A one-dimensional ladder-like coordination polymer: poly[[hexaaquabis(μ-5-nitrobenzene-1,3-dicarboxylato-κ3O,O′,O′′(μ-oxalato-κ4O,O′:O′′,O′′′diyttrium(III] trihydrate

    Directory of Open Access Journals (Sweden)

    Zhong Fu

    2008-01-01

    Full Text Available In the crystal structure of the title one-dimensional coordination polymer, [Y2(C8H3NO62(C2O4(H2O6]·3H2O, each YIII ion is bridged to its neighbours by two 5-nitrobenzene-1,3-dicarboxylate (nbdc dianions and one oxalate dianion (located on an inversion centre to form a ladder-like polymeric structure. The two carboxylate groups of nbdc assume different modes of coordination, one is chelating whereas the other is monodentate. Three water molecules coordinate to the YIII ion to complete an eight-coordinate distorted dodecahedral geometry. The ladder-like polymers are assembled together by hydrogen bonding and π–π stacking [centrio–centriod distance = 3.819 (9 Å] in the crystal structure.

  9. Solid Polymer Nanocomposite Battery Electrolyte

    Data.gov (United States)

    National Aeronautics and Space Administration — Incorporate nano-graphene and nano-metal oxides in polymer electrolyte to enhance ionic conductivity; incorporate ionic liquid to improve ion transport properties in...

  10. High-performance hybrid (electrostatic double-layer and faradaic capacitor-based) polymer actuators incorporating nickel oxide and vapor-grown carbon nanofibers.

    Science.gov (United States)

    Terasawa, Naohiro; Asaka, Kinji

    2014-12-02

    The electrochemical and electromechanical properties of polymeric actuators prepared using nickel peroxide hydrate (NiO2·xH2O) or nickel peroxide anhydride (NiO2)/vapor-grown carbon nanofibers (VGCF)/ionic liquid (IL) electrodes were compared with actuators prepared using solely VGCFs or single-walled carbon nanotubes (SWCNTs) and an IL. The electrode in these actuator systems is equivalent to an electrochemical capacitor (EC) exhibiting both electrostatic double-layer capacitor (EDLC)- and faradaic capacitor (F