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Sample records for coordination polymers based

  1. Nanometrization of Lanthanide-Based Coordination Polymers.

    Science.gov (United States)

    Neaime, Chrystelle; Daiguebonne, Carole; Calvez, Guillaume; Freslon, Stéphane; Bernot, Kevin; Grasset, Fabien; Cordier, Stéphane; Guillou, Olivier

    2015-11-23

    Heteronuclear lanthanide-based coordination polymers are microcrystalline powders, the luminescence properties of which can be precisely tuned by judicious choice of the rare-earth ions. In this study, we demonstrate that such materials can also be obtained as stable solutions of nanoparticles in non-toxic polyols. Bulk powders of the formula [Ln2-2x Ln'2x (bdc)3 ⋅4 H2 O]∞ (where H2 bdc denotes 1,4-benzene-dicarboxylic acid, 0≤x≤1, and Ln and Ln' denote lanthanide ions of the series La to Tm plus Y) afford nanoparticles that have been characterized by dynamic light-scattering (DLS) and transmission electron microscopy (TEM) measurements. Their luminescence properties are similar to those of the bulk materials. Stabilities versus time and versus dilution with another solvent have been studied. This study has revealed that it is possible to tune the size of the nanoparticles. This process offers a reliable means of synthesizing suspensions of nanoparticles with tunable luminescence properties and tunable size distributions in a green solvent (glycerol). The process is also extendable to other coordination polymers and other solvents (ethylene glycol, for example). It constitutes a new route for the facile solubilization of lanthanide-based coordination polymers.

  2. Thermal expansion of d10 dicyanometallate-based coordination polymers

    OpenAIRE

    Korcok, Jasmine Lynn

    2010-01-01

    The thermal expansion of several new d10, dicyanometallate-based coordination polymers was examined by powder and single-crystal X-ray diffraction. In isostructural KNi[Au(CN)2]3, KCd[M(CN)2]3, and In[M(CN)2]3 (M=Ag(I), Au(I)), extremely large positive and negative thermal expansion (PTE/NTE) coefficients were discovered. Weaker metallophilic interactions promote larger PTE and NTE. Similarly, the M[Au(CN)2]2 series (M=Mn, Fe, Co, Zn, Hg) showed sizeable PTE and NTE effects. HgCN(NO3) exhibit...

  3. The assembly of supramolecular boxes and coordination polymers based on bis-zinc-salphen building blocks

    NARCIS (Netherlands)

    Kuil, M.; Puijk, I.M.; Kleij, A.W.; Tooke, D.M.; Spek, A.L.; Reek, J.N.H.

    2009-01-01

    We report the assembly of supramolecular boxes and coordination polymers based on a rigid bis-zinc(II)-salphen complex and various ditopic nitrogen ligands. The use of the bis-zinc(II)-salphen building block in combination with small ditopic nitrogen ligands gave organic coordination polymers both

  4. Complex coacervate core micelles from iron-based coordination polymers.

    Science.gov (United States)

    Wang, Junyou; de Keizer, Arie; Fokkink, Remco; Yan, Yun; Cohen Stuart, Martien A; van der Gucht, Jasper

    2010-07-01

    Complex coacervate core micelles (C3Ms) from cationic poly(N-methyl-2-vinyl-pyridinium iodide)-b-poly(ethylene oxide) (P2MVP(41)-b-PEO(205)) and anionic iron coordination polymers are investigated in the present work. Micelle formation is studied by light scattering for both Fe(II)- and Fe(III)-containing C3Ms. At the stoichiometric charge ratio, both Fe(II)-C3Ms and Fe(III)-C3Ms are stable for at least 1 week at room temperature. Excess of iron coordination polymers has almost no effect on the formed Fe(II)-C3Ms and Fe(III)-C3Ms, whereas excess of P2MVP(41)-b-PEO(205) copolymers in the solution can dissociate the formed micelles. Upon increasing salt concentration, the scattering intensity decreases. This decrease is due to both a decrease in the number of micelles (or an increase in CMC) and a decrease in aggregation number. The salt dependence of the CMC and the aggregation number is explained using a scaling argument for C3M formation. Compared with Fe(II)-C3Ms, Fe(III)-C3Ms have a lower CMC and a higher stability against dissociation by added salt.

  5. Coordination polymer based on (1,2-bis(2-picolinamido) phenyl)copper

    Institute of Scientific and Technical Information of China (English)

    YE Kaiqi; WU Ying; ZHANG Hongyu; YE Ling; YU Jingsheng; YANG Guangdi; WANG Yue

    2005-01-01

    (1,2-bis(2-pyridinecarboxamido)benzene copper Cu(bpb) was synthesized and employed as a building block to construct supramolecular coordination polymer based on intermolecular coordination and hydrogen bonding interactions. X-ray single-crystal diffraction characterization revealed that intermolecular coordination interactions lead to the formation of one-dimensional infinite molecular columns, which array along the same direction in the crystal resulting in the three-dimensional network. The molecular columns are linked together by hydrogen-bonding interactions, which infinitely extend in bc plane. The one-dimensional coordination bonding and two-dimensional hydrogen-bonding interactions result in the formation of supramolecular coordination polymer.

  6. Observation of a large magnetocaloric effect in a 2D Gd(III)-based coordination polymer.

    Science.gov (United States)

    Biswas, Soumava; Adhikary, Amit; Goswami, Soumyabrata; Konar, Sanjit

    2013-10-07

    A new 2D Gd(III)-based coordination polymer has close to the highest cryogenic magnetocaloric effect of any MOF reported so far. The experimental results reveal its structural features and magnetic properties.

  7. Nanoscale coordination polymers for platinum-based anticancer drug delivery.

    Science.gov (United States)

    Rieter, William J; Pott, Kimberly M; Taylor, Kathryn M L; Lin, Wenbin

    2008-09-01

    Pt-containing nanoscale coordination polymer (NCP) particles with the formula of Tb2(DSCP)3(H2O)12 (where DSCP represents disuccinatocisplatin), NCP-1, were precipitated from an aqueous solution of Tb3+ ions and DSCP bridging ligands via the addition of a poor solvent. SEM and TEM images showed that as-synthesized NCP-1 exhibited a spherical morphology with a DLS diameter of 58.3 +/- 11.3 nm. NCP-1 particles were stabilized against rapid dissolution in water by encapsulation in shells of amorphous silica. The resulting silica-coated particles NCP-1' exhibited significantly longer half-lives for DSCP release from the particles (a t1/2 of 9 h for NCP-1' with 7 nm silica coating vs t1/2 of 1 h for as-synthesized NCP-1). In vitro cancer cell cytotoxicity assays with the human colon carcinoma cell line (HT-29) showed that internalized NCP-1' particles readily released the DSCP moieties which were presumably reduced to cytotoxic Pt(II) species to give the Pt-containing NCPs anticancer efficacy superior to the cisplatin standard. The generality of this degradable nanoparticle formulation should allow for the design of NCPs as effective delivery vehicles for a variety of biologically and medically important cargoes such as therapeutic and imaging agents.

  8. Determination of tetracycline in milk by using nucleotide/lanthanide coordination polymer-based ternary complex.

    Science.gov (United States)

    Tan, Hongliang; Ma, Chanjiao; Song, Yonghai; Xu, Fugang; Chen, Shouhui; Wang, Li

    2013-12-15

    The meta-organic coordination polymers have been emerged as fascinating nanomaterials because of their tunable nature. In this work, we employed lanthanide coordination polymer self-assembled from adenosine monophosphate (AMP) and europium ion (Eu(3+)) as receptor reagent and citrate (Cit) as ancillary ligand to construct a fluorescent sensor for the detection of tetracycline (Tc) in milk. The co-coordination of Cit and Tc with Eu(3+) on the surface of the coordination polymer AMP/Eu leads to the formation of ternary complex which emitted strong fluorescence due to the removal of coordinated water molecules and an intramolecular energy transfer from Tc to Eu(3+). The fluorescent intensity of Eu(3+) displayed a good linear response to Tc concentrations in the range of 0.1-20 μM with a detection limit of 60 nM. This method was successfully applied to determine the levels of Tc in milk, which is the first application of coordination polymer as a fluorescent sensor in real sample. Compared with other Eu(3+)-based fluorescent methods for Tc detection, the presented method allows simple, direct analysis of Tc without requiring special reaction media or complicated prepreparation processes. This straightforward strategy could be extended to the preparation of other lanthanide coordination polymer-based fluorescent probes for applications in biosensing, imaging, drug delivery, and so on. Copyright © 2013 Elsevier B.V. All rights reserved.

  9. The assembly of supramolecular boxes and coordination polymers based on bis-zinc-salphen building blocks.

    Science.gov (United States)

    Kuil, Mark; Puijk, Iris M; Kleij, Arjan W; Tooke, Duncan M; Spek, Anthony L; Reek, Joost N H

    2009-01-05

    We report the assembly of supramolecular boxes and coordination polymers based on a rigid bis-zinc(II)-salphen complex and various ditopic nitrogen ligands. The use of the bis-zinc(II)-salphen building block in combination with small ditopic nitrogen ligands gave organic coordination polymers both in solution as well as in the solid state. Molecular modeling shows that supramolecular boxes with small internal cavities can be formed. However, the inability to accommodate solvent molecules (such as toluene) in these cavities explains why coordination polymers are prevailing over well-defined boxes, as it would lead to an energetically unfavorable vacuum. In contrast, for relatively longer ditopic nitrogen ligands, we observed the selective formation of supramolecular box assemblies in all cases studied. The approach can be easily extended to chiral analogues by using chiral ditopic nitrogen ligands.

  10. Two Zn coordination polymers with meso-helical chains based on mononuclear or dinuclear cluster units

    Energy Technology Data Exchange (ETDEWEB)

    Qin, Ling, E-mail: qinling@hfut.edu.cn [Department of Chemical Engineering and Food Processing, Xuancheng Campus, Hefei University of Technology, Xuancheng 242000, Anhui (China); Jiangsu Engineering Technology Research Center of Environmental Cleaning Materials (CEM), School of Environmental Sciences and Engineering, Nanjing University of Information Science and Technology (China); State Key Laboratory of Coordination Chemistry, School of Chemistry and Chemical Engineering, Nanjing National Laboratory of Microstructures, Nanjing University, Nanjing 210093 (China); Qiao, Wen-Cheng; Zuo, Wei-Juan; Zeng, Si-Ying; Mei, Cao; Liu, Chang-Jiang [Department of Chemical Engineering and Food Processing, Xuancheng Campus, Hefei University of Technology, Xuancheng 242000, Anhui (China)

    2016-07-15

    Two zinc coordination polymers {[Zn_2(TPPBDA)(oba)_2]·DMF·1.5H_2O}{sub n} (1), {[Zn(TPPBDA)_1_/_2(tpdc)]·DMF}{sub n} (2) have been synthesized by zinc metal salt, nanosized tetradentate pyridine ligand with flexible or rigid V-shaped carboxylate co-ligands. These complexes were characterized by elemental analyses and X-ray single-crystal diffraction analyses. Compound 1 is a 2-fold interpenetrated 3D framework with [Zn{sub 2}(CO{sub 2}){sub 4}] clusters. Compound 2 can be defined as a five folded interpenetrating bbf topology with mononuclear Zn{sup 2+}. These mononuclear or dinuclear cluster units are linked by mix-ligands, resulting in various degrees of interpenetration. In addition, the photoluminescent properties for TPPBDA ligand under different state and coordination polymers have been investigated in detail. - Graphical abstract: Two zinc coordination polymers have been synthesized by zinc metal salt, nanosized tetradentate pyridine ligand with flexible or rigid V-shaped carboxylate co-ligands. Compound 1 is a 2-fold interpenetrated 3D framework with [Zn{sub 2}(CO{sub 2}){sub 4}] clusters. Compound 2 can be defined as a five folded interpenetrating bbf topology with mononuclear Zn{sup 2+}. In addition, the photoluminescent properties for TPPBDA ligand under different status and coordination polymers have been investigated in detail. Display Omitted - Highlights: • Two Zn coordination polymers based on mononuclear or dinuclear cluster units have been synthesized. • Compound 1 is a 2-fold interpenetrated 3D framework with [Zn{sub 2}(CO{sub 2}){sub 4}] clusters. • Compound 2 is a five folded interpenetrating bbf topology with mononuclear Zn{sup 2+}. • The photoluminescent properties for TPPBDA with different state and two coordination polymers have been investigated.

  11. Artificial tongue based on metal-biomolecule coordination polymer nanoparticles.

    Science.gov (United States)

    Pu, Fang; Ran, Xiang; Ren, Jinsong; Qu, Xiaogang

    2016-02-25

    We construct an array-based recognition system (the so-called artificial tongue) through the self-assembly of nucleotides, dyes and lanthanide ions. Metal ions are selected as model analytes for verifying its discrimination ability. The work provides valuable insights into the application and development of biomolecule-based materials.

  12. A Perylene-Based Microporous Coordination Polymer Interacts Selectively with Electron-Poor Aromatics.

    Science.gov (United States)

    Tran, Ly D; Ma, Jialiu; Wong-Foy, Antek G; Matzger, Adam J

    2016-04-11

    The design, synthesis, and properties of the new microporous coordination polymer UMCM-310 are described. The unique electronic character of the perylene-based linker enables selective interaction with electron-poor aromatics leading to efficient separation of nitroaromatics. UMCM-310 possesses high surface area and large pore size and thus permits the separation of large organic molecules based on adsorption rather than size exclusion.

  13. 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.

  14. A Heterobimetallic Anionic 3,6-Connected 2D Coordination Polymer Based on Nitranilate as Ligand

    Directory of Open Access Journals (Sweden)

    Samia Benmansour

    2016-03-01

    Full Text Available In order to synthesize new coordination polymers with original architectures and interesting magnetic properties, we used the nitranilate ligand (C6O4(NO222− = C6N2O82−, derived from the dianionic ligand dhbq2− (2,5-dihydroxy-1,4-benzoquinone = H2C6O42−. The use of this bis-bidentate bridging ligand led to [(DAMS2{FeNa(C6N2O83}·CH3CN]n (1 (DAMS+ = C16H17N2+ = 4-[4-(dimethylamino-α-styryl]-1-methylpyridinium, a 2D heterometallic coordination polymer presenting an unprecedented structure for any anilato-based compound. This structural type is a 3,6-connected 2D coordination polymer derived from the well-known honeycomb hexagonal structure, where Fe(III ions alternate with Na+ dimers (as Na2O12 units in the vertices of the hexagons and with an additional [Fe(C6N2O83]3− anion located in the center of the hexagons connecting the three Na+ dimers. The magnetic properties of compound 1 show the presence of paramagnetic isolated high spin Fe(III complexes with a zero field splitting, |D| = 8.5 cm−1.

  15. Ligand effects on the structural dimensionality and antibacterial activities of silver-based coordination polymers.

    Science.gov (United States)

    Lu, Xinyi; Ye, Junwei; Sun, Yuan; Bogale, Raji Feyisa; Zhao, Limei; Tian, Peng; Ning, Guiling

    2014-07-14

    Four Ag-based coordination polymers [Ag(Bim)] (1), [Ag2(NIPH)(HBim)] (2), [Ag6(4-NPTA)(Bim)4] (3) and [Ag2(3-NPTA)(bipy)0.5(H2O)] (4) (HBim = 1H-benzimidazole, bipy = 4,4'-bipyridyl, H2NIPH = 5-nitroisophthalic acid, H2NPTA = 3-/4-nitrophthalic acid) have been synthesized by hydrothermal reaction of Ag(i) salts with N-/O-donor ligands. Single-crystal X-ray diffraction indicated that these coordination polymers constructed from mononuclear or polynuclear silver building blocks exhibit three typical structure features from 1-D to 3-D frameworks. These compounds favour a slow release of Ag(+) ions leading to excellent and long-term antimicrobial activities, which is distinguished by their different topological structures, towards both Gram-negative bacteria, Escherichia coli (E. coli) and Gram-positive bacteria, Staphylococcus aureus (S. aureus). In addition, these compounds show good thermal stability and light stability under UV-vis and visible light, which are important characteristics for their further application in antibacterial agents.

  16. 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.

  17. 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.

  18. 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.

  19. 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.

  20. 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.

  1. Tricarboxylate-based Gd(III) coordination polymers exhibiting large magnetocaloric effects.

    Science.gov (United States)

    Liu, Sui-Jun; Cao, Chen; Xie, Chen-Chao; Zheng, Teng-Fei; Tong, Xiao-Lan; Liao, Jin-Sheng; Chen, Jing-Lin; Wen, He-Rui; Chang, Ze; Bu, Xian-He

    2016-05-31

    Two Gd(III) coordination polymers with the formula [Gd(cit)(H2O)]∞ () and [Gd(nta)(H2O)2]∞ () (H4cit = citric acid, H3nta = nitrilotriacetic acid) have been successfully prepared under hydrothermal conditions. Complex exhibits a three-dimensional (3D) structure based on carboxylate-bridged layers, while complex is a double-layer structure containing eight-coordinated Gd(III). Magnetic investigations reveal that weak antiferromagnetic couplings between adjacent Gd(III) ions in both and with different Weiss values result in large cryogenic magnetocaloric effects. It is notable that the maximum entropy changes (-ΔS) of and reach 31.3 J kg(-1) K(-1) and 32.2 J kg(-1) K(-1) at 2 K for a moderate field change (ΔH = 3 T), and a remarkable -ΔS (41.5 J kg(-1) K(-1) for and 42.0 J kg(-1) K(-1) for ) could be obtained for ΔH = 7 T.

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

    NARCIS (Netherlands)

    Yang, J.; Lutz, M.; Grzech, A.; Mulder, F.M.; Dingemans, T.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

  3. Five 8-hydroxyquinolinate-based coordination polymers with tunable structures and photoluminescent properties for sensing nitroaromatics.

    Science.gov (United States)

    Zhang, Liyan; Sun, Liying; Li, Xinyuan; Tian, Yulan; Yuan, Guozan

    2015-01-01

    Using two 8-hydroxyquinolinate ligands (L1-MOM and L2-MOM) containing 3-pyridyl or 4-pyridyl groups, five novel coordination polymers, namely, [Zn3(L1)6] (1), [Zn(L1)2]·2MeOH (2), [Zn(L2)2] (3), [Cd(L2)2] (4), and [Cd4(L1)6]·13H2O (5), were synthesized and characterized by a variety of techniques. Single-crystal X-ray structures have revealed that these coordination polymers exhibit a structural diversification due to the different choices of metal salts and the effect of pyridyl nitrogen position. Compounds 1-5 exhibited different fluorescence emissions and lifetimes upon excitation in the solid state. The sensing behavior of these polymers was also investigated upon exposure to vapors of various nitroaromatic molecules (analytes). The results show that all five polymers are capable of sensing these nitroaromatic molecules in the vapor phase through fluorescence quenching. Interestingly, 3 exhibits superior sensitivity to the analytes in comparison with other polymers. 2-Nitrotoluene quenches the emission of 3 by as much as 96%.

  4. Two Zn coordination polymers with meso-helical chains based on mononuclear or dinuclear cluster units

    Science.gov (United States)

    Qin, Ling; Qiao, Wen-Cheng; Zuo, Wei-Juan; Zeng, Si-Ying; Mei, Cao; Liu, Chang-Jiang

    2016-07-01

    Two zinc coordination polymers {[Zn2(TPPBDA)(oba)2]·DMF·1.5H2O}n (1), {[Zn(TPPBDA)1/2(tpdc)]·DMF}n (2) have been synthesized by zinc metal salt, nanosized tetradentate pyridine ligand with flexible or rigid V-shaped carboxylate co-ligands. These complexes were characterized by elemental analyses and X-ray single-crystal diffraction analyses. Compound 1 is a 2-fold interpenetrated 3D framework with [Zn2(CO2)4] clusters. Compound 2 can be defined as a five folded interpenetrating bbf topology with mononuclear Zn2+. These mononuclear or dinuclear cluster units are linked by mix-ligands, resulting in various degrees of interpenetration. In addition, the photoluminescent properties for TPPBDA ligand under different state and coordination polymers have been investigated in detail.

  5. Two novel metal–organic coordination polymers based on diphosphonate and oxalate: Synthesis, structures and properties

    Energy Technology Data Exchange (ETDEWEB)

    Niu, Qing-Jun; Zheng, Yue-Qing, E-mail: yqzhengmc@163.com; Zhou, Lin-Xia; Zhu, Hong-Lin

    2015-07-15

    Two 2-(1-imidazole)-1-hydroxyl-1,1'-ethylidenediphosphonato and oxalic acid bridged coordination polymers (H{sub 2}en)[Co{sub 3}(H{sub 2}zdn){sub 2}(ox)(H{sub 2}O){sub 2}] (1) and Cd{sub 2}(H{sub 2}zdn)(ox){sub 0.5}(H{sub 2}O) (2) (2-(1-imidazole)-1-hydroxyl-1,1'-ethylidenediphosphonic acid=H{sub 5}zdn; oxalic acid=H{sub 2}ox) were synthesized under hydrothermal conditions and characterized by the infrared (IR), thermogravimetric analyses (TGA), elemental analyses (EA) and X-ray diffraction (XRD). Compound 1 is bridged by phosphonate anions to 1D chain, and further linked by oxalate anions to 2D layer. Compound 2 is bridged by O–P–O units of H{sub 5}zdn to the layer, and then pillared by oxalate anions to generate 3D frameworks. Compound 1 shows anti-ferromagnetic behaviors analyzed with the temperature-dependent zero-field ac magnetic susceptibilities, while compound 2 exhibits an influence on the luminescent property. - Graphical abstract: Linked by oxalate, two zoledronate-based metal–organic frameworks are synthesized, which exhibits the different frameworks. Magnetism and luminescent properties have been studied. The weak antiferromagnetic coupling is conducted in 1. - Highlights: • Compound 1 and 2 are first linked by oxalate anion based on zoledronic acid. • Compound 1 generates a classic “dia Diamond” (6{sup 6}) topology. • Compound 2 exhibits a (4{sup 4}·6{sup 2})(4{sup 4}·6{sup 6}) topology. • Magnetism and luminescent properties of 1 and 2 have been studied, respectively.

  6. 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.

  7. Porphyrin coordination polymer nanospheres and nanorods

    Science.gov (United States)

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

    2013-09-10

    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.

  8. Assembly of three coordination polymers based on a sulfonic-carboxylic ligand showing high proton conductivity.

    Science.gov (United States)

    Zhao, Shu-Na; Song, Xue-Zhi; Zhu, Min; Meng, Xing; Wu, Lan-Lan; Song, Shu-Yan; Wang, Cheng; Zhang, Hong-Jie

    2015-01-21

    Three new coordination polymers (CPs)/metal-organic frameworks (MOFs) with different structures have been synthesized using 4,8-disulfonyl-2,6-naphthalenedicarboxylic acid (H4L) and metal ions, Cu(2+), Ca(2+) and Cd(2+). The Cu compound features a one-dimensional chain structure, further extending into a 2D layer network through H-bond interactions. Both the Ca and Cd compounds show 3D frameworks with (4,4)-connected PtS-type topology and (3,6)-connected bct-type topology, respectively. These CPs/MOFs all exhibit proton conduction behavior, especially for the Cu compound with a proton conductivity of 3.46 × 10(-3) S cm(-1) at 368 K and 95% relative humidity (RH). Additionally, the activation energy (Ea) has also been investigated to deeply understand the proton-conduction mechanism.

  9. 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.

  10. Hg(II Coordination Polymers Based on N,N’-bis(pyridine-4-ylformamidine

    Directory of Open Access Journals (Sweden)

    Wayne Hsu

    2016-04-01

    Full Text Available Reactions of N,N’-bis(pyridine-4-ylformamidine (4-Hpyf with HgX2 (X = Cl, Br, and I afforded the formamidinate complex {[Hg(4-pyf2]·(THF}n, 1, and the formamidine complexes {[HgX2(4-Hpyf]·(MeCN}n (X = Br, 2; I, 3, which have been structurally characterized by X-ray crystallography. Complex 1 is a 2D layer with the {44·62}-sql topology and complexes 2 and 3 are helical chains. While the helical chains of 2 are linked through N–H···Br hydrogen bonds, those of 3 are linked through self-complementary double N–H···N hydrogen bonds, resulting in 2D supramolecular structures. The 4-pyf- ligands of 1 coordinate to the Hg(II ions through one pyridyl and one adjacent amine nitrogen atoms and the 4-Hpyf ligands of 2 and 3 coordinate to the Hg(II ions through two pyridyl nitrogen atoms, resulting in new bidentate binding modes. Complexes 1–3 provide a unique opportunity to envisage the effect of the halide anions of the starting Hg(II salts on folding and unfolding the Hg(II coordination polymers. Density function theory (DFT calculation indicates that the emission of 1 is due to intraligand π→π * charge transfer between two different 4-pyf- ligands, whereas those of 2 and 3 can be ascribed to the charge transfer from non-bonding p-type orbitals of the halide anions to π * orbitals of the 4-pyf- ligands (n→π *. The gas sorption properties of the desolvated product of 1 are compared with the Cu analogues to show that the nature of the counteranion and the solvent-accessible volume are important in determining their adsorption capability.

  11. Self-Assembly of Cluster-Based Nanoscopic Supramolecules into One-Dimensional Coordination Polymers

    Directory of Open Access Journals (Sweden)

    Jian-Jun Zhang

    2009-01-01

    (2, and [(4,4′-bpe(Mn(Salen(H2O2]{(4,4′-bpe2[(Mn(Salen(MeOH2(Mn(Salen2(Nb6Cl12(CN6][(Mn(Salen2(Nb6Cl12(CN6]}·16H2O (3. Single crystal X-ray diffraction analyses show that the frameworks of the three coordination polymers are built of heterotrimeric and/or heteropentameric supramolecular species linked by ditopic organic ligands. The framework of 1 consists of anionic chains built of heterotrimeric dianions [(Mn(Salen2(Nb6Cl12(CN6]2− (T linked by 4,4′-dpyo. The chains run along two directions ([0 2 −2] and [0 3 3] leading to the formation of channels along the crystallographic (a direction where the cations [Mn(Salen(S2]+ and solvent molecules are located. Also, 2 was reported earlier, it possesses a neutral 1D chain built of neutral heterpentameric supramolecules: [(Mn(7‐MeSalen2(Mn(7‐MeSalen(S2(Nb6Cl12(CN6] (P linked by 4,4′-bpe ligands. Hydrogen bonds between non-bridging cyanide ligands and coordinated solvent molecules connect the chains into 2D hydrogen-bonded frameworks. Finally, 3 features an anionic chain, built of alternating heterotrimers [(Mn(Salen2(Nb6Cl12(CN6]2− and heteropentamers [(Mn(Salen(S2(Mn(Salen2(Nb6Cl12(CN6] linked by the organic spacer 4,4′-bpe. The anionic charge is compensated by the in situe-assembled [Mn(Salen(S(4,4′‐bpeMn(Salen(S]2+ dimers. Magnetic measurements reveal that the Mn(III ions are well isolated and only weak magnetic interactions are observed. The thermal stability of the three compounds was investigated.

  12. Two Gd(III) coordination polymers based on a flexible tricarboxylate: Syntheses, structures, luminescence and catalytic properties

    Science.gov (United States)

    Zhu, Yu; Zhu, Min; Liu, Pan; Xia, Li; Wu, Yunlong; Xie, Jimin

    2017-02-01

    Two Gadolinium coordination polymers {[Gd·(TTTA)·(H2O)2]·2H2O}n (1) and [Gd·(TTTA)·DMF]n (2) have been synthesized based on Gd(NO3)3·6H2O and the flexible tripodal ligand 2,2‧,2″-[1,3,5-triazine-2,4,6-triyltris(thio)]tris-acetic acid (H3TTTA) under hydrothermal conditions. In the structure of 1, the tridentate TTTA3- ligands connect the dimeric metal centers into an infinite one dimensional chain. While 2 shows a two dimensional network with tridentate TTTA3- ligands. The two complexes all quench the emission spectra after coordinated to the Gd3+ ions. The catalytic results indicate that two complexes show excellent activities for the cyanosilylation of benzaldehyde and its derivatives. Besides, 2 is better than 1 in the catalytic reactions due to more possibility of metal open sites.

  13. Syntheses, structures, and properties of multidimensional lithium coordination polymers based on aliphatic carboxylic acids.

    Science.gov (United States)

    Cheng, Pei-Chi; Lin, Wei-Cheng; Tseng, Feng-Shuen; Kao, Ching-Che; Chang, Ting-Guang; Senthil Raja, Duraisamy; Liu, Wei-Ren; Lin, Chia-Her

    2013-02-28

    Three lithium coordination polymers, [Li4(H2O)2(EDTA)] (1), [Li4(H2O)4(BTCA)] (2), and (H2NMe2)2[Li2(H2O)2(BTCA)] (3) (H4EDTA = ethylenediaminetetraacetic acid, H4BTCA = 1,2,3,4-butane tetracarboxylic acid, H2NMe2 = dimethyl amine), have been synthesized by reacting lithium salts with aliphatic carboxylic acids using a solvothermal method. The structures of all the three complexes have been determined by single crystal X-ray diffraction studies. The single crystal structure analysis revealed that complex 1 has a three-dimensional framework, whereas complex 2 has 2D sheets and complex 3 has 1D chains. In addition, these lithium complexes contain various inorganic motifs with a tetramer in 1 and 2, and discrete tetrahedra in 3 and have further been connected through organic ligands to construct multidimensional structures. Further, the electrochemical properties of complexes 1–3 have been studied to evaluate these compounds as electrode materials for lithium ion batteries with discharge capacities of around 100 mA h g(-1) in the first thirty cycles.

  14. Understanding the Structure of Reversible Coordination Polymers Based on Europium in Electrostatic Assemblies Using Time-Resolved Luminescence.

    Science.gov (United States)

    Xu, Limin; Xie, Mengqi; Huang, Jianbin; Yan, Yun

    2016-06-14

    In situ characterization of the structure of reversible coordination polymers remains a challenge because of their dynamic and concentration-responsive nature. It is especially difficult to determine these structures in their self-assemblies where their degree of polymerization responds to the local concentration. In this paper, we report on the structure of reversible lanthanide coordination polymers in electrostatic assemblies using time-resolved luminescence (TRL) measurement. The reversible coordinating system is composed of the bifunctional ligand 1,11-bis(2,6-dicarboxypyridin-4-yloxy)-3,6,9-trioxaundecane (L2EO4) and europium ion Eu(3+). Upon mixing with the positively charged diblock copolymer poly(2-vinylpyridine)-b-poly(ethylene oxide) (P2VP41-b-PEO205), electrostatic polyion micelles are formed and the negatively charged L2EO4-Eu coordination complex simultaneously transforms into coordination "polymers" in the micellar core. By virtue of the water-sensitive luminescence of Eu(3+), we are able to obtain the structural information of the L2EO4-Eu coordination polymers before and after the formation of polyion micelles. Upon analyzing the fluorescence decay curves of Eu(3+) before and after micellization, the fraction of Eu(3+) fully coordinated with L2EO4 is found to increase from 32 to 83%, which verifies the occurrence of chain extension of the L2EO4-Eu coordination polymers in the micellar core. Our work provides a qualitative picture for the structure change of reversible coordination polymers, which allows us to look into these "invisible" structures.

  15. Structures and properties of porous coordination polymers based on lanthanide carboxylate building units.

    Science.gov (United States)

    Han, Yinfeng; Li, Xiaoyan; Li, Liqing; Ma, Chunlin; Shen, Zhen; Song, You; You, Xiaozeng

    2010-12-06

    A series of 3-D lanthanide porous coordination polymers, [Ln(6)(BDC)(9)(DMF)(6)(H(2)O)(3)·3DMF](n) [Ln = La, 1; Ce, 2; Nd, 3], [Ln(2)(BDC)(3)(DMF)(2)(H(2)O)(2)](n) [Ln = Y, 4; Dy, 5; Eu, 6], [Ln(2)(ADB)(3)(DMSO)(4)·6DMSO·8H(2)O](n) [Ln = Ce, 7; Sm, 8; Eu, 9; Gd, 10], {[Ce(3)(ADB)(3)(HADB)(3)]·30DMSO·29H(2)O}(n) (11), and [Ce(2)(ADB)(3)(H(2)O)(3)](n) (12) (H(2)BDC = benzene-1,4-dicarboxylic acid and H(2)ADB = 4,4'-azodibenzoic acid), have been synthesized and characterized. In 1-3, the adjacent Ln(III) ions are intraconnected to form 1-D metal-carboxylate oxygen chain-shaped building units, [Ln(4)(CO(2))(12)](n), that constructed a 3-D framework with 4 × 7 Å rhombic channels. In 4-6, the dimeric Ln(III) ions are interlinked to yield scaffolds with 3-D interconnecting tunnels. Compounds 7-10 are all 3-D interpenetrating structures with the CaB6-type topology structure. Compound 11 is constructed by ADB spacers and trinulcear Ce nodes with a NaCl-type topology structure and a 1.9-nm open channel system. In 12, the adjacent Ce(III) ions are intraconnected to form 1-D metal-carboxylate oxygen chain-shaped building units, [Ln(4)(CO(2))(12)](n), and give rise to a 3-D framework. Moreover, 6 exhibits characteristic red luminescence properties of Eu(III) complexes. The magnetic susceptibilities, over a temperature range of 1.8-300 K, of 3, 6, and 7 have also been investigated; the results show paramagnetic properties.

  16. 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.

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

    Energy Technology Data Exchange (ETDEWEB)

    Wang, Jun; Tao, Jianqing; Xu, Xiaojuan; Tan, Chunyun [Yancheng Teachers' College, Yancheng (China)

    2012-11-15

    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{sub 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{sub 2} groups.10 Taking these into consideration, we explored the self-assembly of Cd(II) ion, H{sub 4}FA, and BTX under hydrothermal conditions, and obtained a novel 3D coordination polymer: [Cd{sub 3}(BTX){sub 2}(HFA){sub 2}·{sub 2}H{sub 2}O]{sub n}. Herein, we report the synthesis, crystal structure, and physical properties.

  18. Extended structures of two coordination polymers based on 1,10-phenanthroline derivatives:Preparation, structural characterization and properties

    Indian Academy of Sciences (India)

    Yan-Ju Huang; Ya-Ru Pan; Gang Du; Yi-Xin Cao

    2016-03-01

    In this paper,we report two coordination polymers, [Cd(Medpq)(SO4) (H2O)2]n (1)and {[Mn(Medpq)(QUI)H2O]·H2O}n (2) (H2QUI=2,3-pyridinedicarboxylic acid,Medpq=2-methyldipyrido[3,2-f:2,3-h]quinoxaline) by hydrothermal processing and structural characterization by elemental analysis,thermogravimetric analysis and single-crystal X-ray diffraction. The coordination polymers and 2 have 1D chains formed via coordination bonds, and unique two-dimensional supramolecular structures are further formed due to π-π stacking interactions. The results reveal that the coordination preferences ofmetal 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.

  19. 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.

  20. Towards Acid-Tolerated Ethanol Dehydration: Chitosan-Based Mixed Matrix Membranes Containing Cyano-Bridged Coordination Polymer Nanoparticles.

    Science.gov (United States)

    Wu, C-W; Kang, Chao-Hsiang; Lin, Yi-Feng; Tung, Kuo-Lun; Deng, Yu-Heng; Ahamad, Tansir; Alshehri, Saad M; Suzuki, Norihiro; Yamauchi, Yusuke

    2016-04-01

    Prussian blue (PB) nanoparticles, one of many cyano-bridged coordination polymers, are successfully incorporated into chitosan (CS) polymer to prepare PB/CS mixed matrix membranes (MMMs). The PB nanoparticles are uniformly distributed in the MMMs without the collapse of the original PB structure. As-prepared PB/CS MMMs are used for ethanol dehydration at 25 °C in the pervaporation process. The effect of loading PB in CS matrix on pervaporation performance is carefully investigated. The PB/CS membrane with 30 wt% PB loading shows the best performance with a permeate flux of 614 g. m-2 . h-1 and a separation factor of 1472. The pervaporation using our PB/CS membranes exhibits outstanding performance in comparison with the previously reported CS-based membranes and MMMs. Furthermore, the addition of PB allows PB/CS MMMs to be tolerant of acidic environment. The present work demonstrates good pervaporation performance of PB/CS MMMs for the separation of an ethanol/water (90:10 in wt%) solution. Our new system provides an opportunity for dehydration of bioethanol in the future.

  1. The structures and luminescence properties of lanthanide (Ln = Sm, Eu and Tb) metal-organic coordination polymers based on 5-(2-hydroxyethoxy)isophthalate ligand

    Science.gov (United States)

    Wang, Peng; Zhang, Yu-Jie; Qin, Jie; Chen, Yong; Zhao, Ying

    2015-03-01

    Three unreported isomorphous Ln-containing metal-organic coordination polymeric complexes {LnL(HL)ṡ(H2O)2}n (Ln = Sm (1), Eu (2) and Tb (3), CCDC 971815-971817) were synthesized based on 5-(2-hydroxyethoxy) isophthalic acid (H2L) under hydrothermal conditions. The obtained coordination polymers were characterized by IR, elemental analysis, thermal analysis and X-ray diffraction In solid state, these polymers featured 3-D supramolecular structures constructed by 2-D sheets through H-bonds. Investigation of photoluminescence properties of H2L and 1-3 showed all of them exhibited intense fluorescent emissions in the solid state at room temperature.

  2. Synthesis and structural characterization of a calcium coordination polymer based on a 3-bridging tetradentate binding mode of glycine

    Indian Academy of Sciences (India)

    Subramanian Natarajan; Bikshandarkoil R Srinivasan; J Kalyana Sundar; K Ravikumar; R V Krishnakumar; J Suresh

    2012-07-01

    A new coordination polymer namely [[Ca6(H-gly)12(H2O)18]Cl12·6H2O] (1) (H-gly = glycine) has been isolated from the calcium chloride-glycine-water system and structurally characterized. Each Ca(II) in 1 is eight-coordinated and is bonded to eight oxygen atoms three of which are from terminal water molecules and five oxygen atoms from four symmetry related zwitterionic glycine ligands. The H-gly ligands exhibit two different binding modes viz. a monodentate carboxylate ligation and a 3-tetradentate bridging carboxylate binding mode, which results in the formation of a one-dimensional coordination polymer. In the infinite chain the Ca(II) atoms are organized in a zigzag fashion. A comparative study reveals a rich and diverse structural chemistry of calcium halide-glycine compounds.

  3. Hydrothermal Synthesis and Thermal Analyses of an Infinite Three-dimensional Coordination Polymer Based on Formic Acid: [Zn(HCOO)2(H2O)2]∞

    Institute of Scientific and Technical Information of China (English)

    GUO Jin-Yu; ZHANG Tong-Lai; ZHANG Jian-Guo

    2006-01-01

    The coordination polymer [Zn(HCOO)2(H2O)2]∞ has been synthesized using hydrothermal method and characterized by X-ray single crystal diffraction, elemental analysis, FTIR spectroscopy and TG-DTG analyses. The coordination polymer crystallizes in monoclinic, P21/c space group with crystal parameters of a=0.8688(1) nm, b=0.7143(6) nm, c=0.9305(2) nm, β=97.61(5)°, V=0.5724(2) nm3, Z=4, μ(Mo Kα)=42.50 cm-1. The polymer features with two kinds of zinc centers: one is hexa-coordinated by four water ligands, two oxygen atoms of two formates and the other is coordinated by six oxygen atoms of six formates. By the formates as space linkers,three-dimensional frameworks were formed. Based on thermal analyses, thermal decomposition mechanisms were predicted that at the first step the polymer lost two coordination water molecules and at the second step lost two formates companied by the formation of some kinds of materials.

  4. Hand-Ground Nanoscale Zn(II) -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 E2 (PGE2 ) 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 PGE2 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.

  5. N-(sulfoethyl) iminodiacetic acid-based lanthanide coordination polymers: Synthesis, magnetism and quantum Monte Carlo studies

    Energy Technology Data Exchange (ETDEWEB)

    Zhuang Guilin, E-mail: glzhuang@zjut.edu.cn [Institute of Industrial Catalysis, College of Chemical Engineering and Materials Science, Zhejiang University of Technology, Hangzhou 310032 (China); Chen Wulin [Institute of Industrial Catalysis, College of Chemical Engineering and Materials Science, Zhejiang University of Technology, Hangzhou 310032 (China); Zheng Jun [Center of Modern Experimental Technology, Anhui University, Hefei 230039 (China); Yu Huiyou [Institute of Industrial Catalysis, College of Chemical Engineering and Materials Science, Zhejiang University of Technology, Hangzhou 310032 (China); Wang Jianguo, E-mail: jgw@zjut.edu.cn [Institute of Industrial Catalysis, College of Chemical Engineering and Materials Science, Zhejiang University of Technology, Hangzhou 310032 (China)

    2012-08-15

    A series of lanthanide coordination polymers have been obtained through the hydrothermal reaction of N-(sulfoethyl) iminodiacetic acid (H{sub 3}SIDA) and Ln(NO{sub 3}){sub 3} (Ln=La, 1; Pr, 2; Nd, 3; Gd, 4). Crystal structure analysis exhibits that lanthanide ions affect the coordination number, bond length and dimension of compounds 1-4, which reveal that their structure diversity can be attributed to the effect of lanthanide contraction. Furthermore, the combination of magnetic measure with quantum Monte Carlo(QMC) studies exhibits that the coupling parameters between two adjacent Gd{sup 3+} ions for anti-anti and syn-anti carboxylate bridges are -1.0 Multiplication-Sign 10{sup -3} and -5.0 Multiplication-Sign 10{sup -3} cm{sup -1}, respectively, which reveals weak antiferromagnetic interaction in 4. - Graphical abstract: Four lanthanide coordination polymers with N-(sulfoethyl) iminodiacetic acid were obtained under hydrothermal condition and reveal the weak antiferromagnetic coupling between two Gd{sup 3+} ions by Quantum Monte Carlo studies. Highlights: Black-Right-Pointing-Pointer Four lanthanide coordination polymers of H{sub 3}SIDA ligand were obtained. Black-Right-Pointing-Pointer Lanthanide ions play an important role in their structural diversity. Black-Right-Pointing-Pointer Magnetic measure exhibits that compound 4 features antiferromagnetic property. Black-Right-Pointing-Pointer Quantum Monte Carlo studies reveal the coupling parameters of two Gd{sup 3+} ions.

  6. Synthesis, structure and dielectric properties of a Cd coordination polymer based on homopiperazine

    Science.gov (United States)

    Shi, Qiu-Zhong; Xing, Zheng; Cao, Yong-Nan; Ma, Shi-Bing; Chen, Li-Zhuang

    2017-02-01

    A (4,6)-connected three-dimensional network complex [Cd(hpip)Br2]n (1) [hpip = homopiperazine] was prepared from CdBr2·4H2O and hpip by hydrothermal reaction in water. The structure was characterized by single-crystal X-ray diffraction (XRD), Fourier transform infrared spectroscopy, thermogravimetric analysis and elemental analysis. The asymmetric unit contains one hpip ligand, one Cd(II) cation and two Br- anions. Each Cd(II) cation is coordinated by two N atoms from the ligand and four Br- anions, showing a distorted octahedral geometry. Its dielectric constant was measured at different frequencies with temperature variations.

  7. 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.

  8. A Lead (II 3D Coordination Polymer Based on a Marine Cyclic Peptide Motif

    Directory of Open Access Journals (Sweden)

    Gene-Hsiang Lee

    2013-04-01

    Full Text Available The crystal structure of a naturally occurring cyclic tetrapeptide cyclo(Gly-L-Ser-L-Pro-L-Glu [cyclo(GSPE] was obtained. The conformation of synthesized cyclo(GSPE fixes the coordination to lead ion in a 1:1 ratio. This cyclo(GSPE-Pb complex was constructed as an asymmetric 3D network in the crystalline state. The polymerization of a heavy metal ion with a rigid asymmetric cyclic tetrapeptide represents the first example of a new class of macrocyclic complexes.

  9. 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.

  10. Cadmium coordination polymers based on flexible bis(imidazole) ligands: A rare example for doublet of doublet cadmium polyhedron arrangements

    Science.gov (United States)

    Babu, Chatla Naga; Suresh, Paladugu; Sampath, Natarajan; Prabusankar, Ganesan

    2014-10-01

    Two one-dimensional (1D) coordination polymers, [{LCd(O2NO)2(DMF)2}2{(LCd(O2NO)2(DMF))(DMF)}2]n (1) and [L‧Cd(O2NO)(ONO2)(DMF)2]n (2), having an aryl chromophoric unit and a flexible bis(imidazole) tail, 9,10-bis{(benzimidazol)methyl}anthracene (L) and 1,4-bis{(imidazol)methyl}benzene (L‧), with various coordination modes have been obtained. Molecule 1 represents the first structurally characterized one dimensional coordination polymer consisting of both hepta- and octa-coordinated cadmium centers. In 1, two distorted pentagonal bipyramidal Cd(II) centers and two distorted triangular dodecahedral Cd(II) centers are alternately arranged via bridging bidentate N,N-chelating ligand, L. Whereas, a distorted pentagonal bipyramidal Cd(II) center is formed in 2 where the sterically less crowded L‧ serves as a bridging bidentate N,N-chelating ligand. Furthermore, 1 and 2 have been characterized by elemental analysis, FT-IR, 1H NMR, UV-vis and fluorescent techniques.

  11. 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.

  12. Synthesis and Characterization of a Novel 3D Coordination Polymer Based on Cu(Ⅱ) Cations and Mellitic Acid

    Institute of Scientific and Technical Information of China (English)

    YANG E; QIN Ye-Yan; CAO Xin-Yi; LIN Qi-Pu; YIN Pei-Xiu; YAO Yuan-Gen

    2008-01-01

    A new mellitate complex [Cu3(μ2-mellitate)(μ2-H2O)(H2O)2·H2O]n 1 has been synthesi- zed by the reaction of mellitic acid and Cu(CH3COO)2·H2O in the presence of base. Crystallogra- phic data for 1: C12H80O16Cu3, Mr = 598.80, orthorhombic, Pbcn, a = 8.4378(6), b = 10.0396(7), c = 17.6799(12) A, V = 1497.70(18) A3, Z = 4, Dc = 2.656 g/cm3,μ = 4.327 mm-1, F(000) = 1180, R = 0.0431 and wR = 0.0964 for 1075 observed reflections (Ⅰ> 2σ(Ⅰ)). X-ray crystal structural analysis revealed that the mellitate anions behave as the bridging ligands and link eight copper atoms repeatedly to form a novel three-dimensional metal-organic coordination polymer with two different rhombic tunnels in the solid-state structure.

  13. Syntheses, structures and properties of three cobalt coordination polymers based on flexible bis(triazole) and 5-nitroisophthalate coligands

    Science.gov (United States)

    Chen, Qian; Zhu, Xia; Ding, Jian-Gang; Li, Bao-Long; Li, Hai-Yan

    2013-04-01

    Three coordination polymers {[Co(bte)(NO2-1,3-bdc)(H2O)]ṡH2O}n (1), {[Co(btp)(NO2-1,3-bdc)(H2O)]ṡ2H2O}n (2) and {[Co2(btb)2(NO2-1,3-bdc)2]ṡ2H2O}n (3) were synthesized by the different spacer lengths and conformational flexibilities bte, btp, btb and the rigid NO2-1,3-bdc. 1 forms an independent 1D MONT and a (1D → 2D) interdigitated array. In 2, two identical undulated (4,4) networks are parallel stacking to give a double-layer. In 3, the btb ligands connect the [Co2(NO2-1,3-bdc)2]n ladders to construct an unusual 3D network with point symbol 46ṡ67ṡ82 based on [Co2(COO)2] unit. The thermal stability and the UV-vis spectra of 1, 2 and 3 were investigated.

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

    Science.gov (United States)

    Lu, Xin-Xin; Luo, Yu-Hui; Lu, Chen; Chen, Xin; Zhang, Hong

    2015-12-01

    Three new silver coordination polymers, namely, {Ag3(bpy)6[PW12O40]} (1), {Ag5(H2biim)2(Hbiim-NO2)2[PW12O40]} (2), {Ag7(pytz)4[PW12O40]} (3) (bpy=2,2‧-bipyridine, H2biim=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.

  15. Design and synthesis of two luminescent Zn(II)-based coordination polymers with different structures regulated by different solvent system

    Science.gov (United States)

    Wu, Wei-Ping; Wen, Gui-Lin; Liao, Yi; Wang, Jun; Lu, Lu; Wu, Yu; Xie, Bin

    2016-08-01

    Two new coordination polymers (CPs) [Zn(HL)(H2O)]n (1) and [Zn3(L)2(H2O)2]n·(H2O)n (2), based on a multifunctional ligand combined carboxylate groups and a nitrogen donor group 5-(6-carboxypyridin-2-yl)isophthalic acid (H3L), have been synthesized under different solvent media and fully characterized by powder X-ray diffraction (PXRD), infrared (IR) spectra, elemental analyses (EA) and thermogravimetric analyses (TGA). Single-crystal X-ray diffraction analysis reveals that 1 shows 1D dimeric chain structure, while 2 gives a 3D dense packing framework. Topology analysis illustrates that 2 can be simplified as a 3-nodal net (4, 5, 6-connected net) with the point symbol of {44·62}{46·64}2{48·66·8}. In addition, solid state luminescent properties of two complexes have also been studied in detail, which may act as the potential optical materials.

  16. A series of coordination polymers based on a V-shaped multicarboxylate and bisimidazole ligands: Synthesis, characterization and luminescent properties

    Science.gov (United States)

    Guo, Huadong; Yan, Yongnian; Guo, Xianmin; Wang, Nan; Qi, Yanjuan

    2016-03-01

    Based on a V-shaped multicarboxylic acid and various bisimidazole ligands, six new coordination polymers, namely, [Zn4(otba) (1,4-bix)4]·3H2O (1), [Ni4(otba)2(1,4-bix)3(H2O)2]·2H2O (2), [Zn2(H2otba)2(bib) (H2O)2] (3), [Cd2(H2otba)2(bib)]·2H2O (4), [Zn3(otba)2(bidpe)2(H2O)2] (5), [Ni2(H2otba)2(bidpe)3(H2O)2]·H2O (6) (H4otba = 3,5,3‧,5‧-oxytetrabenzoic acid, 1,4-bix = 1,2-bis(imidazol-1-ylmethyl)benzene, bib = 1,4-bis(imidazol-1-yl)benzene and bidpe = 4,4'-bis(imidazol-1-yl)diphenyl ether) have been hydrothermally synthesized and structurally characterized. Compound 1 displays an uncommon hexanodal 3D 4-connected network. Compound 2 features a trinodal 3D (4, 4, 6)-connected framework. Compound 3 shows an interesting polythreaded 1D→3D species. Compound 4 exhibits a binodal 3D (3, 8)-connected network. Compound 5 displays a three-fold interpenetration of trinodal (3, 3, 4)-connected network. Compound 6 shows a five-fold interpenetration of five-connected bilayer network. The luminescent properties of compounds 1, 3, 4 and 5 were also measured.

  17. Metallogels from Coordination Complexes, Organometallic, and Coordination Polymers.

    Science.gov (United States)

    Dastidar, Parthasarathi; Ganguly, Sumi; Sarkar, Koushik

    2016-09-20

    A supramolecular gel results from the immobilization of solvent molecules on a 3D network of gelator molecules stabilized by various supramolecular interactions that include hydrogen bonding, π-π stacking, van der Waals interactions, and halogen bonding. In a metallogel, a metal is a part of the gel network as a coordinated metal ion (in a discrete coordination complex), as a cross-linking metal node with a multitopic ligand (in coordination polymer), and as metal nanoparticles adhered to the gel network. Although the field is relatively new, research into metallogels has experienced a considerable upsurge owing to its fundamental importance in supramolecular chemistry and various potential applications. This focus review aims to provide an insight into the development of designing metallogelators. Because of the limited scope, discussions are confined to examples pertaining to metallogelators derived from discrete coordination complexes, organometallic gelators, and coordination polymers. This review is expected to enlighten readers on the current development of designing metallogelators of the abovementioned class of molecules. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  18. A new two-dimensional manganese(II) coordination polymer based on thiophene-3,4-dicarboxylic acid.

    Science.gov (United States)

    Wang, Gui-Xia; Shang, Li-Li; Li, Zhao-Hao; Zhao, Bang-Tun

    2014-07-01

    A novel manganese coordination polymer, poly[(μ5-thiophene-3,4-dicarboxylato)manganese(II)], [Mn(C6H2O4S)]n, was synthesized hydrothermally using 3,4-thiophenedicarboxylate (3,4-tdc(2-)) as the organic linker. The asymmetric unit of the complex contains an Mn(2+) cation and one half of a deprotonated 3,4-tdc(2-) anion, both residing on a twofold axis. Each Mn(2+) centre is six-coordinated by O atoms of bridging/chelating carboxylate groups from five 3,4-tdc(2-) anions, forming a slightly distorted octahedron. The Mn(2+) centres are bridged by 3,4-tdc(2-) anions to give an infinite two-dimensional layer which incorporates one-dimensional Mn-O gridlike chains, and in which the 3,4-tdc(2-) anion adopts a novel hexadentate chelating and μ5-bridging coordination mode. The fully deprotonated 3,4-tdc(2-) anion exhibits unexpected efficiency as a ligand towards the Mn(2+) centres, which it coordinates through all of its carboxylate O atoms to provide the novel coordination mode. The IR spectrum of the complex is also reported.

  19. 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.

  20. Experimental and theoretical investigation of vibrational spectra of coordination polymers based on TCE-TTF.

    Science.gov (United States)

    Olejniczak, Iwona; Lapiński, Andrzej; Swietlik, Roman; Olivier, Jean; Golhen, Stéphane; Ouahab, Lahcène

    2011-08-01

    The room-temperature infrared and Raman spectra of a series of four isostructural polymeric salts of 2,3,6,7-tetrakis(2-cyanoethylthio)-tetrathiafulvalene (TCE-TTF) with paramagnetic (Co(II), Mn(II)) and diamagnetic (Zn(II), Cd(II)) ions, together with BF(4)(-) or ClO(4)(-) anions are reported. Infrared and Raman-active modes are identified and assigned based on theoretical calculations for neutral and ionized TCE-TTF using density functional theory (DFT) methods. It is confirmed that the TCE-TTF molecules in all the materials investigated are fully ionized and interact in the crystal structure through cyanoethylthio groups. The vibrational modes related to the C=C stretching vibrations of TCE-TTF are analyzed assuming the occurrence of electron-molecular vibration coupling (EMV). The presence of the antisymmetric C=C dimeric mode provides evidence that charge transfer takes place between TCE-TTF molecules belonging to neighboring polymeric networks.

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

    Energy Technology Data Exchange (ETDEWEB)

    Zhang, Ju-Wen; Zhao, Wei; Lu, Qi-Lin; Luan, Jian; Qu, Yun; Wang, Xiu-Li, E-mail: wangxiuli@bhu.edu.cn

    2014-04-01

    Five new metal–organic coordination polymers ([Cu{sub 3}(μ{sub 2}-OH){sub 2}(atrz){sub 2}(nph){sub 2}(H{sub 2}O){sub 2}]·2H{sub 2}O){sub n} (1), ([Cu{sub 2}(μ{sub 3}-OH)(atrz)(1,2,4-btc)]·2H{sub 2}O){sub n} (2), ([Cu{sub 2}(μ{sub 3}-OH)(atrz)(1,2,4-btc)(H{sub 2}O)]·H{sub 2}O){sub n} (3), [Cu(dth){sub 0.5}(nph)(H{sub 2}O)]{sub n} (4) and [Cu(dth)(Hnip){sub 2}]{sub n} (5) [atrz=4-amino-1,2,4-triazole, dth=N,N'-di(4H-1,2,4-triazole)hexanamide, H{sub 2}nph=3-nitrophthalic acid, 1,2,4-H{sub 3}btc=1,2,4-benzenetricarboxylic acid and H{sub 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{sup II}{sub 4} cluster-based three-dimensional (3D) frameworks with the same components. Polymer 4 possesses a 3D framework with a 4{sup 12}·6{sup 3}-pcu topology. Polymer 5 displays a 3D framework with a 4{sup 4}·6{sup 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.

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

    Energy Technology Data Exchange (ETDEWEB)

    Cao, Ke-Li; Zhang, Yi-Ping; Cai, Yi-Ni; Xu, Xiao-Wei; Feng, Yun-Long, E-mail: sky37@zjnu.cn

    2014-07-01

    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{sub 2}(H{sub 2}O){sub 2}]{sub n}·2nH{sub 2}O (1), which possesses a 1D chain structure. In the presence of ancillary ligands, namely, 1,3-adamantanedicarboxylic acid (H{sub 2}adbc), terephthalic acid (H{sub 2}tpa), thiophene-2,5-dicarboxylic acid (H{sub 2}tdc) and 1,4-benzenedithioacetic acid (H{sub 2}bdtc), four 3D structures [Co{sub 2}L{sub 2}(adbc)]{sub n}·nH{sub 2}O (2), [Co{sub 2}L{sub 2}(tpa)]{sub n} (3), [Co{sub 2}L{sub 2}(tdc)]{sub n} (4), [Co{sub 2}L{sub 2}(bdtc)(H{sub 2}O)]{sub 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.

  3. Two New Iron Coordination Polymers Based on Fe-pyta ChainsIncorporating Pyridine-2,4,6-tricarboxylate

    Institute of Scientific and Technical Information of China (English)

    CHEN Zi-yun; PENG Meng-xia

    2008-01-01

    Reaction of FeCl2·6H2O,pyridine-2,4,6-tricarboxylie acid(H3pyta) and NaOH in the hydrothermal system at 185℃ resulted in the formation of 1D coordination polymer[Fe(Hpyta)(H2O)2](1) based on Fe-Hpyta chains,When the abpt[abpt=4-amino-3,5-bis(4-pyridyl)-1,2,4-triazole]ligand was employed in the reaction system,a 3D supramolecular porous network (H2bpt)[Fe(pyta)(H2O)2]·4H2O(2) was obtained,The framework was constructed with negative (Fe-pyta) chains and the positive H2bpt+ in situ,formed from the abpt reagent,to form 1D channels filled with guest water molecules via hydrogen-bonds,X-Ray diffraction crystal structure analysis shows that complex 1 crystallized in the monoclinic system,space group C2/c,a=1.1490(5) nm,b=0.9008(4) nm,c=1.0058(5) nm,β=107.254(9)°,V=0.9942(8) nm3,Z=4; and complex 2 crystallizes in the triclinic system,space group P(1) with a=0.90392(11) nm,b=0.96027(11) nm,c=1.55540(18)nm,a=73.558(2)°,β=86.126(2)°,y=68.745(2)°,V=1.2059(2) nm3 and Z=2.

  4. Syntheses, structures, molecular and cationic recognitions and catalytic properties of two lanthanide coordination polymers based on a flexible tricarboxylate

    Energy Technology Data Exchange (ETDEWEB)

    Zhu, Yu; Wang, Yan-Mei; Xu, Ji; Liu, Pan; Weththasinha, H.A.B.M.D.; Wu, Yun-Long; Lu, Xiao-Qing; Xie, Ji-Min, E-mail: xiejm391@sohu.com

    2014-11-15

    Two lanthanide coordination polymers, namely, ([La(TTTA)(H{sub 2}O){sub 2}]·2H{sub 2}O){sub n} (La-TTTA) and [Nd(TTTA)(H{sub 2}O){sub 2}]·2H{sub 2}O){sub n} (Nd-TTTA) have been hydrothermally synthesized through the reaction of lanthanide ions (La{sup 3+} and Nd{sup 3+}) with the flexible tripodal ligand 2,2′,2″-[1,3,5-triazine-2,4,6-triyltris(thio)]tris-acetic acid (H{sub 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{sup 3+}, Cu{sup 2+}, Mg{sup 2+}, Cr{sup 3+} and Co{sup 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{sub 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{sup 3+}, Cu{sup 2+}, Mg{sup 2+}, Cr{sup 3+} and Co{sup 2+} ions via quenching the peak around 361 nm. • They act as efficient Lewis acid catalysts for the cyanosilylation reactions in high yields.

  5. Synthesis, crystal structure, and luminescent properties of two coordination polymers based on 1,4-phenylenediacetic acid

    Science.gov (United States)

    Zhang, Meili; Ren, Yixia; Ma, Zhenzhen; Qiao, Lei

    2017-06-01

    Two coordination polymers, [Zn(pda)(bib)]n (1) and [Cd(pda)0.5(bib)Cl]n (2)]. (H2pda = 1,4-phenylenediacetic acid, bib = 1,2-bis(imidazol-1-ylmethyl)benzene), have been synthesized by using Zn(II)/Cd(II) salts with two flexible ligands pda and bib under hydrothermal conditions. Their structures have been characterized by elemental analysis, IR spectroscopy, single-crystal X-ray crystallography and powder X-ray diffraction (PXRD) analysis. Due to the coordination geometry around the metal ions and the diverse coordination modes of the flexible ligands, the obtained complex show diverse structures. In the structure of 1, a pair of bib ligands connect two Zn(II) atoms give rise a 22-membered ring, which is further extended by pda ligands in bidentate coordination mode leading a ring-containing 2D layer. In 2, bib ligands join [Cd2Cl2]2+ dimmers generate 1D polymeric ribbon, the pda ligands further extend such ribbon forming a 2D layer network containing rectangular windows, which discovers the effect of the central metal ions on the formation of metal-organic frameworks. In additional, luminescent properties of two complexes have also been studied, they could be potential fluorescence materials.

  6. 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)fn) 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 H2O2 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.

  7. Topochemical control in desolvation of coordination polymers

    OpenAIRE

    Matteo Lusi

    2015-01-01

    Reactions in the solid state are at the core of crystal engineering as they can result in new crystalline phases that are not always accessible by traditional solution methods. The work of Brammer and co-workers [Wright et al. (2015), IUCrJ, 2, 188–197] represents a clear example of this potential as applied to the synthesis of a silver–phenazine coordination polymer.

  8. A new redox-active coordination polymer with cobalticinium dicarboxylate.

    Science.gov (United States)

    Kondo, Mitsuru; Hayakawa, Yuri; Miyazawa, Makoto; Oyama, Aiko; Unoura, Kei; Kawaguchi, Hiroyuki; Naito, Tetsuyoshi; Maeda, Kenji; Uchida, Fumio

    2004-09-20

    A new two-dimensional coordination polymer with cobalticinium 1,1'-dicarboxylate (ccdc) incorporated in the framework has been prepared, the ccdc functioning as unique monoanionic dicarboxylate ligands. The compound shows a high redox activity based on the ccdc units.

  9. 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.

  10. Synthesis, structures and photocatalytic properties of two new Co(II) coordination polymers based on 5-(benzyloxy)isophthalate ligand

    Science.gov (United States)

    Li, Xia; Li, Jing; Li, Ming-Kai; Fei, Zhou

    2014-02-01

    Two new Co(II) coordination polymer, namely [Co2(L)2(H2O)]n (1) and [Co(L)(phen)(H2O)]n·xH2O (2) (H2L = 5-(benzyloxy)isophthalic acid, phen = 1,10-phenanthroline) have been hydrothermally synthesized and characterized by elemental analysis, powder X-ray diffraction, thermal analysis and single crystal X-ray analysis. The molecular structure of 1 contains two Co(II) ions, two L2- ligands and one coordinated water molecule, which further extends into a complicated 3D framework with the tails of L2- ligands filling in the hexagonal channels, and the molecular structure of 2 contains one Co(II) ions, one L2- ligands, one phen ligands, one coordinated water molecule and half of the water molecule of crystallization, which further extends into a 1D chain structure. In addition, photocatalytic investigation on compounds 1 and 2 reveals that they are active catalyst for degradation of methyl blue.

  11. 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.

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

    Energy Technology Data Exchange (ETDEWEB)

    Li, Gui-Lian; Yin, Wei-Dong; Liu, Guang-Zhen; Ma, Lu-Fang [College of Chemistry and Chemical Engineering, Luoyang Normal University, Luoyang 471022, Henan (China); Wang, Li-Ya, E-mail: gzliuly@126.com [College of Chemistry and Chemical Engineering, Luoyang Normal University, Luoyang 471022, Henan (China); College of Chemistry and Pharmacy Engineering, Nanyang Normal University, Nanyang 473061, Henan (China)

    2014-12-15

    Four new coordination polymers ([Ni(4-Nbdc)(bpa)(H{sub 2}O)]){sub n} (1), ([Co(4-Nbdc)(bpp) (H{sub 2}O)]){sub n} (2), ([Ni(4-Nbdc)(bpp)(H{sub 2}O)]·H{sub 2}O){sub n} (3), and ([Mn{sub 2}(3-Nbdc){sub 2}(bib){sub 3}]·2H{sub 2}O){sub 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{sup 6}) dia topology and (4{sup 4}.6{sup 10}.8)(4{sup 4}.6{sup 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{sup −1}) and Ni(II)–carboxylate chain in 3 (J=1.44 cm{sup −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{sup −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.

  13. Prediction of the spin transition temperature in Fe(II) one-dimensional coordination polymers: an anion based database.

    Science.gov (United States)

    Dîrtu, Marinela M; Rotaru, Aurelian; Gillard, Damien; Linares, Jorge; Codjovi, Epiphane; Tinant, Bernard; Garcia, Yann

    2009-08-17

    One-dimensional (1D) coordination polymers of formula [Fe(NH(2)trz)(3)]A.nH(2)O, {A = TiF(6)(2-), n = 0.5 (1) and n = 1 (2); A = ZrF(6)(2-), n = 0.5 (3) and n = 0 (4); A = SnF(6)(2-), n = 0.5 (5) and n = 1 (6); A = TaF(7)(2-), n = 3 (7) and n = 2.5 (8); A = GeF(6)(2-), n = 1 (9) and n = 0.5 (10), NH(2)trz = 4-amino-1,2,4-triazole} have been synthesized, fully characterized, and their spin crossover behavior carefully studied by SQUID magnetometry, Mossbauer spectroscopy, and differential scanning calorimetry. These materials display an abrupt and hysteretic spin transition around 200 K on cooling, as well as a reversible thermochromic effect. Accurate spin transition curves were derived by (57)Fe Mossbauer spectroscopy considering the corrected f factors for the high-spin and low-spin states determined employing the Debye model. The unusual hysteresis width of 3 (28 K), was attributed to a dense hydrogen bonding network involving the ZrF(6)(2-) counteranion and the 1D chains, an organization which is also revealed in [Cu(NH(2)trz)(3)]ZrF(6).H(2)O (11). Trinuclear spin crossover compounds of formula [Fe(3)(NH(2)trz)(10)(H(2)O)(2)](SbF(6))(6).S {S = 1.5CH(3)OH (12), 0.5C(2)H(5)OH (13)} were also obtained. A structural property relationship was derived between the volume of the inserted counteranion and the transition temperature T(1/2) of the 1D chains. Two linear size regimes were identified for monovalent anions (0.04 or= 0.11 nm(3)) with saturation around T(1/2) = 200 K. These characteristics allowed us to derive an anion based database that is of interest for the prediction of the transition temperature of such functional switchable materials. Diffuse reflectivity measurements under hydrostatic pressure for 3,4 combined with calorimetric data allow an estimation of the electrostatic pressure between cationic chains and counteranions in the crystal lattice of these materials. The chain length distribution that ranges between 1 and 4 nm was also derived.

  14. Transition metal coordination polymers based on tetrabromoterephthalic and bis(imidazole) ligands: Syntheses, structures, topological analysis and photoluminescence properties

    Science.gov (United States)

    Zhang, Xiaowei; Xing, Peiqi; Geng, Xiujuan; Sun, Daofeng; Xiao, Zhenyu; Wang, Lei

    2015-09-01

    Eight new coordination polymers (CPs), namely, [Zn(1,2-mbix)(tbtpa)]n (1), [Co(1,2-mbix)(tbtpa)]n (2), [CdCl(1,2-mbix)(tbtpa)0.5]n (3), {[Cd(1,2-bix)(tbtpa)]·H2O}n (4), {[Cd0.5(1,2-bix)(tbtpa)0.5]·H2O}n (5), {[Co0.5(1,2-bix)(tbtpa)0.5]·2H2O}n (6), {[Co(1,2-bix)(tbtpa)]·H2O}n (7) and {[Co(1,2-bix)(tbtpa)]·Diox·2H2O}n (8), were synthesized under solvothermal conditions based on mix-ligand strategy (H2tbtpa=tetrabromoterephthalic acid and 1,2-mbix=1,2-bis((2-methyl-1H-imidazol-1-yl)methyl)benzene, 1,2-bix=1,2-bis(imidazol-1-ylmethyl)benzene). All of the CPs have been structurally characterized by single-crystal X-ray diffraction analyses and further characterized by elemental analyses, IR spectroscopy, powder X-ray diffraction (PXRD), and thermogravimetric analyses (TGA). X-ray diffraction analyses show that 1 and 2 are isotypics which have 2D highly undulated networks with (4,4)-sql topology with the existence of C-H ⋯Br interactions; for 3, it has a 2D planar network with (4,4)-sql topology with the occurrence of C-H ⋯Cl interactions other than C-H ⋯Br interactions; 4 shows a 3D 2-fold interpenetrated nets with rare 65·8-mok topology which has a self-catention property. As the same case as 1 and 2, 5 and 6 are also isostructural with planar layers with 44-sql topology which further assembled into 3D supramolecular structure through the interdigitated stacking fashion and the C-Br ⋯Cph interactions. As for 7, it has a 2D slightly undulated networks with (4,4)-sql topology which has one dimension channel. While 8 has a 2-fold interpenetrated networks with (3,4)-connect jeb topology with point symbol {63}{65·8}. And their structures can be tuned by conformations of bis(imidazol) ligands and solvent mixture. Besides, the TGA properties for all compounds and the luminescent properties for 1, 3, 4, 5 are discussed in detail.

  15. Synthesis, Crystal Structure, and Luminescence Properties of a New Calcium(II Coordination Polymer Based on L-Malic Acid

    Directory of Open Access Journals (Sweden)

    Duraisamy Senthil Raja

    2013-01-01

    Full Text Available A new calcium coordination polymer [Ca(HL-MA]n (H3L-MA = L-malic acid has been solvothermally synthesized. The structure of the newly synthesized complex has been determined by single-crystal X-ray diffraction analysis and further characterized by elemental analysis, reflectance UV-Vis & IR spectra, powder X-ray diffraction (PXRD, and thermogravimetric analysis (TGA. The single crystal structure analysis showed that the complex forms three-dimensional framework. The new Ca(II complex has displayed very high thermal stability which was inferred from TGA and PXRD results. As far as the optical property of the new complex is concerned, the complex emitted its own characteristic sensitized luminescence.

  16. Syntheses and Characterizations of Two New Coordination Polymers Based on Dicarboxylate and Nitrogen-contained Mixed Ligands

    Institute of Scientific and Technical Information of China (English)

    YU Ling-Ling

    2011-01-01

    Two new carboxylate coordination polymers [Ni(2,3'-oba)(bib)]n] and [Mn(2,4'-oba)(bib)0.5]n(2,3'-oba = 2-(3-carboxyphenoxy)benzoic acid,2,4'-oba = 2-(4-carboxyphenoxy) ben-zoic acid and bib = 1,4-bis(2-methyl-imidazol-yl)butane) have been synthesized and characterized by elemental analysis,IR and X-ray single-crystal diffraction studies.Compound 1 crystallizes in monoclinic,space group P21/c,while compound 2 in the triclinic space group P.Compound 1 displays a one-dimensional ladder-like chain.The dinuclear paddle-wheel secondary building units(SBUs) constructed by four 2,4'-oba2-ligands in compound 2 are linked by bib into a 2D(4,4) layer structure.

  17. Mixed-valence copper coordination polymers based on CuSCN or CuN3 as bridging motifs

    Institute of Scientific and Technical Information of China (English)

    FAN Guang; GAO Shengli; CHEN Sanping; ZENG Minghua; XIE Gang

    2005-01-01

    Two novel mixed valence copper coordination polymers, [Cu(2-pac)2(CuN3)(H2O)]n (1) and [Cu(2-pac)2(CuSCN)2]n (2), have been prepared through hydrothermal synthesis and analyzed for structure determination, which exhibit two- and three-dimensional structures respectively. In complex (1), zigzag chains of [CuN3]n running parallel to the c direction are interconnected by Cu(2pac)2 to form a two-dimensional layer structure. In complex (2), the arrangement of μ-1,1,3 bridging thiocyanate ligand leads to the formation of ten-membered Cu-SCN- Cu-S-Cu-NCS rings, and each Cu atom is further linked by Cu(2-pac)2 to afford a three-dimensional configuration.

  18. Structures and Spectroscopy Studies of Two M(II-Phosphonate Coordination Polymers Based on Alkaline Earth Metals (M = Ba, Mg

    Directory of Open Access Journals (Sweden)

    Kui-Rong Ma

    2013-01-01

    Full Text Available The two examples of alkaline-earth M(II-phosphonate coordination polymers, [Ba2(L(H2O9]·3H2O (1 and [Mg1.5(H2O9]·(L-H21.5·6H2O (2 (H4L = H2O3PCH2N(C4H8NCH2PO3H2, N,N′-piperazinebis(methylenephosphonic acid, (L-H2 = O3PH2CHN(C4H8NHCH2PO3 have been hydrothermally synthesized and characterized by elemental analysis, FT-IR, PXRD, TG-DSC, and single-crystal X-ray diffraction. Compound 1 possesses a 2D inorganic-organic alternate arrangement layer structure built from 1D inorganic chains through the piperazine bridge, in which the ligand L−4 shows two types of coordination modes reported rarely at the same time. In 1, both crystallographic distinct Ba(1 and Ba(2 ions adopt 8-coordination two caps and 9-coordination three caps triangular prism geometry structures, respectively. Compound 2 possesses a zero-dimensional mononuclear structure with two crystallographic distinct Mg(II ions. Free metal cations   [MgO6]n2+ and uncoordinated anions (L-H2n2- are joined together by static electric force. Results of photoluminescent measurement indicate three main emission bands centered at 300 nm, 378.5 nm, and 433 nm for 1 and 302 nm, 378 nm, and 434.5 nm for 2 (λex=235 nm, respectively. The high energy emissions could be derived from the intraligand π∗-n transition stations of H4L (310 nm and 382 nm, λex=235 nm, while the low energy emission (>400 nm of 1-2 may be due to the coordination effect with metal(II ions.

  19. Highly conductive self-assembled nanoribbons of coordination polymers.

    Science.gov (United States)

    Welte, Lorena; Calzolari, Arrigo; Di Felice, Rosa; Zamora, Felix; Gómez-Herrero, Julio

    2010-02-01

    Organic molecules can self-assemble into well-ordered structures, but the conductance of these structures is limited, which is a disadvantage for applications in molecular electronics. Conductivity can be improved by using coordination polymers-in which metal centres are incorporated into a molecular backbone-and such structures have been used as molecular wires by self-assembling them into ordered films on metal surfaces. Here, we report electrically conductive nanoribbons of the coordination polymer [Pt(2)I(S(2)CCH(3))(4)](n) self-assembled on an insulating substrate by direct sublimation of polymer crystals. Conductance atomic force microscopy is used to probe the electrical characteristics of a few polymer chains ( approximately 10) within the nanoribbons. The observed currents exceed those previously sustained in organic and metal-organic molecules assembled on surfaces by several orders of magnitude and over much longer distances. These results, and the results of theoretical calculations based on density functional theory, confirm coordination polymers as candidate materials for applications in molecular electronics.

  20. Cluster-based networks: 1D and 2D coordination polymers based on {MnFe2(μ3-O)}-type clusters.

    Science.gov (United States)

    Dulcevscaia, Galina M; Filippova, Irina G; Speldrich, Manfred; van Leusen, Jan; Kravtsov, Victor Ch; Baca, Svetlana G; Kögerler, Paul; Liu, Shi-Xia; Decurtins, Silvio

    2012-05-07

    A straightforward approach to heterometallic Mn-Fe cluster-based coordination polymers is presented. By employing a mixed-valent μ(3)-oxo trinuclear manganese(II/III) pivalate cluster, isolated as [Mn(II)Mn(III)(2)O(O(2)CCMe(3))(6)(hmta)(3)]·(solvent) (hmta = hexamethylenetetramine; solvent = n-propanol (1), toluene (2)) in the reaction with a μ(3)-oxo trinuclear iron(III) pivalate cluster compound, [Fe(3)O(O(2)CCMe(3))(6)(H(2)O)(3)]O(2)CCMe(3)·2Me(3)CCO(2)H, three new heterometallic {Mn(II)Fe(III)(2)} cluster-based coordination polymers were obtained: the one-dimensional polymer chain compounds {[MnFe(2)O(O(2)CCMe(3))(6)(hmta)(2)]·0.5MeCN}(n) (3) and {[MnFe(2)O(O(2)CCMe(3))(6)(hmta)(2)]·Me(3)CCO(2)H·(n-hexane)}(n) (4) and the two-dimensional layer compound {[MnFe(2)O(O(2)CCMe(3))(6)(hmta)(1.5)]·(toluene)}(n) (5). Single-crystal X-ray diffraction analysis reveals a μ(3)-oxo trinuclear pivalate cluster building block as the main constituent in all polymer compounds. Different M:hmta ratios in 1-5 are related to the different structural functions of the N-containing ligand. In clusters 1 and 2, three hmta ligands are monodentate, whereas in chains 3 and 4 two hmta ligands act as bridging ligands and one is a monodentate ligand; in 5, all hmta molecules act as bidentate bridges. Magnetic studies indicate dominant antiferromagnetic interactions between the metal centers in both homometallic {Mn(3)}-type clusters 1 and 2 and heterometallic {MnFe(2)}-type coordination polymers 3-5. Modeling of the magnetic susceptibility data to a isotropic model Hamiltonian yields least-squares fits for the following parameters: J(1)(Mn(II)-Mn(III)) = -6.6 cm(-1) and J(2)(Mn(III)-Mn(III)) = -5.4 cm(-1) for 1; J(1) = -5.5 cm(-1) and J(2)(Mn(III)-Mn(III)) = -3.9 cm(-1) for 2; J(1)(Mn(II)-Fe(III)) = -17.1 cm(-1) and J(2)(Fe(III)-Fe(III)) = -43.7 cm(-1) for 3; J(1) = -23.8 cm(-1) and J(2) = -53.4 cm(-1) for 4; J(1) = -13.3 cm(-1) and J(2) = -35.4 cm(-1) for 5. Intercluster coupling

  1. A new three-dimensional manganese(II) coordination polymer based on the 1,3,5-tris[(1H-imidazol-1-yl)methyl]benzene ligand.

    Science.gov (United States)

    Lu, Xin Hua; Zhong, Kai Long

    2016-11-01

    The self-assembly of coordination polymers and the crystal engineering of metal-organic coordination frameworks have attracted great interest, but it is still a challenge to predict and control the compositions and structures of the complexes. Employing multidentate organic ligands and suitable metal ions to construct inorganic-organic hybrid materials through metal-ligand coordination and hydrogen-bonding interactions has become a major strategy. Recently, imidazole-containing multidentate ligands that contain an aromatic core have received much attention. A new three-dimensional Mn(II) coordination polymer based on 1,3,5-tris[(1H-imidazol-1-yl)methyl]benzene, namely poly[(ethane-1,2-diol-κO)(μ-sulfato-κ(2)O:O'){μ3-1,3,5-tris[(1H-imidazol-1-yl)methyl]benzene-κ(3)N:N':N''}manganese(II)], [Mn(SO4)(C18H18N6)(C2H6O2)]n, was synthesized and characterized by elemental analysis, IR spectroscopy and single-crystal X-ray diffraction. Crystal structural analysis shows that there are two kinds of crystallographically independent Mn(II) centres, each lying on a centrosymmetric position and having a similar six-coordinated octahedral structure. One is coordinated by four N atoms from four 1,3,5-tris[(1H-imidazol-1-yl)methyl]benzene (timb) ligands and two O atoms from two different bridging sulfate anions. The second is surrounded by two timb N atoms and four O atoms, two from sulfate anions and two from two ethane-1,2-diol ligands. The tripodal timb ligand bridges neighbouring Mn(II) centres to generate a two-dimensional layered structure running parallel to the ab plane. Adjacent layers are further bridged by sulfate anions, resulting in a three-dimensional structure with 3,4,6-c topology. Thermogravimetric analysis of the title polymer shows that it is stable up to 533 K. The first weight loss between 533 and 573 K corresponds to the release of coordinated ethane-1,2-diol molecules, and further decomposition occurred at 648 K.

  2. Hydrogen Bond Networks of Three Cobalt Coordination Polymers Based on Bis(triazole) and Benzenebiscarboxylate Isomers%Hydrogen Bond Networks of Three Cobalt Coordination Polymers Based on Bis(triazole) and Benzenebiscarboxylate Isomers

    Institute of Scientific and Technical Information of China (English)

    钱新; 王菊; 崔艳锋; 李宝龙; 李海燕

    2011-01-01

    Three hydrogen bond networks of cobalt(II) coordination polymers { [Co(btp)2(H2O)2]·2(l,2-Hbdc)·2H2O}n (1), { [Co(btp) (1,3 -bdc)(H2O)]·1.5H2O } n (2) and { [Co(btp)2(H2O)2]·(1,4-bdc) } n (3) were synthesized by 1,3 -bis(1,2,4- triazol- 1-yl)propane (btp) and benzenedicarboxylate position isomers. Complex 1 is comprised of [Co(btp)z(H20)]2n+ 1D cation chains, 1,2-Hbdc anions and lattice water molecules. The structure of 2 is an undulated 2D (4,4) network. Two adjacent networks interpenetrate each other to form a new 2D double-layers network which is sustained by the hydrogen bond interactions in 2. Complex 3 is comprised of [Co(btp)z(H20)]n2n+ 1D cation chains and 1,4-bdc2 anions. These [Co(btp)2(H2O)]n^2+ 1D cations and 1,2-Hbdc-/1,4-bdc2- anions form 2D hydrogen bond networks in 1 and 3. The thermal stabilities of 1, 2 and 3 were investigated.

  3. Characteristic differences in the formation of complex coacervate core micelles from neodymium and zinc-based coordination polymers.

    Science.gov (United States)

    Yan, Yun; Besseling, Nicolaas A M; de Keizer, Arie; Stuart, Martien A Cohen

    2007-05-31

    In this paper we compare the formation of complex coacervate core micelles (C3Ms) from two different tricompontent mixtures, namely neodymium, the bisligand L2EO4 and the poly(cation)-block-poly(neutral) diblock copolymer P2MVP41-b-PEO205, and zinc, L2EO4 and P2MVP41-b-PEO205 mixed systems. Three sets of titration experiments were carried out for each system: (i) titration of diblock copolymer P2MVP41-b-PEO205 with the stoichiometric mixture of metal ions and bisligands, (ii) titration of a mixture of diblock copolymer and bisligand with metal ions, and (iii) titration of a mixture of diblock copolymer and metal ions with bisligands. In all the above three cases, micelles are found to form either in a broad range of charge ratios or in a broad range of metal/bisligand ratios. Upon addition of Nd2-(L2EO4)3 coordination polymer to P2MVP41-b-PEO205 solution, and upon addition of Nd3+ to a mixture of L2EO4 and P2MVP41-b-PEO205, micelles are found to form immediately after the first addition, whereas micelles show up in the similar zinc system only after a certain threshold Zn-(L2EO4) or Zn2+ concentration. This difference can be traced to the different structures of the Nd2-(L2EO4)3 and Zn-(L2EO4) coordination compounds. At very low concentrations, Zn-(L2EO4) are ring-like oligomers, but Nd2-(L2EO4)3 are larger networks. The network structure favors the formation of coacervate micellar core with P2MVP41-b-PEO205. Moreover, excess of Nd3+ ions will break up the C3Ms, while the same amount of Zn2+ has hardly any effect on the C3Ms. The breakdown of C3Ms by Nd3+ is due to the charge inversion of the coordination complex with increasing [Nd3+]/[L2EO4] ratio, which results in repulsive interaction between the coordination complex and the diblock copolymer, whereas no such interaction can occur in the zinc system.

  4. Syntheses, structures and properties of two new coordination polymers based on D-camphoric acid and 2-phenyl-4,6-diamino-1,3,5-triazine

    Energy Technology Data Exchange (ETDEWEB)

    Lun, Huijie; Yang, Jinghe; Jin, Linyu; Cui, Sasa; Bai, Yanlong [Henan Key Laboratory of Polyoxometalate, Institute of Molecular and Crystal Engineering, College of Chemistry and Chemical Engineering, Henan University, Kaifeng, Henan 475004 (China); Zhang, Xudong [State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou, Fujian 350002 (China); Li, Yamin, E-mail: liyamin@henu.edu.cn [Henan Key Laboratory of Polyoxometalate, Institute of Molecular and Crystal Engineering, College of Chemistry and Chemical Engineering, Henan University, Kaifeng, Henan 475004 (China)

    2015-05-15

    By hydrothermal method, two new coordination polymers [Co(ca)(phdat)]{sub n} (1), [Ni(ca)(phdat).0.125H{sub 2}O]{sub n} (2) (H{sub 2}ca=D-camphoric acid, phdat=2-phenyl-4,6-diamino-1,3,5-triazine) have been achieved and structurally characterized by IR, elemental analyses, X-ray single-crystal diffraction and TGA. The X-ray single-crystal diffraction reveals that compounds 1 and 2 are isostructural, both of which exhibit two-dimensional layered network built up from paddle-wheel Co{sub 2}(CO{sub 2}){sub 4}/Ni{sub 2}(CO{sub 2}){sub 4} SBUs by ca{sup 2−} ligand. In the existence of π…π stacking interactions between triazine rings and phenyl rings, the 3D networks are constructed with the hanging phdat filled between the neighboring layers. Furthermore, compounds 1–2 exhibit antiferromagnetic behavior and compound 2 displays a good activity for methanol oxidation. - Graphical abstract: Two new coordination compounds 1–2 have been synthesized and characterized by single-crystal X-ray diffractions, IR spectra, elemental analyses, thermogravimetric analyses, magnetic and electrochemical measurement. - Highlights: • This paper reports two new coordination polymers based on D-camphoric acid. • Both the compounds feather two-dimensional layered networks built up from paddle-wheel SBUs. • The magnetism and electrochemical property are investigated.

  5. 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.

  6. Extending framework based on the linear coordination polymers: Alternative chains containing lanthanum ion and acrylic acid ligand

    Science.gov (United States)

    Li, Hui; Guo, Ming; Tian, Hong; He, Fei-Yue; Lee, Gene-Hsiang; Peng, Shie-Ming

    2006-11-01

    One-dimensional alternative chains of two lanthanum complexes: [La( L1) 3(CH 3OH)(H 2O) 2]·5H 2O ( L1=anion of α-cyano-4-hydroxycinnamic acid ) 1 and [La( L2) 3(H 2O) 2]·3H 2O ( L2=anion of trans-3-(4-methyl-benzoyl)-acrylic acid) 2 were synthesized and structurally characterized by single-crystal X-ray diffraction, element analysis, IR and thermogravimetric analysis. The crystal structure data are as follows for 1: C 31H 36LaN 3O 17, triclinic, P-1, a=9.8279(4) Å, b=11.8278(5) Å, c=17.8730(7) Å, α=72.7960(10)°, β=83.3820(10)°, γ=67.1650(10)º, Z=2, R1=0.0377, wR2=0.0746; for 2: C 33H 37LaO 14, triclinic, P-1, a=8.7174(5) Å, b=9.9377(5) Å, c=21.153(2) Å, α=81.145(2)°, β=87.591(2)°, γ=67.345(5)°, Z=2, R1=0.0869, wR2=0.220. 1 is a rare example of the alternative chain constructed by syn-syn and anti-syn coordination mode of carboxylato ligand arranged along the chain alternatively. La(III) ions in 2 are linked by two η3-O bridges and four bridges (two η2-O and two η3-O) alternatively. Both of the linear coordination polymers grow into two- and three-dimensional networks by packing through extending hydrogen-bond network directed by ligands.

  7. Nanoscale coordination polymers for anticancer drug delivery

    Science.gov (United States)

    Phillips, Rachel Huxford

    This dissertation reports the synthesis and characterization of nanoscale coordination polymers (NCPs) for anticancer drug delivery. Nanoparticles have been explored in order to address the limitations of small molecule chemotherapeutics. NCPs have been investigated as drug delivery vehicles as they can exhibit the same beneficial properties as the bulk metal-organic frameworks as well as interesting characteristics that are unique to nanomaterials. Gd-MTX (MTX = methotrexate) NCPs with a MTX loading of 71.6 wt% were synthesized and stabilized by encapsulation within a lipid bilayer containing anisamide (AA), a small molecule that targets sigma receptors which are overexpressed in many cancer tissues. Functionalization with AA allows for targeted delivery and controlled release to cancer cells, as shown by enhanced efficacy against leukemia cells. The NCPs were doped with Ru(bpy)32+ (bpy = 2,2'-bipyridine), and this formulation was utilized as an optical imaging agent by confocal microscopy. NCPs containing the chemotherapeutic pemetrexed (PMX) were synthesized using different binding metals. Zr-based materials could not be stabilized by encapsulation with a lipid bilayer, and Gd-based materials showed that PMX had degraded during synthesis. However, Hf-based NCPs containing 19.7 wt% PMX were stabilized by a lipid coating and showed in vitro efficacy against non-small cell lung cancer (NSCLC) cell lines. Enhanced efficacy was observed for formulations containing AA. Additionally, NCP formulations containing the cisplatin prodrug disuccinatocisplatin were prepared; one of these formulations could be stabilized by encapsulation within a lipid layer. Coating with a lipid layer doped with AA rendered this formulation an active targeting agent. The resulting formulation proved more potent than free cisplatin in NSCLC cell lines. Improved NCP uptake was demonstrated by confocal microscopy and competitive binding assays. Finally, a Pt(IV) oxaliplatin prodrug was

  8. Synthesis, Structure and Properties of Two Novel 2D Zinc(II) Coordination Polymers based on Fluconazole and Benzene Carboxylic Acid

    Energy Technology Data Exchange (ETDEWEB)

    Pan, Ganghong; Tang, Jingniu; Xu, Wenjia; Liang, Peng; Huang, Zhongjing [Guangxi University for Nationalities, Nanning (China)

    2013-12-15

    The design and synthesis of coordination polymers have aroused great interest owing to their intriguing aesthetic structures and potential applications in nonlinear optics, gas storage, ion exchange, luminescence, magnetism and catalysis. Self-assembly of bridging organic ligands (connectors) and multi-connected metal ions can give rise to various types of interesting coordination polymers. Since metal ion Zn(II) with d{sup 10} electronic configuration permits a variety of coordination numbers and geometries which are not dependent on ligand field stabilization but on ligand size and charge, it is well suited for the construction of various coordination polymers. Its borderline hardness allows the coordination of N, O and S donor atoms.

  9. Effect of pH on complex coacervate core micelles from Fe(III)-based coordination polymer.

    Science.gov (United States)

    Wang, Junyou; de Keizer, Arie; van Leeuwen, Herman P; Yan, Yun; Vergeldt, Frank; van As, Henk; Bomans, Paul H H; Sommerdijk, Nico A J M; Cohen Stuart, Martien A; van der Gucht, Jasper

    2011-12-20

    The effect of pH on iron-containing complex coacervate core micelles [Fe(III)-C3Ms] is investigated in this paper. The Fe(III)-C3Ms are formed by mixing cationic poly(N-methyl-2-vinylpyridinium iodide)-b-poly(ethylene oxide) [P2MVP(41)-b-PEO(205)] and anionic iron coordination polymers [Fe(III)-L(2)EO(4)] at stoichiometric charge ratio. Light scattering and Cryo-TEM have been performed to study the variations of hydrodynamic radius and core structure with changing pH. The hydrodynamic radius of Fe(III)-C3Ms is determined mainly by the corona and does not change very much in a broad pH range. However, Cryo-TEM pictures and magnetic relaxation measurements indicate that the structure of the micellar cores changes upon changing the pH, with a more crystalline, elongated shape and lower relaxivity at high pH. We attribute this to the formation of mixed iron complexes in the core, involving both the bis-ligand and hydroxide ions. These complexes are stabilized toward precipitation by the diblock copolymer.

  10. 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

    2017-08-03

    A novel ratiometric fluorescence nanosensor for superoxide anion (O2(•-) ) 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 O2(•-) . The resulting AuNPs-BSA@Tb/GMP NCP ratiometric fluorescence nanosensor for the detection of O2(•-) 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.

  11. Four new coordination polymers based on carboxyphenyl-substituted dipyrazinylpyridine ligand: Syntheses, structures, magnetic and luminescence properties

    Science.gov (United States)

    Yuan, Fei; Zhang, Lu; Hu, Huai-Ming; Bai, Chao; Xue, Ganglin

    2017-01-01

    Four new coordination polymers, namely, [Co(L)2]n (1) and [Co(L)(tp)0.5]n·nH2O (2), [Zn(L)2]n·0.5nH2O (3) and [Zn(L)(suc)0.5]n·nH2O (4) (HL = 4-(3-carboxyphenyl)-2,6-di(pyrazinyl)pyridine, H2tp = benzene-1,4-dicarboxylic acid, H2suc = succinic acid), were constructed by changing metal ion and introducing auxiliary ligand under hydrothermal condition. X-ray single diffraction studies reveal that compounds 1 and 3 have similar structures and crystallized in the monoclinic system with P21/c space group, which show infinite zigzag chains and are further extended into a 2D supramolecular layer by inter-molecular hydrogen bonds. Compounds 2 and 4 display infinite ladder chains and are further extended into a 3D supramolecular network by inter-molecular hydrogen bonds. Additionally, magnetic and photoluminescence properties of 1-4 have been investigated.

  12. 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.

  13. The Enhancement on Proton Conductivity of Stable Polyoxometalate-Based Coordination Polymers by the Synergistic Effect of MultiProton Units.

    Science.gov (United States)

    Li, Jing; Cao, Xue-Li; Wang, Yuan-Yuan; Zhang, Shu-Ran; Du, Dong-Ying; Qin, Jun-Sheng; Li, Shun-Li; Su, Zhong-Min; Lan, Ya-Qian

    2016-06-27

    Two novel polyoxometalate (POM)-based coordination polymers, namely, [Co(bpz)(Hbpz)][Co(SO4 )0.5 (H2 O)2 (bpz)]4 [PMo(VI) 8 Mo(V) 4 V(IV) 4 O42 ]⋅13 H2 O (NENU-530) and [Ni2 (bpz)(Hbpz)3 (H2 O)2 ][PMo(VI) 8 Mo(V) 4 V(IV) 4 O44 ]⋅8 H2 O (NENU-531) (H2 bpz=3,3',5,5'-tetramethyl-4,4'-bipyrazole), were isolated by hydrothermal methods, which represented 3D networks constructed by POM units, the protonated ligand and sulfate group. In contrast with most POM-based coordination polymers, these two compounds exhibit exceptional excellent chemical and thermal stability. More importantly, NENU-530 shows a high proton conductivity of 1.5×10(-3)  S cm(-1) at 75 °C and 98 % RH, which is one order of magnitude higher than that of NENU-531. Furthermore, structural analysis and functional measurement successfully demonstrated that the introduction of sulfate group is favorable for proton conductivity. Herein, the syntheses, crystal structures, proton conductivity, and the relationship between structure and property are presented.

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

    Science.gov (United States)

    Huang, Ya-Jing; Zheng, Yue-Qing; Wang, Jin-Jian; Zhou, Lin-Xia

    2017-02-01

    A new bismuth-based polymer, [Hbpe][Bi(Hpydc)2(pydc)]·H2O (H2pydc=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 Bi2O3 shows [Hbpe][Bi(Hpydc)2(pydc)]·H2O has the higher photocatalytic performance, with the degradation rate of 97% and 2% within 100 min for [Hbpe][Bi(Hpydc)2(pydc)]·H2O and commercial Bi2O3 respectively. Additionally, the five cycle reproducibility results of [Hbpe][Bi(Hpydc)2(pydc)]·H2O implies that it can be used as a stable photocatalyst.

  15. Interpenetration in coordination polymers: structural diversities toward porous functional materials

    Directory of Open Access Journals (Sweden)

    Ritesh Haldar

    2015-03-01

    Full Text Available Interpenetration is a natural phenomenon frequently encountered in porous coordination polymers (PCPs or metal-organic frameworks (MOFs. Traditionally interpenetration has been considered as a threat to permanent porosity and several strategies have been adopted to control the framework interpenetration. Recent literature reports have unveiled that interpenetration has paramount importance in several material properties particularly in storage and separation of small gas molecules. Such frameworks also show interesting structural flexibility based on shearing or movement of the nets and also reveals guest induced dynamic structural transformation for modulated specific functions. In this review, we will emphasize several interpenetration phenomena observed in coordination polymers, their intriguing structural aspects and fascinating material properties.

  16. High-performance supercapacitor based on nitrogen-doped porous carbon derived from zinc(II)-bis(8-hydroxyquinoline) coordination polymer.

    Science.gov (United States)

    Chen, Xiang Ying; Xie, Dong Hua; Chen, Chong; Liu, Jian Wei

    2013-03-01

    Nitrogen-doped porous carbon electrodes with remarkable specific capacitance have been fabricated by the rational carbonization of zinc(II)-bis(8-hydroxyquinoline) (abbr. Znq(2)) coordination polymer, and heating treatment with CO(NH(2))(2). The experimental results demonstrate that the mass ratio of carbon precursor and CO(NH(2))(2) plays a key role in the formation of porous carbon with various nitrogen content as well as specific surface areas and pore structures. The cyclic voltammetry and galvanostatic charge-discharge measurements show that the capacitive performance has been remarkably improved by doping with nitrogen. The specific capacitance of 219.2 F g(-1) is achieved at the current density of 1 A g(-1) with nitrogen-doped porous carbon, increasing up to ca. 56.8% compared to that with pristine porous carbon. The nitrogen-doped porous carbon electrode exhibits enhance capacitance retention as ca. 45.2% at 20 A g(-1) as well as cycling stability (ca. 7.6% loss after 3000 cycles). The present carbonization method as well as the nitrogen-doping method for porous carbon from coordination polymer can enrich the strategies for the production of carbon-based electrodes materials in the application of electrochemical capacitors.

  17. 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)

  18. Controlled isotropic or anisotropic nanoscale growth of coordination polymers: formation of hybrid coordination polymer particles.

    Science.gov (United States)

    Lee, Hee Jung; Cho, Yea Jin; Cho, Won; Oh, Moonhyun

    2013-01-22

    The ability to fabricate multicompositional hybrid materials in a precise and controlled manner is one of the primary goals of modern materials science research. In addition, an understanding of the phenomena associated with the systematic growth of one material on another can facilitate the evolution of multifunctional hybrid materials. Here, we demonstrate precise manipulation of the isotropic and/or anisotropic nanoscale growth of various coordination polymers (CPs) to obtain heterocompositional hybrid coordination polymer particles. Chemical composition analyses conducted at every growth step reveal the formation of accurately assembled hybrid nanoscale CPs, and microscopy images are used to examine the morphology of the particles and visualize the hybrid structures. The dissimilar growth behavior, that is, growth in an isotropic or anisotropic fashion, is found to be dependent on the size of the metal ions involved within the CPs.

  19. Ytterbium Coordination Polymer with Four Different Coordination Numbers: The First Structural Characterization of Lanthanide Phthalate Complex

    Institute of Scientific and Technical Information of China (English)

    WAN,Yong-Hong(万永红); JIN,Lin-Pei(金林培); WANG,Ke-Zhi(王科志)

    2002-01-01

    The novel ytterbium coordination polymer is a two-dimensional framework in which the central metal ions have four different coordination numhers and form four kinds of coordination polyhedra. The four kinds of coordination polyhedra connect into infinite chains by sharing oxygen atoms

  20. Synthesis, structural characterization and antitumor activity of a Ca(II) coordination polymer based on 4-formyl-1,3-benzenedisulfonate-2-furoic acid hydrazide ligands

    Science.gov (United States)

    Tai, Xi-Shi; Wang, Xin

    2017-03-01

    A new Ca(II) coordination polymer, {[CaL(H2O)4] · (H2O)4} n (L = 4-formyl-1,3-benzenedisulfonate-2-furoic acid hydrazide) has been prepared by one-pot synthesis method. And it was characterized by elemental analysis, IR and thermal analysis. The result of X-ray single-crystal diffraction analysis shows that the Ca(II) complex molecules form one-dimensional chain structure by the bridging oxygen atoms. The anti-tumor activity of L ligand and the Ca(II) coordination polymer has also been studied.

  1. 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.

  2. One novel multidimensional organic-inorganic hybrid based on polyoxometalates and copper chlorine coordination polymers with 4,4′-bipyridine ligands

    Institute of Scientific and Technical Information of China (English)

    Li Chun Xuan; Qing Jiang Pan

    2012-01-01

    One novel organic-inorganic hybrid materials with 4,4′-bipy ligands and copper chlorine coordination polymers as linkers,with new topology,{[CuI(4,4′-bipy)]10Cl2(SiW12O40)2}·6H2O (1) (4,4′-bipy =4,4′-bipyridine),has been hydrothermally synthesized.The single crystal X-ray structural analysis reveals that the structure of 1 is constructed from classical Keggin anions and [CuI(4,4′-bipy)] cations into a novel,three-dimensional (3D) polyoxometalates (POMs)based network.From the topological view,compound 1 is a novel (3.44.52.63)(32.44.56.69) topology.The electrochemical and photocatalysis properties of 1 have been investigated in details.

  3. 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.

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

    Science.gov (United States)

    Yan, Yun; de Keizer, Arie; Cohen Stuart, Martien A; Drechsler, Markus; Besseling, Nicolaas A M

    2008-09-01

    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 bisligand molecules. The influence of added salt, polymer concentration, and charge composition was investigated by using light scattering and cryo-TEM techniques. The scattering intensity decreases strongly with increasing salt concentration until a critical salt concentration beyond which no micelles exist. The critical micelle concentration increases almost exponentially with the salt concentration. From the scattering results it follows that the aggregation number decreases with the square root of the salt concentration, but the hydrodynamic radius remains constant or increases slightly. It was concluded that the density of the core decreases with increasing ionic strength. This is in agreement with theoretical predictions and is also confirmed by cryo-TEM measurements. A complete composition diagram was constructed based on the composition boundaries obtained from light scattering titrations.

  5. Multifunctional Magnetic Gd(3+) -Based Coordination Polymer Nanoparticles: Combination of Magnetic Resonance and Multispectral Optoacoustic Detections for Tumor-Targeted Imaging in vivo.

    Science.gov (United States)

    An, Qiao; Liu, Jing; Yu, Meng; Wan, Jiaxun; Li, Dian; Wang, Changchun; Chen, Chunying; Guo, Jia

    2015-11-11

    To overcome traditional barriers in optical imaging and microscopy, optoacoustic-imaging has been changed to combine the accuracy of spectroscopy with the depth resolution of ultrasound, achieving a novel modality with powerful in vivo imaging. However, magnetic resonance imaging provides better spatial and anatomical resolution. Thus, a single hybrid nanoprobe that allows for simultaneous multimodal imaging is significant not only for cutting edge research in imaging science, but also for accurate clinical diagnosis. A core-shell-structured coordination polymer composite microsphere has been designed for in vivo multimodality imaging. It consists of a Fe3 O4 nanocluster core, a carbon sandwiched layer, and a carbocyanine-Gd(III) (Cy-Gd(III) ) coordination polymer outer shell (Fe3 O4 @C@Cy-Gd(III) ). Folic acid-conjugated poly(ethylene glycol) chains are embedded within the coordination polymer shell to achieve extended circulation and targeted delivery of probe particles in vivo. Control of Fe3 O4 core grain sizes results in optimal r2 relaxivity (224.5 × 10(-3) m(-1) s(-1) ) for T2 -weighted magnetic resonance imaging. Cy-Gd(III) coordination polymers are also regulated to obtain a maximum 25.1% of Cy ligands and 5.2% of Gd(III) ions for near-infrared fluorescence and T1 -weighted magnetic resonance imaging, respectively. The results demonstrate their impressive abilities for targeted, multimodal, and reliable imaging.

  6. Central metal ion exchange in a coordination polymer based on lanthanide ions and di(2-ethylhexyl)phosphoric acid: exchange rate and tunable affinity.

    Science.gov (United States)

    Tasaki-Handa, Yuiko; Abe, Yukie; Ooi, Kenta; Tanaka, Mikiya; Wakisaka, Akihiro

    2014-01-01

    In this paper the exchange of lanthanide(III) ions (Ln(3+)) between a solution and a coordination polymer (CP) of di(2-ethylhexyl)phosphoric acid (Hdehp), [Ln(dehp)3], is studied. Kinetic and selectivity studies suggest that a polymeric network of [Ln(dehp)3] has different characteristics than the corresponding monomeric complex. The reaction rate is remarkably slow and requires over 600 h to reach in nearly equilibrium, and this can be explained by the polymeric crystalline structure and high valency of Ln(3+). The affinity of the exchange reaction reaches a maximum with the Ln(3+) possessing an ionic radius 7% smaller than that of the central Ln(3+), therefore, the affinity of the [Ln(dehp)3] is tunable based on the choice of the central metal ion. Such unique affinity, which differs from the monomeric complex, can be explained by two factors: the coordination preference and steric strain caused by the polymeric structure. The latter likely becomes predominant for Ln(3+) exchange when the ionic radius of the ion in solution is smaller than the original Ln(3+) by more than 7%. Structural studies suggest that the incoming Ln(3+) forms a new phase though an exchange reaction, and this could plausibly cause the structural strain.

  7. Anion-dependent formation of four coordination polymers based on N,N‧-di(3-pyridine) oxamide (DPOM): Crystal structures and luminescence

    Science.gov (United States)

    Deng, Ji-Hua; Wen, Ya-Qiong; Luo, Xu-Zhong; Zhong, Di-Chang

    2017-09-01

    Presented in this article are the anion-tuning formation, crystal structures and luminescent properties of four coordination polymers of N,N‧-di(3-pyridine) oxamide (DPOM), including two one-dimensional (1D) chain/ladder polymers, [Ni(DPOM)(H2O)4]SO4·2H2O (1) and [Cd4(DPOM)6(NO3)8] (2), as well as two 3D coordination polymers, [Zn2(DPOM)(H2O)4(SO4)2] (3) and [Cd2(DPOM)(H2O)4(SO4)2] (4). The results of single crystal X-ray diffraction analyses indicate that in these coordination polymers, DPOM ligand serves as a bridge, connecting metal ions by both terminal pyridine N atoms. 1 is a 1D chain structure formed by the bridge of DPOM. 2 is a 1D ladder-like structure featuring Cd(NO3)2 structural units bridged by DPOM ligands. Both 3 and 4 are 3D pillar-layer structures with the 2D inorganic layer ZnSO4/CdSO4 pillared by DPOM ligands. The results of photoluminescent measurements illustrate that upon excitation, 2-4 can emit fluorescence in 408, 416, and 422 nm in the solid state, respectively.

  8. Syntheses and structural characterization of mercury (II) coordination polymers with neutral bidentate flexible pyrazole-based ligands

    Science.gov (United States)

    Lalegani, Arash; Khaledi Sardashti, Mohammad; Salavati, Hossein; Asadi, Amin; Gajda, Roman; Woźniak, Krzysztof

    2016-03-01

    Mercury(II) coordination compounds [Hg(μ-bbd)(μ-SCN)4]n(1) and [Hg(bpp)(SCN)2] (2) were synthesized by using the neutral flexible bidentate N-donor ligands 1,4-bis(3,5-dimethypyrazol-1-yl)butane (bbd) and 1,3-bis(3,5-dimethylpyrazolyl)propane (bpp), NCS- ligand and appropriate mercury(II) salts. Compound 1 forms a polymeric network with moieties which are connected by SCN groups and the mercury ions present as HgN3S2 trigonal bipyramides. The crystal structure of 2 is build of monomers and the mercury(II) ion adopts an HgN2S2 tetrahedral geometry. In the complex 1, each bbd acts as bridging ligand connecting Hg(μ-SCN)4 ions, while in the complex 2, the bpp ligand is coordinated to an mercury(II) ion in a cyclic-bidentate fashion forming an eight-membered metallocyclic ring. Moreover, in the tetrahedral structure of 2, the neutral molecules form a 1D chain structure through the C-H···N hydrogen bonds, whereas in 1 no hydrogen bonds are observed. Coordination compounds 1 and 2 have been characterized by infrared spectroscopy, elemental analyses and single-crystal X-ray diffraction.

  9. 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

    2008-11-01

    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.

  10. Stable Polymer Micelles Formed by Metal Coordination

    NARCIS (Netherlands)

    Wang, Junyou; Stuart, Martien A. Cohen; Marcelis, Antonius T. M.; Colomb-Delsuc, Mathieu; Otto, Sijbren; van der Gucht, Jasper

    2012-01-01

    Metal-containing polymer micelles have attracted much attention due to their potential for medical and nanotechnological applications. In this paper, we present a method to prepare stable metal-containing polymer micelles. A diblock copolymer poly(4-vinylpyridine)-b-poly(ethylene oxide) (P4VP(48)-b-

  11. Hydrogen bonding and multiphonon structure in copper pyrazine coordination polymers.

    Science.gov (United States)

    Brown, S; Cao, J; Musfeldt, J L; Conner, M M; McConnell, A C; Southerland, H I; Manson, J L; Schlueter, J A; Phillips, M D; Turnbull, M M; Landee, C P

    2007-10-15

    We report a systematic investigation of the temperature-dependent infrared vibrational spectra of a family of chemically related coordination polymer magnets based upon bridging bifluoride (HF(2)-) and terminal fluoride (F-) ligands in copper pyrazine complexes including Cu(HF(2))(pyz)(2)BF(4), Cu(HF(2))(pyz)(2)ClO(4), and CuF(2)(H(2)O)(2)(pyz). We compare our results with several one- and two-dimensional prototype materials including Cu(pyz)(NO(3))(2) and Cu(pyz)(2)(ClO(4))(2). Unusual low-temperature hydrogen bonding, local structural transitions associated with stronger low-temperature hydrogen bonding, and striking multiphonon effects that derive from coupling of an infrared-active fundamental with strong Raman-active modes of the pyrazine building-block molecule are observed. On the basis of the spectroscopic evidence, these interactions are ubiquitous to this family of coordination polymers and may work to stabilize long-range magnetic ordering at low temperature. Similar interactions are likely to be present in other molecule-based magnets.

  12. 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.

  13. Extending the lanthanide-terephthalate system: Isolation of an unprecedented Tb(III)-based coordination polymer with high potential porosity and luminescence properties

    Science.gov (United States)

    Le Natur, François; Calvez, Guillaume; Freslon, Stéphane; Daiguebonne, Carole; Bernot, Kevin; Guillou, Olivier

    2015-04-01

    A novel coordination polymer with chemical formula {[Tb(bdc)1.5(H2O)]ṡ(DMF)(H2O)}∞ (1) has been synthesized by reaction between 1,4-benzene-dicarboxylic acid (H2bdc) and di-cationic hexanuclear entity [Tb6O(OH)8(NO3)6(H2O)12]2+ in an ethylene glycol (EG)/N,N-dimethylformamide (DMF) mixture. This compound has been obtained as single crystals by slow evaporation in air at room temperature. If the hexanuclear entity is destroyed during the reaction, the coordination polymer that is obtained is original and presents promising potential micro-porosity and luminescent properties. It crystallizes in the monoclinic system, space group C12/c1 (No. 15) with the cell parameters a = 23.7540(1) Å, b = 10.5390(4) Å, c = 19.7580(3) Å, β = 125.8100(1)° and Z = 8.

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

    Science.gov (United States)

    Feng, Xun; Liu, Jing; Li, Jin; Ma, Lu-Fang; Wang, Li-Ya; Ng, Seik-Weng; Qin, Guo-Zhan

    2015-10-01

    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.

  15. 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.

  16. Construction of copper-based coordination polymers with 1D chain, 2D plane and wavy networks: Syntheses, structures, thermal behaviors and photoluminescence properties

    Indian Academy of Sciences (India)

    Jianghua Li; Chi Zhang

    2015-11-01

    Three Cu-based coordination polymers (CPs), including [CuII ( -1 -NCS)2 (O-1 -DMF)2 (2 -3,3’-bptz)] (1), [CuI (1,3-2-NCS)(2-3,3’-bptz)] (2) and [(CuI (1,3-μ2- NCS))(2-4,4’-bptz)] (3) (DMF = , -dimethyl formamide, 3,3’-bptz = 3,6-bis(3-pyridyl)tetrazine and 4,4’-bptz = 3,6-bis(4-pyridyl)tetrazine) have been successfully constructed by solution diffusion reactions by using Cu(NO3)2 ·3H2O or CuNCS and KNCS with 3,3’-bptz / 4,4’-bptz ligands, respectively. The resulting crystalline materials have been characterized by the single-crystal X-ray diffraction analyses, elemental analyses, FT-IR spectra, thermogravimetric analyses and powder X-ray diffraction (PXRD). Single crystal X-ray analyses revealed that CP 1 is organized in one-dimensional (1D) chain in which the Cu(II) ions are coordinated by 1 -NCS− anions and 1-DMF molecules, and linked by 2-3,3’-bptz bridging ligands. CPs ,2 and 3 are structural isomers. CP 2 exhibits two-dimensional (2D) (4,4)-plane-like network in which Cu(I) ions are linked by 2-NCS − and 2-3,3’-bptz ligands. In CP 3, Cu(I) ions are connected by 2 -NCS − and 2-4,4’-bptz ligands to form 2D saw-tooth wavy network. In addition, the photoluminescence properties of CPs 1-3 were also investigated in the solid state at room temperature.

  17. Structural and Magnetic Properties of Copper(II) Coordination Polymers Containing Fluoride-Based Anions and Ancillary Organic Ligands

    Science.gov (United States)

    Conner, M.; McConnell, A.; Schlueter, J.; Manson, J.

    2006-02-01

    The fluoride (F-) and bifluoride (HF 2 - ) anions have been little used in the self-assembly of molecular and polymeric magnets. We have recently synthesized several new compounds, namely CuF2(3-OHpy)4 (OHpy = hydroxypyridine) (1), Cu(SiF6)(2,6-me2pyz)4 (me2pyz = dimethylpyrazine) (2), CuF2(H2O)2(pyz) (pyz = pyrazine) (3) and [Cu(HF2)(pyz)2]BF4 (4). Compound 1 contains coordinate covalent and hydrogen bonding interactions that link the Cu(II) ions into 3D networks while 2 features square-pyramidal Cu(II) ions that are weakly bridged by SiF 6 2- anions into 1D chains. Preliminary structural data indicate that compound 3 contains 1D Cu-pyz-Cu chains while 4 contains two dimensional [Cu(pyz)2]2+ layers, which held together via HF 2 - anions so as to form an unprecedented 3D network. The magnetic properties of each are briefly described herein.

  18. 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.

  19. Visible and NIR photoluminescence properties of a series of novel lanthanide-organic coordination polymers based on hydroxyquinoline-carboxylate ligands.

    Science.gov (United States)

    Gai, Yan-Li; Xiong, Ke-Cai; Chen, Lian; Bu, Yang; Li, Xing-Jun; Jiang, Fei-Long; Hong, Mao-Chun

    2012-12-17

    A series of novel two-dimensional (2D) lanthanide coordination polymers with 4-hydroxyquinoline-2-carboxylate (H(2)hqc) ligands, [Ln(Hhqc)(3)(H(2)O)](n)·3nH(2)O (Ln = Eu (1), Tb (2), Sm (3), Nd (4), and Gd (5)) and [Ln(Hhqc)(ox)(H(2)O)(2)](n) (Ln = Eu (6), Tb (7), Sm (8), Tm (9), Dy (10), Nd (11), Yb (12), and Gd (13); H(2)ox = oxalic acid), have been synthesized under hydrothermal conditions. Complexes 1-5 are isomorphous, which can be described as a two-dimensional (2D) hxl/Shubnikov network based on Ln(2)(CO(2))(4) paddle-wheel units, and the isomorphous complexes 6-13 feature a 2D decker layer architecture constructed by Ln-ox infinite chains cross-linked alternatively by bridging Hhqc(-) ligands. The room-temperature photoluminescence spectra of complexes Eu(III) (1 and 6), Tb(III) (2 and 7), and Sm(III) (3 and 8) exhibit strong characteristic emissions in the visible region, whereas Nd(III) (4 and 11) and Yb(III) (12) complexes display NIR luminescence upon irradiation at the ligand band. Moreover, the triplet state of H(2)hqc matches well with the emission level of Eu(III), Tb(III), and Sm(III) ions, which allows the preparation of new optical materials with enhanced luminescence properties.

  20. Synthesis,Structure and Luminescence of Two Coordination Polymers Based on 1,4-Benzenedicarboxylate and 2-(3-Pyridyl)benzimidazole Ligands

    Institute of Scientific and Technical Information of China (English)

    LI wei; LI Ming-Xing; HE Xiang; SHAO Min; AN Bao-Li

    2008-01-01

    Hydrothermal reactions of Cd(Ⅱ)/Zn(Ⅱ)nitrates with 1,4-benzenedicarboxylic acid(H2Bdc)and 2-(3-pyridyl)-benzimidazole(3-PyHBIm)afforded complexes {[Cd(3-PyHBlm)(Bdc)(H2O)2](H2Bdc)1/2]n(1)and [Zn(3-PyHBIm)2-(Bdc)(H2O)2]n(2).X-ray structural analysis reveals that both complexes are ID coordination polymers.In complex 1,3-PyHBIm coordinates to Cd(Ⅱ)unidentately via a pyridyl N-donor.Bdc2-anion acts as a tetradentate ligand and coordinates to Cd(Ⅱ)to form a zigzag chain where two H2O coordinate in cis-fashion.H2Bdc guest molecule is involved in the hydrogen-bonding network,which leads to a 3D supramolecular architecture.In complex 2,Bdc2-acts as a bidentate ligand and coordinates to Zn(Ⅱ)to form a linear infinite chain where two H2O molecules coordi-nate in trans-fashion.The complexes are thermally stable and exhibit luminescence in the solid state.

  1. Assembly and Characterization of Coordination Polymer Nanostructural Materials at Interfaces

    Institute of Scientific and Technical Information of China (English)

    2007-01-01

    1 Results Molecular self-assembly of one-/two-dimensional (1D/2D) nanostructures has recently received great interest because the specific structures of crystals determine their unique physical and chemical properties. Coordination polymers contain two central components, connectors and linkers. Transition metal ions are often used as versatile connectors, with coordination numbers ranging from 2 to 7 dependant on the oxidation states of the metal ions. Multidentate ligands are often used as linkers, wh...

  2. Mixed ligand coordination polymer based on 5-nitroisophthalic acid and 1-(4-nitrophenyl)-1,2,4-triazole: Synthesis, characterization, magnetic and photocatalytic properties

    Science.gov (United States)

    Li, Le; Ju, Wen-Wen; Tao, Jian-Qing; Xin, Rong; Wang, Jun; Xu, Xiao-Juan

    2015-09-01

    A new Cu(II) coordination polymer, namely, [Cu(NPT)2(NO2-BDC)]n (1) (NO2-H2BDC = 5-nitro-1,3-benzenedicarboxylic acid, NPT = 4-(4-nitrophenyl)-1,2,4-triazole) has been synthesized under hydrothermal condition and characterized by elemental analysis, and single-crystal X-ray diffraction. Single-crystal X-ray diffraction study reveals that complex 1 features one-dimensional chain structure. The magnetic studies reveal that the antiferromagnetic interactions exist between the adjacent CuII ions. Moreover, complex 1 displays highly photocatalytic degradation activity for the degradation of rhodamine B, methylene blue and methyl orange.

  3. Two novel interpenetrated zinc(Ⅱ) and cadmium(Ⅱ) coordination polymers based on 4-imidazole-benzoate: Syntheses, crystal structures and properties

    Institute of Scientific and Technical Information of China (English)

    BAI ZhengShuai; CHEN ShuiSheng; ZHANG ZhengHua; CHEN ManSheng; LIU GuangXiang; SUN WeiYin

    2009-01-01

    Two novel interpenetrated coordination polymers, [Zn(IBA)2]n (1) and {[Cd(IBA)2(H2O)]-4H2O}n (2),have been synthesized by using 4-imidazole-benzoic acid (HIBA) as ligand under hydrothermal con-ditions. Complex I crystallizes in a chiral space group and has a two-fold interpenetrated 2D network structure with (4,4) topology, while complex 2 is a 3D porous dia network with four nets interpene-trating each other. The SHG activity of 1 and the photoluminescent property of 2 have been investi-gated.

  4. A one-dimensional coordination polymer based on Cu3-oximato metallacrowns bridged by benzene-1,4-dicarboxylato ligands: structure and magnetic properties.

    Science.gov (United States)

    Croitor, Lilia; Coropceanu, Eduard B; Petuhov, Oleg; Krämer, Karl W; Baca, Svetlana G; Liu, Shi-Xia; Decurtins, Silvio; Fonari, Marina S

    2015-05-07

    A one-dimensional linear coordination polymer {[Cu3(μ3-OH)(2-pyao)3(bdc)]·6(H2O)}n () composed of trinuclear [Cu3(μ3-OH)(2-pyao)3](2+) metallacrown cores bridged by bis-carboxylato linkers has been obtained by treatment of copper(ii) fluoride with pyridine-2-aldoxime (2-pyaoH) ligand and benzene-1,4-dicarboxylic acid (H2bdc). Magnetic susceptibility measurements show strong antiferromagnetic interactions between Cu(ii) centers within the trinuclear metallacrown core with J = -430 cm(-1).

  5. Metal ions directed assembly of two coordination polymers based on an organic phosphonate anion and a multidentate N-donor ligand

    Science.gov (United States)

    Kan, Wei-Qiu; Xu, Ji-Ming; Wen, Shi-Zheng; Yang, Lin

    2017-01-01

    Two new coordination polymers [Cd(4,4‧-tmbpt)(HL)(H2O)] (1) and [Cu(4,4‧-tmbpt)(HL)]·H2O (2) (H3L = 2‧-carboxybiphenyl-4-ylmethylphosphonic and 4,4‧-tmbpt = 1-((1H-1,2,4-triazol-1-yl)methyl)-3,5-bis(4-pyridyl)-1,2,4-triazole) have been synthesized hydrothermally. The two compounds have the same metal to ligand ratio, but different metal ions. As a result, the two compounds display different 2D layer structures, which is mainly caused by the different coordination numbers of the different metal ions. The effects of the metal ions on the structures, the optical band gaps and photoluminescent and photocatalytic properties of the compounds have been studied.

  6. Coordination polymer based on Cu(II), Co(II) and 4,4'-bipyridine-2,6,2',6'-tetracarboxylate: synthesis, structure and adsorption properties.

    Science.gov (United States)

    Zhao, Zhou; He, Xiang; Zhao, Yongmei; Shao, Min; Zhu, Shourong

    2009-04-21

    4,4'-Bipyridine-2,6,2',6'-tetracarboxylic acid H4L.3H2O, () and its copper(II) and cobalt (II) coordination polymers [Cu2L(H2O)4]2n () and {[Co(H2O)6].[Co3L2(H2O)2].10H2O}3n () have been hydrothermally synthesized. Compound packs into a crystal via H-bonds. Complex is a 2D coordination grid, in which Cu is in an elongated octahedral constructed by a mer-geometry pyridyl-2,6-dicarboxylate, one bridging carboxylate oxygen and two water molecules. The L4- is central symmetrical. Each pyridyl-2,6-dicarboxylate chelete to Cu(II) and one carboxylate bridge Cu(II) ions in a 1,1-fashion. The 2D coordination polymer links to adjacent layers via H-bonds. Complex is a metal-organic framework with 11.6x10.5 A rectangular channels. All Co(II) ions are located in an octahedral coordination environment. The rectangular channels are composed of Co2+-L4- walls and the walls are linked through carboxylate oxygen atoms and Co(II) ions. Co(H2O)6(2+) as counter ions fill in porous channel. The removal of water molecules from at 210 degrees C or higher affords the porous material [Co4L2]n, which can adsorb 16 (36%) methanol or 9 (32%) ethanol in the vapour phase. The porosity of is higher than reported 4,4'-bipyridine-2,6,2',6'- tetracarboxylate complexes. The framework of remains but the crystallinity is lost upon removal of the H2O molecules. The dehydrated framework of partially recovery crystallinity after it adsorbs H2O, CH3OH and C2H5OH. The methanol in the framework can be replaced by H2O reversibly.

  7. A High Dimensional Coordination Polymer Based on [β-Mo8O26]4- Inorganic Building Block: Synthesis, Structure and Topology

    Institute of Scientific and Technical Information of China (English)

    DU Xiao-Di; LI Chun-Yang; JIN Gang; CHANG Jia-Zhong; WANG Zhen-Ling

    2012-01-01

    A high dimensional copper coordination polymer {[Cu2(btb)2(H2O)4( -Mo8O26)] H2O}n(1, btb = 1,4-bis(1,2,4-triazol-1-yl)butane) based on [ -Mo8O26]4 anions and flexible bis(triazole) ligands has been synthesized and characterized by elemental analysis, IR spectra, single-crystal X-ray diffraction and thermal analysis. The crystallographic data show that complex 1 crystallizes in triclinic space group P with a = 9.7550(10), b = 10.3996(11), c = 10.9516(11), = 77.622(2), = 89.602(2), = 87.610(2), V = 1084.25(19)3, C16H34Cu2Mo8 N12O31, Mr = 1785.15, Dc = 2.734 g cm 3, μ(MoKα) = 3.303 mm 1, F(000) = 856, GOF = 1.060, Z = 1, the final R = 0.0376 and wR = 0.0982 for I 〉 2 (I). In 1, the inorganic building block [ -Mo8O26]4 anions are connected with each other to generate one-dimensional chains. Then the chains are further connected by Cu2+ ions to form a three-dimensional (3D) inorganic framework [Cu2( -Mo8O26)]n containing quadrangular channels, with the pcu alpha-Po primitive cubic topology. The btb ligands are encapsulated into the void of the 3D inorganic framework forming a new three-dimensional architecture. The thermal analysis illustrates that complex 1 retains a comparatively good thermal stability.

  8. Single cyanide-bridged Mo(W)/S/Cu cluster-based coordination polymers: Reactant- and stoichiometry-dependent syntheses, effective photocatalytic properties

    Science.gov (United States)

    Zhang, Jinfang; Wang, Chao; Wang, Yinlin; Chen, Weitao; Cifuentes, Marie P.; Humphrey, Mark G.; Zhang, Chi

    2015-11-01

    The systematic study on the reaction variables affecting single cyanide-bridged Mo(W)/S/Cu cluster-based coordination polymers (CPs) is firstly demonstrated. Five anionic single cyanide-bridged Mo(W)/S/Cu cluster-based CPs {[Pr4N][WS4Cu3(CN)2]}n (1), {[Pr4N][WS4Cu4(CN)3]}n (2), {[Pr4N][WOS3Cu3(CN)2]}n (3), {[Bu4N][WOS3Cu3(CN)2]}n (4) and {[Bu4N][MoOS3Cu3(CN)2]}n (5) were prepared by varying the molar ratios of the starting materials, and the specific cations, cluster building blocks and central metal atoms in the cluster building blocks. 1 possesses an anionic 3D diamondoid framework constructed from 4-connected T-shaped clusters [WS4Cu3]+ and single CN- bridges. 2 is fabricated from 6-connected planar 'open' clusters [WS4Cu4]2+ and single CN- bridges, forming an anionic 3D architecture with an "ACS" topology. 3 and 4 exhibit novel anionic 2-D double-layer networks, both constructed from nest-shaped clusters [WOS3Cu3]+ linked by single CN- bridges, but containing the different cations [Pr4N]+ and [Bu4N]+, respectively. 5 is constructed from nest-shaped clusters [MoOS3Cu3]+ and single CN- bridges, with an anionic 3D diamondoid framework. The anionic frameworks of 1-5, all sustained by single CN- bridges, are non-interpenetrating and exhibit huge potential void volumes. Employing differing molar ratios of the reactants and varying the cluster building blocks resulted in differing single cyanide-bridged Mo(W)/S/Cu cluster-based CPs, while replacing the cation ([Pr4N]+ vs. [Bu4N]+) was found to have negligible impact on the nature of the architecture. Unexpectedly, replacement of the central metal atom (W vs. Mo) in the cluster building blocks had a pronounced effect on the framework. Furthermore, the photocatalytic activities of heterothiometallic cluster-based CPs were firstly explored by monitoring the photodegradation of methylene blue (MB) under visible light irradiation, which reveals that 2 exhibits effective photocatalytic properties.

  9. Anion-dependent construction of a series of fluorescent coordination polymers based on 1D zinc∩4,4‧-bis(imidazol-1-yl)-biphenyl substrates

    Science.gov (United States)

    Zou, Kang-Yu; Zou, Qian; Han, Tong; Liu, Yi-Chen; Wang, Jun-Jie; Zhang, Xue; Li, Zuo-Xi

    2016-03-01

    In this work, the rod-like ligand 4,4‧-bis(imidazol-1-yl)-biphenyl (bibp) has been utilized as a building block to carry out counterion effects on the structural diversities of coordination polymers. A series of new zinc complexes, [Zn(trans-bibp)Cl2]∞ (1), [Zn(trans-bibp)Br2]∞ (2), {[Zn(cis-bibp)(Ac)2]·(H2O)}∞ (3), [Zn(trans-bibp)SO4]∞ (4), {[Zn2(cis-bibp)2(ipa)2]·(H2O)}∞ (5, H2ipa=isophthalic acid) and {[Zn(trans-bibp)(cis-bibp)]·(ClO4)2(CHCl3)2(CH3OH)}∞ (6) have been successfully synthesized. Complexes 1 and 2 are iso-structural, which show a 1D W-type chain [Zn(trans-bibp)]∞. Complex 3 exhibits a 2D wave-like layer formed by the hydrogen bond among the 1D linear chain [Zn(cis-bibp)]∞. Complex 4 displays a 2D fish-bone lattice, which is generated from connecting the 1D W-type chain [Zn(trans-bibp)]∞ by the μ2-SO42- . Complex 5 presents an interesting 2D-3D 65·8 architecture, including two 1D chains [Zn(ipa)]∞ and [Zn(cis-bibp)]∞. Complex 6 demonstrates a 2D wave-like layer [Zn(trans-bibp)(cis-bibp)]∞. The structural diversities among 1-6 have been carefully discussed, and the role of counterion in the self-assembly of coordination polymer have also been well documented from the coordination affinity and bridging mode. Furthermore, the solid-state fluorescence properties of 1-6 at room temperature have been studied.

  10. Syntheses, structures and luminescence of three copper(I) cyanide coordination polymers based on trigonal 1,3,5-tris(1H-imidazol-1-yl)benzene ligand

    Science.gov (United States)

    Shao, Min; Li, Ming-Xing; Lu, Li-Ruo; Zhang, Heng-Hua

    2016-09-01

    Three Cu(I)-cyanide coordination polymers based on trigonal 1,3,5-tris(1H-imidazol-1-yl)benzene (tib) ligand, namely [Cu3(CN)3(tib)]n (1), [Cu4(CN)4(tib)]n (2), and [Cu2(CN)2(tib)]n (3), have been prepared and characterized by elemental analysis, IR, PXRD, thermogravimetry and single-crystal X-ray diffraction analysis. Complex 1 displays a 3D metal-organic framework with nanosized pores. Complex 2 is a 3D coordination polymer assembled by three μ2-cyanides and a μ3-cyanide with a very short Cu(I)···Cu(I) metal bond(2.5206 Å). Complex 3 is a 2D coordination polymer constructing from 1D Cu(I)-cyanide zigzag chain and bidentate tib spacer. Three Cu(I) complexes are thermally stable up to 250-350 °C. Complexes 1-3 show similar orange emission band at 602 nm originating from LMCT mechanism.

  11. Double-electrochromic coordination polymer network films.

    Science.gov (United States)

    Maier, Anna; Cheng, Kalie; Savych, Julia; Tieke, Bernd

    2011-07-01

    Formation and characteristic properties of organized double-electrochromic films consisting of electrochromic poly(4-(2,2':6,2″-terpyridyl)phenyliminofluorene) (P-1)-zinc ion complexes and electrochromic anions are reported. The anions are 2,2'-azino-bis(3-ethylbenzo-thiazoline-6-sulfonate) (ABTS) and poly((4-sulfonatophenyl)iminofluorene) (P-2). The films were prepared upon multiple sequential adsorption of P-1 and the zinc salts of ABTS and P-2 on solid supports using coordinative interactions between the Zn ions and the terpyridine (tpy) ligands. The ABTS and P-2 ions are incorporated in the films via electrostatic forces neutralizing the charge of the complexed divalent zinc (Zn(2+)) ions. The optical, electrochemical, and electrochromic properties of the films are described. Films consisting of the Zn ion complex of P-1 and ABTS are yellow in the neutral state and change their color to brownish gray and finally blue, if anodically oxidized at ∼640 mV vs FOC. Films containing the Zn ion complex of P-1, with P-2 as a counterion, are yellow in the neutral state and change color to dark red and finally blue, if anodically oxidized at ∼450 mV vs FOC. Compared with previously reported films of the Zn ion complex of P-1 with nonelectroactive hexafluorophosphate as the counterion, the new films exhibit faster response times, as well as higher contrast, and the colors in the oxidized state are modified. The films are stable under ambient conditions and might be useful as active layers in electrochromic devices.

  12. A lanthanum pyromellitate coordination polymer with threedimensional structure

    Indian Academy of Sciences (India)

    S V Ganesan; Srinivasan Natarajan

    2004-03-01

    A new three-dimensional metal-organic coordination polymer, [La2(H2O)2(H2BTEC)(BTEC)], 1, was hydrothermally synthesized and characterized by single crystal X-ray diffraction. The threedimensional framework is built up from La2O16 dimers connected by carboxylate anions. The polymer exhibits strong photoluminescence at room temperature with the main emission band at 390 nm (ex = 338 nm). Crystal data: triclinic, space group (-1), = 6.4486(3), = 9.4525(5), = 9.6238(5) Å, = 88.24(1), = 74.67(2), = 76.76(1)°, = 550.45(5).

  13. Synthesis, structure, thermostability and luminescence properties of Zn(II) and Cd(II) coordination polymers based on dimethysuccinate and flexible 1,4-bis(imidazol-1-ylmethyl)benzene ligands.

    Science.gov (United States)

    Liu, Yang; Feng, Yong Lan; Fu, Wei Wei

    2016-09-01

    The design and synthesis of functional coordination polymers is motivated not only by their structural beauty but also by their potential applications. Zn(II) and Cd(II) coordination polymers are promising candidates for producing photoactive materials because these d(10) metal ions not only possess a variety of coordination numbers and geometries, but also exhibit luminescence properties when bound to functional ligands. It is difficult to predict the final structure of such polymers because the assembly process is influenced by many subtle factors. Bis(imidazol-1-yl)-substituted alkane/benzene molecules are good bridging ligands because their flexibility allows them to bend and rotate when they coordinate to metal centres. Two new Zn(II) and Cd(II) coordination polymers based on mixed ligands, namely, poly[[μ2-1,4-bis(imidazol-1-ylmethyl)benzene-κ(2)N(3):N(3')]bis(μ3-2,2-dimethylbutanoato-κ(3)O(1):O(4):O(4'))dizinc(II)], [Zn2(C6H8O4)2(C14H14N4)]n, and poly[[μ2-1,4-bis(imidazol-1-ylmethyl)benzene-κ(2)N(3):N(3')]bis(μ3-2,2-dimethylbutanoato-κ(5)O(1),O(1'):O(4),O(4'):O(4))dicadmium(II)], [Cd2(C6H8O4)2(C14H14N4)]n, have been synthesized under hydrothermal conditions and characterized by single-crystal X-ray diffraction, elemental analysis, IR spectroscopy and thermogravimetric analysis. Both complexes crystallize in the monoclinic space group C2/c with similar unit-cell parameters and feature two-dimensional structures formed by the interconnection of S-shaped Zn(Cd)-2,2-dimethylsuccinate chains with 1,4-bis(imidazol-1-ylmethyl)benzene bridges. However, the Cd(II) and Zn(II) centres have different coordination numbers and the 2,2-dimethylsuccinate ligands display different coordination modes. Both complexes exhibit a blue photoluminescence in the solid state at room temperature.

  14. Ligand and Metalloligand Design for Macrocycles, Multimetallic Arrays, Coordination Polymers and Assemblies

    OpenAIRE

    E. C. Constable; Housecroft, C. E.

    2016-01-01

    This overview of ligand design focuses on three areas: (i) principles of ligand binding, the formation of complexes, and popular strategies for ligand synthesis; (ii) ligand design in macrocyclic complexes, coordination polymers and networks and metallopolygons, and assembly strategies based upon the use of metalloligand building blocks; (iii) ligand design for the extraction and transport of metals. This area of coordination chemistry is too large to permit a comprehensive survey in the spac...

  15. Synthesis and characterization of two novel coordination polymers based on the rigid 1H-1,2,3-triazole-4,5-dicarboxylic acid ligand

    Institute of Scientific and Technical Information of China (English)

    2010-01-01

    Two novel three-dimensional (3-D) coordination polymers, [Pb(HTDA)]n (1) and [Co5(TDA)2(H2TDA)2(H2O)8]n (2) [H3TDA = 1H-1,2,3-triazole-4,5-dicarboxylic acid], have been prepared by hydrothermal reactions and characterized by elemental analysis, infrared spectroscopy and single-crystal X-ray diffraction. Compound 1 is constructed from rod-shaped secondary building units (SBUs) and exhibits a 3-D network with (410·65)(410·63·82) topology. Compound 2 is built up from ligands bridging three different cobalt ions and exhibits a 3-D network with (4·82)3(4·82·103) topology. In addition, the thermal stabilities of the two compounds, the photoluminescence properties of compound 1 and the magnetic properties of compound 2 have been studied.

  16. Single cyanide-bridged Mo(W)/S/Cu cluster-based coordination polymers: Reactant- and stoichiometry-dependent syntheses, effective photocatalytic properties

    Energy Technology Data Exchange (ETDEWEB)

    Zhang, Jinfang, E-mail: zjf260@jiangnan.edu.cn [China-Australia Joint Research Center for Functional Molecular Materials, School of Chemical and Material Engineering, Jiangnan University, Wuxi 214122 (China); Wang, Chao [China-Australia Joint Research Center for Functional Molecular Materials, School of Chemical and Material Engineering, Jiangnan University, Wuxi 214122 (China); Wang, Yinlin; Chen, Weitao [China-Australia Joint Research Center for Functional Molecular Materials, Scientific Research Academy, Jiangsu University, Zhenjiang 212013 (China); Cifuentes, Marie P.; Humphrey, Mark G. [Research School of Chemistry, Australian National University, Canberra ACT 0200 (Australia); Zhang, Chi, E-mail: chizhang@jiangnan.edu.cn [China-Australia Joint Research Center for Functional Molecular Materials, School of Chemical and Material Engineering, Jiangnan University, Wuxi 214122 (China)

    2015-11-15

    The systematic study on the reaction variables affecting single cyanide-bridged Mo(W)/S/Cu cluster-based coordination polymers (CPs) is firstly demonstrated. Five anionic single cyanide-bridged Mo(W)/S/Cu cluster-based CPs {[Pr_4N][WS_4Cu_3(CN)_2]}{sub n} (1), {[Pr_4N][WS_4Cu_4(CN)_3]}{sub n} (2), {[Pr_4N][WOS_3Cu_3(CN)_2]}{sub n} (3), {[Bu_4N][WOS_3Cu_3(CN)_2]}{sub n} (4) and {[Bu_4N][MoOS_3Cu_3(CN)_2]}{sub n} (5) were prepared by varying the molar ratios of the starting materials, and the specific cations, cluster building blocks and central metal atoms in the cluster building blocks. 1 possesses an anionic 3D diamondoid framework constructed from 4-connected T-shaped clusters [WS{sub 4}Cu{sub 3}]{sup +} and single CN{sup −} bridges. 2 is fabricated from 6-connected planar ‘open’ clusters [WS{sub 4}Cu{sub 4}]{sup 2+} and single CN{sup −} bridges, forming an anionic 3D architecture with an “ACS” topology. 3 and 4 exhibit novel anionic 2-D double-layer networks, both constructed from nest-shaped clusters [WOS{sub 3}Cu{sub 3}]{sup +} linked by single CN{sup −} bridges, but containing the different cations [Pr{sub 4}N]{sup +} and [Bu{sub 4}N]{sup +}, respectively. 5 is constructed from nest-shaped clusters [MoOS{sub 3}Cu{sub 3}]{sup +} and single CN{sup −} bridges, with an anionic 3D diamondoid framework. The anionic frameworks of 1-5, all sustained by single CN{sup −} bridges, are non-interpenetrating and exhibit huge potential void volumes. Employing differing molar ratios of the reactants and varying the cluster building blocks resulted in differing single cyanide-bridged Mo(W)/S/Cu cluster-based CPs, while replacing the cation ([Pr{sub 4}N]{sup +} vs. [Bu{sub 4}N]{sup +}) was found to have negligible impact on the nature of the architecture. Unexpectedly, replacement of the central metal atom (W vs. Mo) in the cluster building blocks had a pronounced effect on the framework. Furthermore, the photocatalytic activities of heterothiometallic

  17. Ytterbium Coordination Polymer with Four Different Coordination Numbers:The First Structural Characterization of Lanthanide Phthalate Complex

    Institute of Scientific and Technical Information of China (English)

    万永红; 金林培; 等

    2002-01-01

    The novel ytterbium coordination polymer is a t4wo-dimensional framework in which the central metal ions have four different coordination numbers and form four kinds of coordination poly-hedra,The four kinds of coordination polyhedra connect into infinite chains by sharing oxygen atoms.

  18. Studies on the Coordination Polymer of Copper Electropolyurushiol

    Institute of Scientific and Technical Information of China (English)

    2001-01-01

    The coordination polymer of copper electropolyurushiol(EPU-Cu2+) was obtained by the reaction of copper chloride with electropolyurushiol (EPU) in an isopropyl alcohol solution. The properties of EPU-Cu2+ were studied by means of ESR, FTIR, XPS, DMTA and TG-DTA.The results of AES show that the content of Cu2+ was 8.63%. The electric resistances of EPUCu2+ and EPU were determined to be 9.37×1010Ω and 7.90×1010Ω respectively. It was also ascertained that in EPU-Cu2+ each Cu2+ is coordinated with two units hydroxyl in EPU, making the EPU-Cu2+ cross-link further. As a result, the title polymer exhibits an insolubility in most of organic solutions, a higher glass transition temperature and thermal resistance.

  19. Self-Assembly of Discrete Metallocycles versus Coordination Polymers Based on Cu(I and Ag(I Ions and Flexible Ligands: Structural Diversification and Luminescent Properties

    Directory of Open Access Journals (Sweden)

    Javier Vallejos

    2016-02-01

    Full Text Available Three new Ag(I and one Cu(I coordination compounds with two different positional isomers, propane-1,3-diyl bis(pyridine-4-carboxylate (L1 and propane-1,3-diyl bis(pyridine-3-carboxylate (L2, of a bis-(pyridyl-carboxylate ligand have been synthesized. X-ray diffraction analysis revealed that the self-assembly of L1 with AgCF3SO3 and AgClO4 salts leads to the formation of discrete binuclear metallocycles {Ag(L1CF3SO3}2 (1 and {Ag(L1ClO4}2 (2, respectively. However, self-assembly of the other ligand, L2, with AgCF3SO3 and CuCl salts, results in a 1-D zig-zag chain {Ag(L2CF3SO3}∞ (3 and a 1-D double-stranded helical chain {Cu2Cl2(L22}∞ (4 coordination polymers, respectively. Solid emission spectra recorded at room temperature show interesting luminescence properties for all four compounds in the range from 438 to 550 nm, especially for compound 4 that was found to change its emission color when the wavelength of the excitation radiation is switched from 332 to 436 nm.

  20. Heterotopic silver-NHC complexes: from coordination polymers to supramolecular assemblies

    NARCIS (Netherlands)

    Rubio, M.; Siegler, M. A.; Spek, A.L.; Reek, J.N.H.

    2010-01-01

    New coordination polymers based on different combinations of silver atoms and pyridyl-substituted N-heterocyclic carbene moieties are described. The addition of Zn(ii) templates leads to Ag-Zn supramolecular assemblies via selective ZnN interactions; a process that can be reverted.

  1. Heterotopic silver-NHC complexes: from coordination polymers to supramolecular assemblies

    NARCIS (Netherlands)

    Rubio, M.; Siegler, M.A.; Spek, A.L.; Reek, J.N.H.

    2010-01-01

    New coordination polymers based on different combinations of silver atoms and pyridyl-substituted N-heterocyclic carbene moieties are described. The addition of Zn(II) templates leads to Ag-Zn supramolecular assemblies via selective Zn⋯N interactions; a process that can be reverted.

  2. Anion effect on the topological frameworks of a series of manganese coordination polymers based on 1,4-bis(imidazol-1-yl)-benzene: Syntheses, crystal structures and magnetic properties

    Science.gov (United States)

    Ye, Gan; Zou, Kang-Yu; Yang, Ying; Wang, Jun-Jie; Gou, Xiao-Feng; Li, Zuo-Xi

    2015-05-01

    In this work, the rod-like ligand 1,4-bis(imidazol-1-yl)-benzene (bib) has been utilized as a building block to perform counterion researches on the structural diversities of coordination polymers. A series of new manganese compounds, {[Mn(bib)3(ClO4)2](CHCl3)2}n (1), [Mn(bib)2(N3)2]n (2), [Mn(bib)2(HCO2)2]n (3), [Mn(bib)2(Ac)2]n (4), {[Mn(bib)2(CF3SO3)2](CH2Cl2)4}n (5), and [Mn(bib)2(SO4)]n (6) have been successfully synthesized. Compound 1 shows a 3D interpenetrating α-Po network only based on the bib linker. Compounds 2 and 3 exhibit a 2D (4,4) layer with parallel and incline interpenetration, respectively. Compounds 4 and 5 display a parallel-packing 2D (4,4) layer with the porosity of 23.4% and 61.4%, respectively. Compound 6 furnishes a 3D α-Po framework with a 2D (4,4) layer pillared by the μ2-SO42- ion. The structural diversities among 1-6 have been carefully discussed, and the roles of counterions (from coordination affinity and molecular size) in the self-assembly of coordination polymers have also been well documented. Furthermore, magnetic properties of 6 have been carefully studied.

  3. Crystal structure and photoluminescence of a new two-dimensional Cd(II) coordination polymer based on 3-(carboxymethoxy)-2-naphthoic acid

    Energy Technology Data Exchange (ETDEWEB)

    Kong, Zhi-Guo; Guo, Sheng-Nan; Miao, Jia-Qi; An, Miao [Jilin Normal Univ., College of Chemistry, Siping (China); Ministry of Education, Siping (China). Key Lab. of Preparation and Applications of Enviromental Friendly Materials

    2015-11-01

    A new Cd(II) coordination polymer, [Cd(CNA)]{sub n} (1) (H{sub 2}CNA = 3-(carboxymethoxy)-2-naphthoic acid), was hydrothermally synthesized and structurally characterized by single-crystal X-ray diffraction. The crystals are monoclinic, space group P{sub 2}1/c with a = 16.9698(18), b = 7.8314(8), c = 8.9553(10) Aa, β = 100.657(2) {sup circle}, V = 1169.6(2) Aa{sup 3}, Z = 4, D{sub calcd.} = 2.03 g cm{sup -3}, μ(MoK{sub α}) = 1.9 mm{sup -1}, F(000) = 696 e, R = 0.0305, wR = 0.0784 for 172 refined parameters and 2285 data. Each CNA anion bridges three Cd(II) cations to give rise to a two-dimensional network structure. Topologically, if each CNA anion is regarded as a linker, and each Cd(II) atom considered as a 4-connected node, the structure is simplified as a 4-connected (4,4) network. The solid state photoluminescent properties of the compound were also studied at room temperature.

  4. Structural variability, Hirshfeld surface analysis and properties of three Zn(II) coordination polymers based on flexible bis(thiabendazole) and aromatic dicarboxylate co-ligands

    Science.gov (United States)

    Chang, Hai-Ning; Liu, Ce; Hao, Zeng-Chuan; Cui, Guang-Hua

    2017-02-01

    Three zinc(II) coordination polymers (CPs), {[Zn(L)0.5(tbta)]·0.5 L·2.5H2O}n (1), {[Zn(L)0.5(mip)]·H2O}n (2) and {[Zn(L)0.5(npht)(H2O)]·0.5H2O}n (3) (L = 1,4-bis(thiabendazole)butane, H2tbta = tetrabromoterephthalic acid, H2mip = 5-methylisophthalic acid, H2npht = 3-nitrophthalic acid) have been hydrothermally synthesized and structurally characterized. Single-crystal X-ray diffraction analyses reveal that CP 1 shows a 2D honeycomb-like (6, 3) network. CP 2 displays a hybrid helical chain, and further assembled into a 2D supramolecular layer via weak Csbnd H⋯O hydrogen bonding interactions, whereas CP 3 is a right-handed helical chain and finally extended into a 3D supramolecular structure by classical Osbnd H⋯O hydrogen bonds and π-π stacking interactions. Further, the Hirshfeld surfaces, fingerprint plots, fluorescence properties and catalytic performances of three CPs for the degradation of methyl orange dye in a Fenton-like process have been investigated.

  5. Crystal structure of a layered coordination polymer based on a 44 net containing Cd2+ ions and 1,5-bis(pyridin-4-ylpentane linkers

    Directory of Open Access Journals (Sweden)

    William T. A. Harrison

    2014-08-01

    Full Text Available The title compound, poly[[diaquabis[1,5-bis(pyridin-4-ylpentane-κ2N:N′]cadmium] bis(perchlorate 1,5-bis(pyridin-4-ylpentane ethanol monosolvate], [Cd(C15H18N22(H2O2](ClO42·C15H18N2·C2H6O, is a layered coordination polymer built up from highly squashed 44 nets in which the octahedral trans-CdO2N4 nodes (Cd site symmetry -1 are linked by the bifunctional ligands, forming infinite (110 sheets. The cationic sheets are charge-balanced by interlayer perchlorate ions. A free 1,5-bis(pyridin-4-ylpentane molecule and an ethanol molecule of crystallization are also found in the intersheet region. A number of O—H...O, O—H...N and C—H...O hydrogen bonds help to consolidate the layered structure.

  6. Two new Zn(II) coordination polymers based on mixed pipemidic acid and flexible aromatic dicarboxylic acid ligands: Syntheses, crystal structures and luminescent properties

    Science.gov (United States)

    Jia, Yanxia; Zhou, Pingping

    2016-09-01

    Two new Zn(II) coordination polymers, namely [Zn(4,4‧-sdb) (HPPA)]n (1) and [Zn(2,2‧-bpdc)0.5(PPA)]n (2) (4,4‧-H2sdb = 4,4‧-sulfonyldibenzoate, 2,2‧-H2bpdc = 2,2‧-biphenyldicarboxylic acid, HPPA = pipemidic acid) were successfully obtained under hydrothermal conditions. These two compounds were further characterized by single-crystal X-ray diffraction analyses, elemental analyses, powder X-ray diffraction (PXRD) analyses and IR spectra. Compound 1 features a 1D chain structure, which further extended into a 3D supramolecular framework via intermolecular hydrogen bonds and weak van der Waals interactions, and compound 2 features a 3D framework with 6-connected α-Po-type topology. The structural regulation for these two compounds was successfully achieved by changing the flexible aromatic dicarboxylic acid ligand. Moreover, the thermal stabilities and luminescent properties for these two compounds were also investigated.

  7. 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

    Science.gov (United States)

    Wang, Chao; Zhao, Jun; Xia, Liang; Wu, Xue-Qian; Wang, Jian-Fang; Dong, Wen-Wen; Wu, Ya-Pan

    2016-06-01

    Three new coordination polymers, namely, {[Ni(H2L)(bix)(H2O)2]·2h2O}n (1), {[Ni(HL)(Hdpa)(H2O)2]·H2O}n (2), {[Ni(L)0.5(bpp)(H2O)]·H2O}n (3) (H4L=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 H4L ligand and different N-donor co-ligands, have been synthesized under hydrothermal conditions. Compound 1 features a 3D 4-connected 66-dia-type framework with H4L ligand adopts a μ2-bridging mode with two symmetry-related carboxylate groups in μ1-η1:η0 monodentate mode. Compound 2 displays a 1D [Ni(HL)(Hdpa)]n ribbon chains motif, in which the H4L ligand adopts a μ2-bridging mode with two carboxylate groups in μ1-η1:η1 and μ1-η1:η0 monodentate modes, while 3 possesses a (4,4)-connected 3D frameworks with bbf topology, with H4L ligand displays a μ4-bridging coordination mode. The H4L 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.

  8. A ladder coordination polymer based on Ca(2+) and (4,5-dicyano-1,2-phenylene)bis(phosphonic acid): crystal structure and solution-state NMR study.

    Science.gov (United States)

    Venkatramaiah, Nutalapati; Mendes, Ricardo F; Silva, Artur M S; Tomé, João P C; Almeida Paz, Filipe A

    2016-09-01

    The preparation of coordination polymers (CPs) based on either transition metal centres or rare-earth cations has grown considerably in recent decades. The different coordination chemistry of these metals allied to the use of a large variety of organic linkers has led to an amazing structural diversity. Most of these compounds are based on carboxylic acids or nitrogen-containing ligands. More recently, a wide range of molecules containing phosphonic acid groups have been reported. For the particular case of Ca(2+)-based CPs, some interesting functional materials have been reported. A novel one-dimensional Ca(2+)-based coordination polymer with a new organic linker, namely poly[[diaqua[μ4-(4,5-dicyano-1,2-phenylene)bis(phosphonato)][μ3-(4,5-dicyano-1,2-phenylene)bis(phosphonato)]dicalcium(II)] tetrahydrate], {[Ca2(C8H4N2O6P2)2(H2O)2]·4H2O}n, has been prepared at ambient temperature. The crystal structure features one-dimensional ladder-like ∞(1)[Ca2(H2cpp)2(H2O)2] polymers [H2cpp is (4,5-dicyano-1,2-phenylene)bis(phosphonate)], which are created by two distinct coordination modes of the anionic H2cpp(2-) cyanophosphonate organic linkers: while one molecule is only bound to Ca(2+) cations via the phosphonate groups, the other establishes an extra single connection via a cyano group. Ladders close pack with water molecules through an extensive network of strong and highly directional O-H...O and O-H...N hydrogen bonds; the observed donor-acceptor distances range from 2.499 (5) to 3.004 (6) Å and the interaction angles were found in the range 135-178°. One water molecule was found to be disordered over three distinct crystallographic positions. A detailed solution-state NMR study of the organic linker is also provided.

  9. Designer coordination polymers: dimensional crossover architectures and proton conduction.

    Science.gov (United States)

    Yamada, Teppei; Otsubo, Kazuya; Makiura, Rie; Kitagawa, Hiroshi

    2013-08-21

    Coordination polymers (CPs) have large degrees of freedom in framework compositions and in the structures and environment of the inner pores. This review focuses on the recent significant progress achieved by controlling these degrees of freedom. Two breakthroughs are reviewed for constructing sophisticated structures of CP frameworks, especially in dimensional crossover regions. The first is the synthesis of quasi one-dimensional halogen-bridged coordinative tubes by applying state-of-the-art techniques of coordination chemistry. The electronic state of the coordinative tube was studied by structural, spectroscopic and theoretical methods and found to be distinct from conventional one-dimensional systems. The second breakthrough is the achievement of a quasi-two-dimensional architecture by combining Langmuir-Blodgett and layer-by-layer methods. Two-dimensional LB CP films were prepared on liquid; the films were stacked layer by layer, and a crystalline quasi-two-dimensional structure was constructed. This review also covers the design of the environment of the inner pore, where hydrogen bond networks with various acidic sites were modified. By appropriate design of the hydrogen bond network, proton-conductive CPs are invented, which are summarized in this review. Types of proton donor sites are discussed and classified, and superprotonic conductive CPs were achieved in these investigations. These results will provide new strategies for constructing functional materials for smart devices.

  10. Cd(II)-coordination polymers based on tetracarboxylic acid and diverse bis(imidazole) ligands: Synthesis, structural diversity and photoluminescence properties

    Science.gov (United States)

    Arıcı, Mürsel; Yeşilel, Okan Zafer; Taş, Murat

    2017-01-01

    Three new Cd(II)-coordination polymers, namely, {[Cd2(μ6-ao2btc)(μ-1,5-bipe)2]·2H2O}n (1), {[Cd2(μ6-ao2btc)(μ-1,4-bix)2]n·2DMF} (2) and {[Cd2(μ8-abtc)(μ-1,4-betix)]·DMF·H2O}n (3) (ao2btc=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 Cd2(CO2)4-type binuclear SBU. Moreover, thermal and photoluminescence properties of the complexes were determined in detailed.

  11. Theoretical investigation of polymer chain stability in the metal coordinated azorubine and cyclam complex

    Energy Technology Data Exchange (ETDEWEB)

    Vlassa, Mihaela, E-mail: mihaela_cecilia@yahoo.com [' ' Babes-Bolyai' ' University, Raluca Ripan Institute of Research in Chemistry, 30 Fantanele Str., 400294 Cluj-Napoca (Romania); Bende, Attila, E-mail: bende@itim-cj.ro [Molecular and Biomolecular Physics Department, National Institute for Research and Development of Isotopic and Molecular Technologies, Str. Donat 67-103, Cluj Napoca RO-400293 (Romania)

    2015-08-18

    Highlights: • Ni(II)- and Zn(II)-coordinated cyclam–azorubine complexes are described using DFT. • Ni(II) coordinated system shows a reasonably small singlet–triplet energy gap. • Intersystem crossing gives high barrier between singlet and triplet geometries. • For the Zn(II) case only the singlet state is energetically favorable. • The stability of a longer polymer (oligomer) chain was described using DFTB. - Abstract: Theoretical investigations have been performed for unit systems with Ni(II) and Zn(II) coordination between azorubine and 1,4,8,11-tetraazacyclotetradecane (cyclam) complexes using the conventional DFT and the DFT-based tight binding (DFTB) methods. Two different geometries (short and long) and spin states (singlet and triplet) of the model system built by two mesylate groups and the cyclam ring together with Ni(II) and Zn(II) ions were energetically characterized. For the Ni(II) coordination complex the triplet geometry is preferred, but one could not exclude also the presence of the singlet spin configuration due to the huge energy barrier defined by the intersystem crossing. The intersystem crossing geometry of the singlet–triplet transition was studied in details and the corresponding spin–orbit couplings were discussed. For the Zn(II) coordination complex only the singlet state was found. Polymer chain build up from four unit systems presents irregular forms with strong coordination bonds between units.

  12. Cationic zinc (II) dimers and one dimensional coordination polymer from ionic carboxylic acid

    Indian Academy of Sciences (India)

    Paladugu Suresh; Ganesan Prabusankar

    2014-09-01

    A rare example of chelating two tetra cationic paddle-wheel zinc dimers were synthesized from the reaction between flexible imidazolium carboxylate (LH2Br2) and corresponding zinc precursors. A zinc coordination polymer was synthesised by treating in situ generation of 2 in the presence of 4,4′-bipyridine. These new molecules, dimers and polymer, were characterized by FT-IR, NMR, UV-vis, fluorescent and single crystal X-ray diffraction techniques. Zinc polymer is the first example of 1D coordination polymer constructed by tetra cationic zinc dimer as a secondary building unit in coordination polymer.

  13. 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.

  14. Synthesis and structural characterization of silver(I), copper(I) coordination polymers and a helicate palladium(II) complex of dipyrrolylmethane-based dipyrazole ligands: the effect of meso substituents on structural formation.

    Science.gov (United States)

    Guchhait, Tapas; Barua, Bhagyasree; Biswas, Aritra; Basak, Biswanath; Mani, Ganesan

    2015-05-21

    A new class of multidentate dipyrrolylmethane based ditopic tecton, 1,9-bis(3,5-dimethylpyrazolylmethyl)dipyrrolylmethane, containing diethyl (L1) or cyclohexylidene (L2) substituents at the meso carbon atom were readily synthesized in 28-45% yields in two different ways starting from dipyrrolylmethanes. A one dimensional coordination polymer structure ([(L2)Ag][BF4])n was obtained when L2 was treated with AgBF4, whereas the analogous reaction between L1 and AgBF4 afforded the dicationic binuclear metallacycle complex [(L1)2Ag2][BF4]2. In addition, yet another coordination polymeric structure [(L1)CuI]n was obtained from the reaction between L1 and CuI. The analogous reaction of L1 with [Pd(PhCN)2Cl2] afforded the binuclear palladium complex [(L1)2Pd2Cl4] having a double-stranded helicate structure. The observed structural differences are attributed to the effects of the substituents present at the meso carbon atom of the ligand, in addition to the nature of the metal centre, coordination number and the preferred geometry.

  15. Synthesis and Crystal Structure of One Mixed- ligand Coordination Polymer Based on the Novel Terphenyl-2,5,2',5'-tetracarboxylic Acid Ligand%Synthesis and Crystal Structure of One Mixed- ligand Coordination Polymer Based on the Novel Terphenyl-2,5,2',5'-tetracarboxylic Acid Ligand

    Institute of Scientific and Technical Information of China (English)

    ZHANG Xiu-Tang; ZHANG Lu-Qing; ZHANG Liang-Dong; FAN Li-Ming; WEI Pei-Hai; ZHANG Shu-Xiang

    2012-01-01

    Solvothermal reaction of aromatic terphenyl-2,5,2',5'-tetracarboxylic acid (Hnqptc) ligand and the transitional metal cation of Mn11 in the presence of 3-(2-pyridyl)pyrazole (pp) affords one new coordination polymer, [Mn(qptc)0.5(pp)2]n·n(H2O) (1). The structure has been determined by single-crystal X-ray diffraction analyses and further characterized by elemental analyses, IR, TGA, and magnetism. The carboxyl groups of qptc4 exhibit a μ1-η1:η0 coordination mode, and the qptc4- acts as a H-shaped ligand linking the Mn11 centers together to form a 2D polymeric [Mn(qptc)0.5]n layer. The crystal of 1 crystallizes in orthorhombic, space group Pbca with a = 9.3119(12), b = 20.848(3), c = 26.134(3) A, V= 5073.4(11) A3, Z= 8, C27HIgMnN6O5,Mr=562.42, Dc = 1.473 g/cm3, F(000) = 2304 and μ(MoKa) = 0.571 mm-1. The final R = 0.0468 and wR = 0.1196 for 4429 observed reflections with I 〉 2σ(I) and R = 0.0797 and wR = 0.1383 for all data.

  16. Facile synthesis of novel Ni(II)-based metal-organic coordination polymer nanoparticle/reduced graphene oxide nanocomposites and their application for highly sensitive and selective nonenzymatic glucose sensing.

    Science.gov (United States)

    Lu, Wenbo; Qin, Xiaoyun; Asiri, Abdullah M; Al-Youbi, Abdulrahman O; Sun, Xuping

    2013-01-21

    The present paper reports on the facile preparation of novel Ni(II)-based metal-organic coordination polymer nanoparticle/reduced graphene oxide (NiCPNP/rGO) nanocomposites for the first time. The formation of the nanocomposites occurs in a single step, carried out by hydrothermal treatment of the mixture of tannic acid functioned graphene oxide and NiCl(2) aqueous solution in N,N-dimethylformamide. It is found that the NiCPNP/rGO nanocomposite-modified electrode shows high electrocatalytic activity for glucose oxidation in alkaline medium. This nonenzymatic glucose sensor exhibits high selectivity toward glucose and the linear range and limit of detection are estimated to be from 0.01 to 8.75 mM (r: 0.997) and 0.14 μM with a signal-to-noise ratio of 3, respectively. The application of this glucose sensor in human blood serum has also been demonstrated successfully.

  17. Coordination Polymers of Palladium Bridged by Carboxylate and Dimethylaminoalkylselenolate Ligands.

    Science.gov (United States)

    Paluru, Dilip K; Dey, Sandip; Wadawale, Amey P; Bhuvanesh, Nattamai; Grupp, Anita; Kaim, Wolfgang; Jain, Vimal K

    2016-02-04

    Coordination polymers of palladium stabilized by dimethylaminoalkylselenolate and carboxylate ligands are reported. The reaction of [PdCl(SeCH2 CH2 NMe2 )]3 with AgOTf followed by treatment with sodium acetate afforded [Pd(0) Pd(II) 4 (SeCH2 CH2 NMe2 )3 (OAc)3 ](OTf)2 (1) in which one of the Pd atoms is in the zero oxidation state. In the absence of NaOAc, a tetranuclear complex, [Pd(II) 4 (SeCH2 CH2 NMe2 )4 (OTf)](OTf)3 (2), is isolated from the same reaction. Subsequent treatment with NaO2 CR afforded [Pd4 (SeCH2 CH2 NMe2 )4 (O2 CR)4 ] (R=tBu (3) and Ph (4)). The reaction of [PdCl(SeCH2 CH2 CH2 NMe2 )]2 with AgOTf and NaOAc yielded an ionic binuclear complex, [Pd(II) 2 (SeCH2 CH2 CH2 NMe2 )2 (OAc)](OTf) (5). These complexes have been characterized by NMR spectroscopy, crystal structures, and in some cases by X-ray photoelectron spectroscopy, cyclic voltammetry and mass spectrometry. Complexes 1 and 5 are associated through secondary interactions and coordinate bonds, respectively, to generate polymeric structures in the solid state. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  18. A framework for predicting surface areas in microporous coordination polymers.

    Science.gov (United States)

    Schnobrich, Jennifer K; Koh, Kyoungmoo; Sura, Kush N; Matzger, Adam J

    2010-04-20

    A predictive tool termed the linker to metal cluster (LiMe) ratio is introduced as a method for understanding surface area in microporous coordination polymers (MCPs). Calibrated with geometric accessible surface area computations, the LiMe ratio uses molecular weight of building block components to indicate the maximum attainable surface area for a given linker and metal cluster combination. MOF-5 and HKUST-1 are used as prototypical structures to analyze MCPs with octahedral M(4)O(CO(2)R)(6) and paddlewheel M(2)(CO(2)R)(4) metal clusters. Insight into the effects of linker size, geometry, number of coordinating groups, and framework interpenetration is revealed through the LiMe ratio analysis of various MCPs. Experimental surface area deviation provides indication that a material may suffer from incomplete guest removal, structural collapse, or interpenetration. Because minimal data input are required, the LiMe ratio surface area analysis is suggested as a quick method for experimental verification as well as a guide for the design of new materials.

  19. Two new coordination polymers, a trinuclear metal complex and their interconversion depending on the solvent.

    Science.gov (United States)

    Koike, Shiori; Hirakawa, Takeshi; Yamanishi, Katsunori; Kondo, Mitsuru

    2014-09-14

    Two new 1-D coordination polymers and a discrete trinuclear complex with a double-ring framework were synthesized and structurally characterized. The unique irreversible conversion from one of the 1-D coordination polymers to the trinuclear complex by contact with MeCN is described.

  20. 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.

  1. 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.

  2. Application of a silver-olefin coordination polymer as a catalytic curing agent for self-healing epoxy polymers

    Science.gov (United States)

    Everitt, D. T.; Coope, T. S.; Trask, R. S.; Wass, D. F.; Bond, I. P.

    2015-05-01

    A silver-olefin based coordination polymer was prepared in a simple, one step process to act as an initiator to facilitate the ring-opening polymerization of epoxides. Thermal analysis found the complex to be capable of curing a range of commercially available epoxy resins used in the manufacture of conventional composite materials. Curing of the oligomeric diglycidyl ether bisphenol A resin, Epon 828, in combination with a non-toxic solvent, ethyl phenylacetate, was studied by differential scanning calorimetry. The mechanical characterization of the resultant cured polymers was conducted by single lap shear tests. Tapered double cantilever beam (TDCB) test specimens containing 2.5 pph of silver-olefin initiator, both with and without embedded microcapsules, were analyzed for their healing performance. Healing efficiency values were found to be strongly dependent on the applied healing temperature. A mean recovery of 74% fracture load was found in TDCB samples after being healed at 70 °C for 48 h.

  3. Conducting Polymer Based Nanobiosensors

    Directory of Open Access Journals (Sweden)

    Chul Soon Park

    2016-06-01

    Full Text Available In recent years, conducting polymer (CP nanomaterials have been used in a variety of fields, such as in energy, environmental, and biomedical applications, owing to their outstanding chemical and physical properties compared to conventional metal materials. In particular, nanobiosensors based on CP nanomaterials exhibit excellent performance sensing target molecules. The performance of CP nanobiosensors varies based on their size, shape, conductivity, and morphology, among other characteristics. Therefore, in this review, we provide an overview of the techniques commonly used to fabricate novel CP nanomaterials and their biosensor applications, including aptasensors, field-effect transistor (FET biosensors, human sense mimicking biosensors, and immunoassays. We also discuss prospects for state-of-the-art nanobiosensors using CP nanomaterials by focusing on strategies to overcome the current limitations.

  4. Control of hierarchical polymer mechanics with bioinspired metal-coordination dynamics

    OpenAIRE

    Grindy, Scott C.; Learsch, Robert; Mozhdehi, Davoud; Cheng, Jing; Barrett, Devin G.; Guan, Zhibin; Messersmith, Phillip B.; Holten-Andersen, Niels

    2015-01-01

    In conventional polymer materials, mechanical performance is traditionally engineered via material structure, using motifs such as polymer molecular weight, polymer branching, or copolymer-block design 1 . Here, by means of a model system of 4-arm poly(ethylene glycol) hydrogels crosslinked with multiple, kinetically distinct dynamic metal-ligand coordinate complexes, we show that polymer materials with decoupled spatial structure and mechanical performance can be designed. By tuning the rela...

  5. Temperature-controlled Hydrothermal Synthesis of Copper(Ⅰ or Ⅱ) Coordination Polymers via a Variety of Copper Coordination Modes

    Institute of Scientific and Technical Information of China (English)

    QU Xue-jian; WANG Shuang; ZHANG Dao-jun; JING Xue-min; ZHANG Li-rong; LI Guang-hua; HUO Qi-sheng; LIU Yun-ling

    2012-01-01

    Two 1D coordination polymers Cu2Ⅰ(C6N3H4)2(1) and CuⅡ(C6N3H4)2·H2O(2) based on benzotriazole(Bta)were hydrothermally synthesized by controlling the crystallization temperature.Single-crystal X-ray diffraction (XRD) analyses reveal that compound 1 is a 1D tubular structure constructed from two types of 1D chains {—Cu—N=N—N—}n,where the Cu(Ⅰ) ions adopt linear,triangular,and tetrahedral coordination modes to connect two types of Bta ligands via π-π interaction inside the tubular-like chain.For compound 2,the Cu(Ⅱ) ions assume a quadrilateral coordination mode linking to the Bta ligands to give 1D straight chains,which stacks through π-π interactions to construct a 2D layer structure.Further characterizations including elemental analyses,infrared IR spectra,thermogravimetric(TG) analyses and luminescence properties have been done.

  6. Carbon dioxide (CO2) absorption behavior of mixed matrix polymer composites containing a flexible coordination polymer.

    Science.gov (United States)

    Culp, Jeffrey T; Sui, Lang; Goodman, Angela; Luebke, David

    2013-03-01

    Mixed matrix membranes (MMMs) comprised of metal organic frameworks (MOFs) dispersed in organic polymers are popular materials under study for potential applications in gas separations. However, research on MMMs containing structurally dynamic sorbents known as flexible MOFs has only very recently appeared in the literature. The thermodynamic requirements of the structure transition between the low porosity and high porosity phases of flexible MOFs may provide a mechanism for high adsorption selectivity in these materials. A fundamental question in MMMs containing flexible MOFs is how the constraint of the polymer matrix on the intrinsic expansion of the flexible MOF particles that occurs during gas adsorption might affect the thermodynamics of this structural phase transition and influence the gas adsorption properties of the embedded MOF. To investigate the fundamental nature of this flexible MOF-polymer interface, thin films of ~20 um thickness were prepared using the flexible linear chain coordination polymer catena-bis(dibenzoylmethanato)-(4,4'bipyridyl)nickel(II) "Ni(Bpy)(DBM)(2)" embedded as 35 wt% dispersions in Matrimid®, polystyrene, and polysulfone. The adsorption of CO(2) in the polymers and embedded particles was studied using in situ ATR-FTIR spectroscopy and variable temperature volumetric CO(2) adsorption/desorption isotherms. Interestingly, no effect of the polymer matrix on the gas adsorption behavior of the embedded Ni(Bpy)(DBM)(2) particles was observed. The composite samples all showed the same threshold pressures for CO(2) absorption and desorption hysteresis associated with the structural phase change in the polymer embedded Ni(Bpy)(DBM)(2) particles as was observed in the pristine polycrystalline sample. The current results contrast those recently reported for a MMM containing the flexible MOF "NH(2)-MIL-53" where a significant increase in the threshold pressure for CO(2) adsorption associated with the structural phase change of the MOF was

  7. Mesoscopic architectures of porous coordination polymers fabricated by pseudomorphic replication.

    Science.gov (United States)

    Reboul, Julien; Furukawa, Shuhei; Horike, Nao; Tsotsalas, Manuel; Hirai, Kenji; Uehara, Hiromitsu; Kondo, Mio; Louvain, Nicolas; Sakata, Osami; Kitagawa, Susumu

    2012-06-24

    The spatial organization of porous coordination polymer (PCP) crystals into higher-order structures is critical for their integration into separation systems, heterogeneous catalysts, ion/electron transport and photonic devices. Here, we demonstrate a rapid method to spatially control the nucleation site, leading to the formation of mesoscopic architecture made of PCPs, in both two and three dimensions. Inspired by geological processes, this method relies on the morphological replacement of a shaped sacrificial metal oxide used both as a metal source and as an 'architecture-directing agent' by an analogous PCP architecture. Spatiotemporal harmonization of the metal oxide dissolution and the PCP crystallization allowed the preservation of very fine mineral morphological details of periodic alumina inverse opal structures. The replication of randomly structured alumina aerogels resulted in a PCP architecture with hierarchical porosity in which the hydrophobic micropores of the PCP and the mesopores/macropores inherited from the parent aerogels synergistically enhanced the material's selectivity and mass transfer for water/ethanol separation.

  8. Anion effect on the topological frameworks of a series of manganese coordination polymers based on 1,4-bis(imidazol-1-yl)-benzene: Syntheses, crystal structures and magnetic properties

    Energy Technology Data Exchange (ETDEWEB)

    Ye, Gan; Zou, Kang-Yu; Yang, Ying [Key Laboratory of Synthetic and Natural Functional Molecule Chemistry of Ministry of Education, Shaanxi Key Laboratory of Physico-Inorganic Chemistry, College of Chemistry and Materials Science, Northwest University, Xi’an 710069 (China); Wang, Jun-Jie [College of Chemistry and Chemical Engineering, Anyang NormalUniversity, Anyang, Henan 455000 (China); Gou, Xiao-Feng [Key Laboratory of Synthetic and Natural Functional Molecule Chemistry of Ministry of Education, Shaanxi Key Laboratory of Physico-Inorganic Chemistry, College of Chemistry and Materials Science, Northwest University, Xi’an 710069 (China); Li, Zuo-Xi, E-mail: lizx@nwu.edu.cn [Key Laboratory of Synthetic and Natural Functional Molecule Chemistry of Ministry of Education, Shaanxi Key Laboratory of Physico-Inorganic Chemistry, College of Chemistry and Materials Science, Northwest University, Xi’an 710069 (China)

    2015-05-15

    In this work, the rod-like ligand 1,4-bis(imidazol-1-yl)-benzene (bib) has been utilized as a building block to perform counterion researches on the structural diversities of coordination polymers. A series of new manganese compounds, ([Mn(bib){sub 3}(ClO{sub 4}){sub 2}](CHCl{sub 3}){sub 2}){sub n} (1), [Mn(bib){sub 2}(N{sub 3}){sub 2}]{sub n} (2), [Mn(bib){sub 2}(HCO{sub 2}){sub 2}]{sub n} (3), [Mn(bib){sub 2}(Ac){sub 2}]{sub n} (4), ([Mn(bib){sub 2}(CF{sub 3}SO{sub 3}){sub 2}](CH{sub 2}Cl{sub 2}){sub 4}){sub n} (5), and [Mn(bib){sub 2}(SO{sub 4})]{sub n} (6) have been successfully synthesized. Compound 1 shows a 3D interpenetrating α-Po network only based on the bib linker. Compounds 2 and 3 exhibit a 2D (4,4) layer with parallel and incline interpenetration, respectively. Compounds 4 and 5 display a parallel-packing 2D (4,4) layer with the porosity of 23.4% and 61.4%, respectively. Compound 6 furnishes a 3D α-Po framework with a 2D (4,4) layer pillared by the μ{sub 2}-SO{sub 4}{sup 2−} ion. The structural diversities among 1–6 have been carefully discussed, and the roles of counterions (from coordination affinity and molecular size) in the self-assembly of coordination polymers have also been well documented. Furthermore, magnetic properties of 6 have been carefully studied. - Graphical abstract: Six new compounds have been successfully synthesized. Structural studies reveal that the topology, entanglement and porosity are tunable by the counterion. Furthermore, the weak ferromagnetic coupling is conducted in 6. - Highlights: • Six new Mn{sup II} compounds have been synthesized. • Compounds 1–3 exhibit diverse interpenetrating frameworks. • Compounds 4 and 5 exhibit 3D packing porous architectures. • The tunable effect of counterion has been documented. • Magnetic properties of 6 have been studied by fitting the data.

  9. A new two-dimensional Cd(II) coordination polymer based on 2-(1H-imidazol-1-ylmethyl)-6-methyl-1H-benzimidazole and benzene-1,2-dicarboxylate: synthesis, crystal structure and characterization.

    Science.gov (United States)

    Yang, Huai Xia; Yang, Yan Qiu; Cheng, Di; Li, Ya Xue; Meng, Xiang Ru

    2017-10-01

    In the construction of coordination polymers, many factors can influence the formation of the final architectures, such as the nature of the metal centres, the organic ligands and the counter-anions. In the coordination polymer poly[aqua(μ-benzene-1,2-dicarboxylato-κ(4)O(1),O(1'):O(2),O(2'))[μ-2-(1H-imidazol-1-ylmethyl)-6-methyl-1H-benzimidazole-κ(2)N(2):N(3)]cadmium(II)], [Cd(C12H12N4)(C8H4O4)(H2O)]n or [Cd(immb)(1,2-bdic)(H2O)]n, each Cd(II) ion is seven-coordinated by two N atoms from two symmetry-related 2-(1H-imidazol-1-ylmethyl)-6-methyl-1H-benzimidazole (immb) ligands, by four O atoms from two symmetry-related benzene-1,2-dicarboxylate (1,2-bdic(2-)) ligands and by one water molecule, leading to a CdN2O5 distorted pentagonal bipyramidal coordination environment. The immb and 1,2-bdic(2-) ligands bridge Cd(II) ions and form a two-dimensional network structure. O-H...O and N-H...O hydrogen bonds stabilize the structure. In addition, the IR spectroscopic properties, PXRD patterns, thermogravimetric behaviour and fluorescence properties of the title polymer have been investigated.

  10. Polymer-based solar cells

    Directory of Open Access Journals (Sweden)

    Alex C. Mayer

    2007-11-01

    Full Text Available A significant fraction of the cost of solar panels comes from the photoactive materials and sophisticated, energy-intensive processing technologies. Recently, it has been shown that the inorganic components can be replaced by semiconducting polymers capable of achieving reasonably high power conversion efficiencies. These polymers are inexpensive to synthesize and can be solution-processed in a roll-to-roll fashion with high throughput. Inherently poor polymer properties, such as low exciton diffusion lengths and low mobilities, can be overcome by nanoscale morphology. We discuss polymer-based solar cells, paying particular attention to device design and potential improvements.

  11. Metal Coordination Polymers as Potential High-Energy Lithographic Resists

    Science.gov (United States)

    1989-05-15

    resists,I ~ ~ ~ 1-&obalt polymers--- - dfiroiuinpIrms (CotiueC-positive6 resjits ,-beta- diketones 19 At8tTRACT (Cniu nreverse ifnecessary and odentify by...have synthesized several cobalt(III) coordi- nation polymers, one of which was briefly described earlier (5,6). The general synthesis for three... diketones from ad- jacent units in the polymer chains. The corresponding sulfone polymer can be synthesized from the oxidation of the sulfoxide

  12. Beyond Single-Wavelength SHG Measurements: Spectrally-Resolved SHG Studies of Tetraphosphonate Ester Coordination Polymers.

    Science.gov (United States)

    Zaręba, Jan K; Białek, Michał J; Janczak, Jan; Nyk, Marcin; Zoń, Jerzy; Samoć, Marek

    2015-11-16

    Powder second-harmonic generation (SHG) efficiencies are usually measured at single wavelengths. In the present work, we provide a proof of concept of spectrally resolved powder SHG measured for a newly obtained series of three non-centrosymmetric coordination polymers (CPs). CPs are constructed from tetrahedral linker-tetraphenylmethane-based tetraphosphonate octaethyl ester and cobalt(II) ions of mixed, octahedral (Oh), and tetrahedral (Td), geometries and different sets of donors (CoO6 vs CoX3O). Isostructurality of the obtained materials allowed for the determination of anion-dependent tunability of SHG optical spectra and their relationship with solid-state absorption spectra.

  13. Polymer-Based Therapeutics

    OpenAIRE

    Liu, Shuang; Maheshwari, Ronak; Kiick, Kristi L.

    2009-01-01

    Polymeric materials have been applied in therapeutic applications, such as drug delivery and tissue regeneration, for decades owing to their biocompatibility and suitable mechanical properties. In addition, select polymer–drug conjugates have been used as bioactive pharmaceuticals owing to their increased drug efficacy, solubility, and target specificity compared with small-molecule drugs. Increased synthetic control of polymer properties has permitted the production of polymer assemblies for...

  14. Conformation driven complexation of two analogous benzimidazole based tripodal ligands with Ag(I) resulting in a trigonal prism and a coordination polymer

    Indian Academy of Sciences (India)

    Suman Bhattacharya; Binoy K Saha

    2016-02-01

    Two analogous tripodal ligands, namely, 1,3,5-tris(benzimidazol-1-ylmethyl)-2,4,6-triethylbenzene (1-Et) and 1,3,5-tris(benzimidazol-1-ylmethyl)-2,4,6-trimethoxybenzene (1-OMe) have been used for complexation with silver(I) tetrafluoroborate. A trinuclear Ag(I) salt, formulated as $\\mathbf{[Ag_3(1-Et)_2]^{3+}(BF_4){}^{−}_{3}\\bullet 7CH_3CN\\bullet yH_2O}$ was formed in the complexation reaction of 1-Et with silver(I) tetrafluoroborate, which consists of a trigonal prismatic cation formed by three bicoordinated Ag(I) coordinated with two 1-Et ligands. In case of the 1-OMe ligand, however, a one dimensional ladder, formulated as $\\mathbf{[(Ag(1-OMe)OH_2)^{+}(BF_4)^{−}\\bullet MeOH]_{\\infty}}$ was obtained which is constituted of a tetracoordinated Ag(I) center in a distorted tetrahedral environment. The crystal structures of the ligand hydrates namely $\\mathbf{1-Et\\bullet H_2O}$ and $\\mathbf{1-OMe\\bullet 3.6H_2O}$ have been discussed along with the structure of methanol solvate-hydrate of 1-Et. The imidazole rings of the Bim groups in 1-Et in the crystal structures of the ligand as well as in its coordination complex with the Ag(I) are pointed inward with respect to the central ring, whereas it is pointed outwards in the crystal structures of 1-OMe as well as its Ag(I) complex.

  15. A one-dimensional barium(II) coordination polymer with a coordinated nitro group of 2-nitrobenzoate

    Indian Academy of Sciences (India)

    Bikshandarkoil R Srinivasan; Santosh Y Shetgaonkar; Pallepogu Raghavaiah

    2008-03-01

    The aqueous reaction of barium carbonate with 2-nitrobenzoic acid (2-nbaH) results in the formation of a one-dimensional coordination polymer, catena-poly[[hexa(aqua)dibarium(II)]bis[(2-2-nitrobenzoate-O,O,O-NO2)(2-2-nitrobenzoate-O,O,O')

  16. Soft porous crystal meets TCNQ: charge transfer-type porous coordination polymers

    OpenAIRE

    Shimomura, Satoru; Kitagawa, Susumu

    2011-01-01

    The significant progress of porous coordination polymers (or metal–organic frameworks) has been attracting the attention of a lot of scientists in various disciplines and encouraging their entry into this field. The synergy of diverse scientific senses brings further spread of the chemistry of porous coordination polymers. In this review, we introduced the recent developments in PCPs resulting from the hybridization with TCNQ chemistry. Electronic and structural diversities of TCNQ provide no...

  17. Cu6S4 cluster based twelve-connected face-centered cubic and Cu19I4S12 cluster based fourteen-connected body-centered cubic topological coordination polymers.

    Science.gov (United States)

    Hao, Zheng-Ming; Fang, Rui-Qin; Wu, Hai-Shun; Zhang, Xian-Ming

    2008-09-15

    Hydrothermal reaction of Cu(MeCO2)2, (4-pyridylthio)acetic acid and NH4SCN resulted in a twelve-connected face-centered cubic topological metal-organic framework [Cu3(pdt)2(CN)] (pdt = pyridinethiolate) in which Cu6S4 clusters act as twelve-connected nodes and pyridine rings and cyanides act as connectors. As an extension, an unprecedented fourteen-connected body-centered cubic coordination polymer [Cu19I4(pdt)12(SH)3] has been synthesized by three methods, in which nanosized chiral Cu19I4S12 clusters act as fourteen-connected nodes and triple pyridine rings and hydrosulfides act as connectors. The in situ S-C(sp(3)), S-C(sp(2)), and S-C(sp) cleavage reactions have been observed in the work.

  18. Construction of Six Coordination Polymers Based on a 5,5′-(1,2-Ethynyl)bis-1,3-benzenedicarboxylic Ligand: Synthesis, Structure, Gas Sorption, and Magnetic Properties

    KAUST Repository

    Zheng, Bing

    2013-03-06

    Six novel coordination polymers based on a multifunctional ligand, 5,5\\'-(1,2-ethynyl)bis-1,3-benzenedicarboxylic (H4EBDC), namely, |(C3H7NO)2(H2O)7(C 2H5OH)3| [Zn2(C18H 6O8)(C10H8N2) 2] (1), |(C3H7NO)3(H2O)30- (CH3CN)2|[Zn 6(C18H6O8)3(C 6H12N2O2)2] (2), |(C 3H7NO)2- (H2O)2(H 3O)2|[Cd3(C18H6O 8)2] (3), |(C3H7NO)|[Mn- (C 18H8O8)(C3H7NO) 2] (4), |(C3H7NO)2(H2O)(C 2H7N)3| [Mn6(C18H 7O8)4(H2O)8] (5), and [Mn2(C18H6O8)(C3H 7NO)2] (6), have been constructed under solvothermal conditions and structurally characterized by single-crystal X-ray diffraction. In these compounds, the ligand, H4EBDC, exhibits different coordination modes and conformations, constructing various architectures by bridging a variety of metal ions or polynuclear clusters. Compound 1 forms a three-dimensional (3D) FSC network constructed from two-dimensional (2D) layer motifs joined by EBDC4- and 4,4\\'-bipyridine bridges. Compound 2 possesses an NbO topology by linking Zn2(CO2)4 units with the ligand, coordinated amine molecules fill the pores, while compound 3 exhibits a 3D FLU network with Cd2+ as the cation and features an infinite framework built from tricadmium clusters. Compound 4 is based on PtS net, constructed of 4-connected rectangular H4EBDC units with tetrahedral monometallic Mn(CO2)4 nodes. Compound 5 is composed of 2D layers with (3,6)-connected KGD topology, and compound 6 consists of a 3D PtS-X network, built by bridging a metal chain with the ligand. The structures of these compounds have been discussed together with their corresponding properties, such as gas storage, separation, and magnetic properties. © 2013 American Chemical Society.

  19. 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.

  20. Linear rheology of water-soluble reversible neodymium (III) coordination polymers

    NARCIS (Netherlands)

    Vermonden, T.; Steenbergen, van M.J.; Besseling, N.A.M.; Marcelis, A.T.M.; Hennink, W.E.; Sudhölter, E.J.R.; Cohen Stuart, M.A.

    2004-01-01

    The rheology of reversible coordination polymer networks in aqueous solution is studied. The polymers are formed by neodymium(III) ions and bifunctional ligands, consisting of two pyridine-2,6-dicarboxylate groups connected at the 4-positions by an ethylene oxide spacer. Neodymium(III) ions can bind

  1. Syntheses, structures and photoluminescent properties of Zn(Ⅱ)/Co(Ⅱ) coordination polymers based on flexible tetracarboxylate ligand of 5,5‧-(butane-1,4-diyl)-bis(oxy)-di isophthalic acid

    Science.gov (United States)

    Gao, Yan-Peng; Guo, Le; Dong, Wei; Jia, Min; Zhang, Jing-Xue; Sun, Zhong; Chang, Fei

    2016-08-01

    Three new mixed-ligand metal-organic frameworks based on 5,5‧-(butane-1,4- diyl)-bis(oxy)-diisophthalic acid and transitional metal cations with the help of two ancillary bridging N-donor pyridyl and imidazole linkers, [Zn(L)0.5(4,4‧-bpy)]·2(H2O) (1), [M(L)0.5(bib)]·4(H2O) (M = Zn (2), Co (3)), (4,4‧-bpy=4,4‧-bipyridine, bib=1,4-bis (1H-imidazol-1-yl)-butane), have been synthesized under solvothermal conditions. Their structures and properties were determined by single-crystal and powder X-ray diffraction analyses, IR spectra, elemental analyses and thermogravimetric analyses (TGA). Compounds 1-3 display a 3D 3-fold interpenetrated frameworks linked by the L4- ligands, ancillary N-donor linkers and the free water molecules in the crystal lattice. Topological analysis reveals that 1-3 are a (4,4)-connected bbf topology net with the (64·82)(66) topology. The effects of the L4- anions, the N-donor ligands, and the metal ions on the structures of the coordination polymers have been discussed. Furthermore, luminescence properties and thermogravimetric properties of these compounds were investigated.

  2. Syntheses, structures and characterization of isomorphous Co(II) and Ni(II) coordination polymers based on 2-[(1H-imidazol-1-yl)methyl]-6-methyl-1H-benzimidazole and benzene-1,4-dicarboxylate.

    Science.gov (United States)

    Huang, Qiu Ying; Zhao, Yang; Meng, Xiang Ru

    2017-08-01

    Careful choice of the organic ligands is one of the most important parameters in the rational design and synthesis of coordination polymers. Aromatic polycarboxylates have been widely used in the preparation of metal-organic polymers since they can utilize various coordination modes to form diverse structures and can act as hydrogen-bond acceptors and donors in the assembly of supramolecular structures. Nitrogen-heterocyclic organic compounds have also been used extensively as ligands for the construction of polymers with interesting structures. In the polymers catena-poly[[[diaquabis{2-[(1H-imidazol-1-yl)methyl]-6-methyl-1H-benzimidazole-κN(3)}cobalt(II)]-μ2-benzene-1,4-dicarboxylato-κ(2)O(1):O(4)] dihydrate], {[Co(C8H4O4)(C12H11N4)2(H2O)2]·2H2O}n, (I), and catena-poly[[[diaquabis{2-[(1H-imidazol-1-yl)methyl]-6-methyl-1H-benzimidazole-κN(3)}nickel(II)]-μ2-benzene-1,4-dicarboxylato-κ(2)O(1):O(4)] dihydrate], {[Ni(C8H4O4)(C12H11N4)2(H2O)2]·2H2O}n, (II), the Co(II) or Ni(II) ion lies on an inversion centre and exhibits a slightly distorted octahedral coordination geometry, coordinated by two N atoms from two imidazole rings and four O atoms from two monodentate carboxylate groups and two water molecules. The dicarboxylate ligands bridge metal ions forming a polymeric chain. The 2-[(1H-imidazol-1-yl)methyl]-6-methyl-1H-benzimidazole ligands coordinate to the Co(II) or Ni(II) centres in monodentate modes through an imidazole N atom and are pendant on opposite sides of the main chain. The two structures are isomorphous. In the crystal, the one-dimensional chains are further connected through O-H...O, O-H...N and N-H...O hydrogen bonds, leading to a three-dimensional supramolecular architecture. In addition, the IR spectroscopic properties, PXRD patterns, thermogravimetric behaviours and fluorescence properties of both polymers have been investigated.

  3. Theoretical investigation of polymer chain stability in the metal coordinated azorubine and cyclam complex

    Science.gov (United States)

    Vlassa, Mihaela; Bende, Attila

    2015-08-01

    Theoretical investigations have been performed for unit systems with Ni(II) and Zn(II) coordination between azorubine and 1,4,8,11-tetraazacyclotetradecane (cyclam) complexes using the conventional DFT and the DFT-based tight binding (DFTB) methods. Two different geometries (short and long) and spin states (singlet and triplet) of the model system built by two mesylate groups and the cyclam ring together with Ni(II) and Zn(II) ions were energetically characterized. For the Ni(II) coordination complex the triplet geometry is preferred, but one could not exclude also the presence of the singlet spin configuration due to the huge energy barrier defined by the intersystem crossing. The intersystem crossing geometry of the singlet-triplet transition was studied in details and the corresponding spin-orbit couplings were discussed. For the Zn(II) coordination complex only the singlet state was found. Polymer chain build up from four unit systems presents irregular forms with strong coordination bonds between units.

  4. Synthesis and structural characterization of a single-crystal to single-crystal transformable coordination polymer.

    Science.gov (United States)

    Tian, Yuyang; Allan, Phoebe K; Renouf, Catherine L; He, Xiang; McCormick, Laura J; Morris, Russell E

    2014-01-28

    A single-crystal to single-crystal transformable coordination polymer compound was hydrothermally synthesized. The structural rearrangement is induced by selecting a ligand that contains both strong and weaker coordinating groups. Both hydrated and dehydrated structures were determined by single crystal X-ray analysis.

  5. Structural diversity of four coordination polymers based on 5-nitro-1,2,3-benzenetricarboxylic acid (H3nbta): Solvothermal syntheses, structural characterizations and properties

    Science.gov (United States)

    Shi, Chenjie; Wang, Zikai; Chen, Yifan; Zhang, Xiaoyu; Zhao, Yue; Tao, Yuehong; Wu, Hua

    2017-09-01

    Four 3D coordination compounds, named [Cd3(nbta)2(bix)2(H2O)2]·H2O (1), Zn3(nbta)2(biim)3 (2), Zn6(nbta)4(btd)5 (3) and [Co3(nbta)2(bid)(H2O)8]·4H2O (4) (bix=1,4-bis(imidazole-1-ylmethyl)benzene, biim=1,1‧-(1,4-butanediyl)bis(imidazole), btd=1,10-bis(1,2,4-triazol-1-yl)decane, bid=1,10-bis(imidazole-1-yl)decane), and H3nbta=5-nitro-1,2,3-benzenetricarboxylic acid), have been synthesized by solvothermal methods and structurally characterized by X-ray diffraction studies. In compound 1, every nbta3- anion connects four CdII ions to give a 2D layer, and the layers are pillared by bix ligands to generate a 3D framework with a Schläfli symbol of (3·4·63·7)(4·64·8)(43·63)(34·42·66·76·88·92). For compound 2, every nbta3- anion connects three ZnII ions to give a 2D layer structure, the 2D layers are further connected into a facinating 3D framework by biim ligands with (3,4)-connected (3·6·7)(3·5·62·7·8)(3·52·6·8·9)(5·6·8·10·112) topology. In compound 3, the nbta3- anions are connected by ZnII ions to generate a 2D layer, and the layers are bridged by btd ligands to build a fascinating 3D framework with (4·6·7·8·92)(4·6·8·92·10)(4·93·102)(4·6·8·9·102)(4·6·7·8·9·10)(4·6·7·8·102)(42·6·7·8·9) topology. In compound 4, the nbta3- aions are connected by CoII ions into a 2D layer, the 2D layers are linked by bid ligands to generate a 3D 103 topological framework. Furthermore, the IR spectra, TGA, PXRD, elemental analyses, the solid-state luminescence of compounds 1-3 have been studied.

  6. A series of Ti(IV)/Ti(III) coordination polymers: structures and surface photoelectric properties.

    Science.gov (United States)

    Li, Lei; Zhang, Li; Liu, Dong-Wei; Jin, Jing; Chi, Yu-Xian; Niu, Shu-Yun

    2012-02-01

    Three titanium coordination polymers, {[Ti(SO(4))(2)(H(2)O)]·0.5bipy·2H(2)O}(n)1, {[Ti1(SO(4))(2)(H(2)O)]·[Ti2(SO(4))(2)(H(2)O)]·bipy·5H(2)O}(n)2 and [Ti(tea)](n)3 (bipy=4,4'-bipyridine, H(3)tea=triethanolamine) were synthesized and characterized by IR, UV-Vis absorption spectra, TG analysis, X-ray single crystal diffraction and surface photovoltage spectroscopy (SPS). The surface photoelectric properties of titanium coordination polymers were discussed emphatically by the SPS. The results of single crystal diffraction indicate that polymers 1 and 2 possess 1D infinite structure bridged by SO(4)(2-) groups and coordinated water molecules and further connected into supramolecular structures by hydrogen bonds. Polymer 3 possesses 2D infinite structure bridged by weak sub-coordinated Ti-O bonds. The results of SPS show that there are obvious photovoltage responses in the range of 300-500 nm, which indicates that they possess photoelectric conversion ability. The SPS of three titanium polymers were analyzed comparatively. It is found that the valence of central metal ions, coordination micro-environment and kinds of coordination atoms influence the results of the SPS. The SPS is associated with UV-Vis absorption spectra.

  7. A series of Ti(IV)/Ti(III) coordination polymers: Structures and surface photoelectric properties

    Science.gov (United States)

    Li, Lei; Zhang, Li; Liu, Dong-Wei; Jin, Jing; Chi, Yu-Xian; Niu, Shu-Yun

    2012-02-01

    Three titanium coordination polymers, {[Ti(SO 4) 2(H 2O)]·0.5bipy·2H 2O} n1, {[Ti1(SO 4) 2(H 2O)]·[Ti2(SO 4) 2(H 2O)]·bipy·5H 2O} n2 and [Ti(tea)] n3 (bipy = 4,4'-bipyridine, H 3tea = triethanolamine) were synthesized and characterized by IR, UV-Vis absorption spectra, TG analysis, X-ray single crystal diffraction and surface photovoltage spectroscopy (SPS). The surface photoelectric properties of titanium coordination polymers were discussed emphatically by the SPS. The results of single crystal diffraction indicate that polymers 1 and 2 possess 1D infinite structure bridged by SO 42- groups and coordinated water molecules and further connected into supramolecular structures by hydrogen bonds. Polymer 3 possesses 2D infinite structure bridged by weak sub-coordinated Ti-O bonds. The results of SPS show that there are obvious photovoltage responses in the range of 300-500 nm, which indicates that they possess photoelectric conversion ability. The SPS of three titanium polymers were analyzed comparatively. It is found that the valence of central metal ions, coordination micro-environment and kinds of coordination atoms influence the results of the SPS. The SPS is associated with UV-Vis absorption spectra.

  8. catena-Poly[[di-μ2-aqua-hexaaquabis(μ3-4-oxidopyridine-2,6-dicarboxylato)trimanganese(II)] trihydrate]: a new one-dimensional coordination polymer based on a trinuclear Mn(II) complex of chelidamic acid.

    Science.gov (United States)

    Mirzaei, Masoud; Eshtiagh-Hosseini, Hossein; Karrabi, Zahra; Notash, Behrouz

    2013-10-01

    4-Hydroxypyridine-2,6-dicarboxylic acid (chelidamic acid, hypydc[H]H2) reacts with MnCl2·2H2O in the presence of piperazine in water to afford the title complex, {[Mn3(C7H2NO5)2(H2O)8]·3H2O}n or {[Mn3(hypydc)2(H2O)8]·3H2O}n. This compound is a one-dimensional coordination polymer, with the twofold symmetric repeat unit containing three metal centres. Two different coordination geometries are observed for the two independent Mn(II) metal centres, viz. a distorted pentagonal bipyramid and a distorted octahedron. The 4-oxidopyridine-2,6-dicarboxylate anions and two of the water molecules act as bridging ligands. The zigzag-like geometry of the coordination polymer is stabilized by hydrogen bonds. O-H···O and C-H···O hydrogen bonds and water clusters consolidate the three-dimensional network structure.

  9. Syntheses, crystal structures, and luminescence of two lanthanide coordination polymers based on 5-(3‧,4‧-bis(tetrazol-5″-yl)phenoxy)isophthalic acid and 1,10-phenanthroline

    Science.gov (United States)

    Chen, Xiaoli; Li, Congcong; Ai, Fengfeng; Qu, Xu; Liu, Kang

    2017-04-01

    Two new lanthanide coordination polymers, [Ln(btpa)(phen)2(OH)]n·nH2O (Ln= Tb 1, Pr 2) (H2btpa=5-(3‧,4‧-bis(tetrazol-5″-yl)phenoxy)isophthalic acid, phen=1,10-phenanthroline), have been successfully synthesized and structurally characterized by elemental analyses, IR spectroscopy, single-crystal X-ray diffraction, TGA and powder X-ray diffraction analyses. Coordination polymers 1-2 are isomorphism structures, showing a 1D chain bearing hooks structure. LnⅢ ion in 1-2 adopt nine-coordinated mode to construct a tricapped trigonal prism configuration. The adjacent chains form a 2D supramolecular network via π … π stacking interactions between the pyridine rings of phen ligands. Then the neighbouring 2D supramolecular networks recognizing each other form a 3D supramolecular structure through π … π interaction between benzene rings of (btpa)2- ligands. The luminescence experiments show that TbIII complex exhibits typical metal-centered emissions in the visible region in the solid state.

  10. Polyphosphazine-based polymer materials

    Science.gov (United States)

    Fox, Robert V.; Avci, Recep; Groenewold, Gary S.

    2010-05-25

    Methods of removing contaminant matter from porous materials include applying a polymer material to a contaminated surface, irradiating the contaminated surface to cause redistribution of contaminant matter, and removing at least a portion of the polymer material from the surface. Systems for decontaminating a contaminated structure comprising porous material include a radiation device configured to emit electromagnetic radiation toward a surface of a structure, and at least one spray device configured to apply a capture material onto the surface of the structure. Polymer materials that can be used in such methods and systems include polyphosphazine-based polymer materials having polyphosphazine backbone segments and side chain groups that include selected functional groups. The selected functional groups may include iminos, oximes, carboxylates, sulfonates, .beta.-diketones, phosphine sulfides, phosphates, phosphites, phosphonates, phosphinates, phosphine oxides, monothio phosphinic acids, and dithio phosphinic acids.

  11. Conductive polymer-based material

    Science.gov (United States)

    McDonald, William F.; Koren, Amy B.; Dourado, Sunil K.; Dulebohn, Joel I.; Hanchar, Robert J.

    2007-04-17

    Disclosed are polymer-based coatings and materials comprising (i) a polymeric composition including a polymer having side chains along a backbone forming the polymer, at least two of the side chains being substituted with a heteroatom selected from oxygen, nitrogen, sulfur, and phosphorus and combinations thereof; and (ii) a plurality of metal species distributed within the polymer. At least a portion of the heteroatoms may form part of a chelation complex with some or all of the metal species. In many embodiments, the metal species are present in a sufficient concentration to provide a conductive material, e.g., as a conductive coating on a substrate. The conductive materials may be useful as the thin film conducting or semi-conducting layers in organic electronic devices such as organic electroluminescent devices and organic thin film transistors.

  12. Lead(II) coordination polymers based on rigid-flexible 3,5-bis-oxyacetate-benzoic acid: Structural transition driven by temperature control

    Science.gov (United States)

    Chen, Yong-Qiang; Tian, Yuan

    2017-03-01

    Three Pb(II) complexes {[Pb3(BOABA)2(H2O)]·H2O}n (1), {[Pb4(BOABA)2(μ4-O)(H2O)2]·H2O}n (2), and [Pb3(BOABA)2(H2O)]n (3) (H3BOABA=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 Pb4(μ4-O)(COO)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.

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

    Energy Technology Data Exchange (ETDEWEB)

    Chen Jianshan; Sheng Tianlu; Hu Shengmin; Xiang Shengchang; Fu Ruibiao; Zhu Qilong [State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou, Fujian 350002 (China); Wu Xintao, E-mail: wxt@fjirsm.ac.cn [State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou, Fujian 350002 (China)

    2012-08-15

    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{sub 2}O){sub 2}]{sub n} (3), [Cu(cbop){sub 2}(4,4 Prime -bipy)(H{sub 2}O)]{sub n} (4) (cbop=(S)-N-(4-cyanobenzoic)-5-oxoproline, 4,4 Prime -bipy=4,4 Prime -bipyridine), {l_brace}[Cu(nbop){sub 2}(4,4 Prime -bipy)]{center_dot}4H{sub 2}O{r_brace}{sub n} (5) (nbop=(S)-N-(4-nitrobenzoic)-5-oxoproline), {l_brace}[Cd(nbop){sub 2}(4,4 Prime -bipy)]{center_dot}2H{sub 2}O{r_brace}{sub n} (6), and [Ni(nbop){sub 2}(4,4 Prime -bipy)(H{sub 2}O){sub 2}]{sub 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 Prime -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: Black-Right-Pointing-Pointer Two new chiral aminocarboxylate derivates were firstly synthesized. Black-Right-Pointing-Pointer Five new homochiral metal organic complexes were obtained hydrothermally based on these ligands. Black-Right-Pointing-Pointer Intramolecular amidation was taken place on the aminocarboxylate derivates during the formation of these complexes. Black-Right-Pointing-Pointer In situ

  14. Bringing an "old" biological buffer to coordination chemistry: new 1D and 3D coordination polymers with [Cu(4)(Hbes)(4)] cores for mild hydrocarboxylation of alkanes.

    Science.gov (United States)

    Kirillov, Alexander M; Coelho, Jaime A S; Kirillova, Marina V; da Silva, M Fátima C Guedes; Nesterov, Dmytro S; Gruenwald, Katrin R; Haukka, Matti; Pombeiro, Armando J L

    2010-07-19

    New water-soluble 1D and 3D Cu(II)/Na coordination polymers 1-3 bearing unprecedented [Cu(4)(Hbes)(4)] cores have been easily generated by aqueous-medium self-assembly and fully characterized, thus opening up the use of the common biological buffer H(3)bes, (HO(3)SCH(2)CH(2))N(CH(2)CH(2)OH)(2), in synthetic coordination chemistry. Apart from representing the first isolated and structurally characterized coordination compounds derived from H(3)bes, 1-3 show a remarkable promoting effect in the mild aqueous-medium hydrocarboxylation, by CO and H(2)O, of gaseous alkanes (C(3)H(8) and n-C(4)H(10)) to the corresponding carboxylic acids, which are obtained in up to 95% yields based on the alkane.

  15. Syntheses, structures and photoluminescent properties of Zn(Ⅱ)/Co(Ⅱ) coordination polymers based on flexible tetracarboxylate ligand of 5,5′-(butane-1,4-diyl)-bis(oxy)-di isophthalic acid

    Energy Technology Data Exchange (ETDEWEB)

    Gao, Yan-Peng [Inner Mongolia Key Lab Chem & Phys Rare Earth Mat, College of Chemistry and Chemical Engineering, Inner Mongolia University, Hohhot 010021 (China); Department of Chemistry and Chemical Engineering, Ordos College of Inner Mongolia University, Ordos 017000 (China); Department of Chemistry and Chemical Engineering, Ordos Applied Technology College, Ordos 017000 (China); Guo, Le [Department of Chemistry and Chemical Engineering, Ordos College of Inner Mongolia University, Ordos 017000 (China); Department of Chemistry and Chemical Engineering, Ordos Applied Technology College, Ordos 017000 (China); Dong, Wei; Jia, Min; Zhang, Jing-Xue; Sun, Zhong [Inner Mongolia Key Lab Chem & Phys Rare Earth Mat, College of Chemistry and Chemical Engineering, Inner Mongolia University, Hohhot 010021 (China); Chang, Fei, E-mail: ndchfei@imu.edu.cn [Inner Mongolia Key Lab Chem & Phys Rare Earth Mat, College of Chemistry and Chemical Engineering, Inner Mongolia University, Hohhot 010021 (China)

    2016-08-15

    Three new mixed-ligand metal-organic frameworks based on 5,5′-(butane-1,4- diyl)-bis(oxy)-diisophthalic acid and transitional metal cations with the help of two ancillary bridging N-donor pyridyl and imidazole linkers, [Zn(L){sub 0.5}(4,4′-bpy)]·2(H{sub 2}O) (1), [M(L){sub 0.5}(bib)]·4(H{sub 2}O) (M = Zn (2), Co (3)), (4,4′-bpy=4,4′–bipyridine, bib=1,4-bis (1H-imidazol-1-yl)-butane), have been synthesized under solvothermal conditions. Their structures and properties were determined by single-crystal and powder X-ray diffraction analyses, IR spectra, elemental analyses and thermogravimetric analyses (TGA). Compounds 1–3 display a 3D 3-fold interpenetrated frameworks linked by the L{sup 4−} ligands, ancillary N-donor linkers and the free water molecules in the crystal lattice. Topological analysis reveals that 1–3 are a (4,4)-connected bbf topology net with the (6{sup 4}·8{sup 2})(6{sup 6}) topology. The effects of the L{sup 4−} anions, the N-donor ligands, and the metal ions on the structures of the coordination polymers have been discussed. Furthermore, luminescence properties and thermogravimetric properties of these compounds were investigated. - Graphical abstract: Three new compounds of MOFs have been prepared and characterized. The luminescence properties and thermogravimetric properties of compounds were investigated. Display Omitted.

  16. Three new three-dimensional organic-inorganic hybrid compounds based on PMo12O40(n-) (n = 3 or 4) polyanions and Cu(I)-pyrazine/Cu(I)-pyrazine-Cl porous coordination polymers.

    Science.gov (United States)

    Qi, Ming-Li; Yu, Kai; Su, Zhan-Hua; Wang, Chun-Xiao; Wang, Chun-Mei; Zhou, Bai-Bin; Zhu, Chun-Cheng

    2013-06-07

    Three new organic-inorganic hybrid compounds based on PMo12O40(n-) (n = 3 or 4) polyanions and Cu(I)-pz/Cu(I)-pz-Cl porous coordination polymers: [Cu(I)(pz)]3[PMo(VI)12O40] (1), [Cu(I)(pz)1.5]4[PMo(V)Mo(VI)11O40]·pz·2H2O (2), [Cu(I)3(pz)3Cl][Cu(I)2(pz)3(H2O)][PMo(V)Mo(VI)11O40] (3) (pz = pyrazine) have been hydrothermally prepared and characterized by elemental analysis, IR, TG, XRD, XPS and single-crystal X-ray diffraction. Compound 1 presents a three-dimensional Cu(I)-pz framework with cube-like chambers, into which PMo(VI)12O40(3-) Keggin ions are incorporated. Compound 2 shows a three-dimensional sandwich-like framework, and PMo(V)Mo(VI)11O40(4-) polyanions are located in the octagonal voids of every two-dimensional Cu(I)-pz 4(1)8(2) network structure. Compound 3 exhibits a two-dimensional Cl-bridged Cu(I)-pz-Cl double-layer structure, and two kinds of PMo(V)Mo(VI)11O40(4-) polyanions as bridging linkers connect two adjacent double-layers to form a three-dimensional organic-inorganic framework through Cu(I)-O bonds. Additionally, their electrochemical characters, electrocatalytic behaviors and solid state fluorescent properties at room temperature have been investigated in detail.

  17. 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

    Science.gov (United States)

    Arıcı, Mürsel; Zafer Yeşilel, Okan; Büyükgüngör, Orhan

    2017-05-01

    Four coordination polymers including, [Co(μ-Htbip)2(μ-dib)]n (1), [Co(μ-tbip)(μ-dmib)0.5]n (2), [Zn2(μ-tbip)(μ3-tbip)(μ-dmib)1.5]n (3) and [Cd(μ3-tbip)(μ-dib)0.5 (H2O)]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.

  18. Coordination polymer core/shell structures: Preparation and up/down-conversion luminescence.

    Science.gov (United States)

    Li, Bingmei; Xu, Hualan; Xiao, Chen; Shuai, Min; Chen, Weimin; Zhong, Shengliang

    2016-10-01

    Coordination polymer (CP) core-shell nanoparticles with Gd-based CP (GdCP) as core and Eu-based CP (EuCP) as shell have been successfully prepared. Allantoin was employed as the organic building block without the assistance of any template. The composition, size and structure of the core-shell nanospheres were well characterized by scanning electron microscopy (SEM), transmission electron microscopy (TEM), energy dispersive X-ray (EDX), powder X-ray diffraction (PXRD), Fourier transform infrared spectroscopy (FT-IR), thermo-gravimetric analysis (TG). Results show that the resultant cores are uniform nanospheres with diameter of approximately 45nm, while the diameters of the core-shell nanospheres are increased to approximately 60nm. The core-shell products show enhanced luminescence efficiency than the core under 980nm laser excitation and decreased down-conversion luminescence when excited at 394nm.

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

    Science.gov (United States)

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

    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(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.

  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. Porphyrin-Cored Polymer Nanoparticles: Macromolecular Models for Heme Iron Coordination.

    Science.gov (United States)

    Rodriguez, Kyle J; Hanlon, Ashley M; Lyon, Christopher K; Cole, Justin P; Tuten, Bryan T; Tooley, Christian A; Berda, Erik B; Pazicni, Samuel

    2016-10-03

    Porphyrin-cored polymer nanoparticles (PCPNs) were synthesized and characterized to investigate their utility as heme protein models. Created using collapsible heme-centered star polymers containing photodimerizable anthracene units, these systems afford model heme cofactors buried within hydrophobic, macromolecular environments. Spectroscopic interrogations demonstrate that PCPNs display redox and ligand-binding reactivity similar to that of native systems and thus are potential candidates for modeling biological heme iron coordination.

  2. 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.

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

    Science.gov (United States)

    Meundaeng, Natthaya; Rujiwatra, Apinpus; Prior, Timothy J.

    2017-01-01

    We have successfully prepared crystals of thiazole-5-carboxylic acid (5-Htza) (L) and three new thiazole-5-carboxylate-based Cu2+ coordination polymers with different dimensionality, namely, 1D [Cu2(5-tza)2(1,10-phenanthroline)2(NO3)2] (1), 2D [Cu(5-tza)2(MeOH)2] (2), and 3D [Cu(5-tza)2]·H2O (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)2]·1.5H2O upon heat treatment for 2 h. This 2D network can adsorb water and convert to 3 upon exposure to air.

  4. Hyperbranched Polymer-Based Electrolyte for Lithium Polymer Batteries

    Institute of Scientific and Technical Information of China (English)

    Takahito Itoh

    2005-01-01

    @@ 1Introduction Solid polymer electrolytes have attracted much attention as electrolyte materials for all solid-state recharge able lithium batteries, and poly ( ethylene oxide) ( PEO)-based polymer electrolytes are among the most intensively studied systems[1-3]. Hyperbranched polymers have unique properties such as completely amorphous, highly soluble in common organic solvent and processible because of the highly branched nature[4,5].

  5. Coordination polymers assembled through pi-pi interactions

    CERN Document Server

    Plummer, E A

    2001-01-01

    Chapter one is a review of the relevant literature. In chapter two the coordination chemistry of biphenyl-tailed terpyridines with octahedral metal dications is investigated. The effect of different metal ions on their aggregation modes in the solid state is also investigated. In chapter three the coordination chemistry of polyaryl-tailed terpyridines with octahedral metal dications is investigated. The effect of different aryl tails on their aggregation modes in the solid state is investigated. In chapter four the pi-pi aggregation of molecular boxes through biphenyl tails is studied. In chapter five the immobilisation of aryl tailed complexes into polyelectrolyte films has been investigated, and the arrangement of these complexes in the films has been compared with same complexes in the crystal, thus moving from three dimensional aggregation to two dimensions.

  6. 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

    2013-05-01

    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.

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

    Science.gov (United States)

    Jin, Jing; Han, Xiao; Meng, Qin; Li, Dan; Chi, Yu-Xian; Niu, Shu-Yun

    2013-01-01

    Five Cd(II)/Zn(II) complexes [Cd(1,2-bdc)(pz)2(H2O)]n (1), [Cd1Cd2(btec)(H2O)6]n (2), [Cd(3,4-pdc) (H2O)]n (3), [Zn(2,5-pdc)(H2O)4]·2H2O (4) and {[Zn(2,5-pdc)(H2O)2]·H2O}n (5) (H2bdc=1,2-benzenedicarboxylic acid, pz=pyrazole, H4btec=1,2,4,5-benzenetetracarboxylic acid, H2pdc=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.

  8. 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%.

  9. Two new two-dimensional coordination polymers based on isophthalate and a flexible N-donor ligand containing benzimidazole and pyridine rings: synthesis, crystal structures and a solid-state UV-Vis study.

    Science.gov (United States)

    Hasi, Qi Meige; Fan, Yan; Hou, Chen; Yao, Xiao Qiang; Liu, Jia Cheng

    2016-10-01

    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. N-Donor ligands with diverse coordination modes and conformations 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 and are thus good candidates for the construction of supramolecular architectures. Two new transition metal complexes, namely poly[diaqua(μ4-1,4-bis{[1-(pyridin-3-ylmethyl)-1H-benz[d]imidazol-2-yl]methoxy}benzene)bis(μ2-isophthalato)dicobalt(II)], [Co(C8H4O4)(C34H28N6O2)0.5(H2O)]n, (1), and poly[diaqua(μ4-1,4-bis{[1-(pyridin-3-ylmethyl)-1H-benz[d]imidazol-2-yl]methoxy}benzene)bis(μ2-isophthalato)dicadmium(II)], [Cd(C8H4O4)(C34H28N6O2)0.5(H2O)]n, have been constructed using a symmetric N-donor ligand and a carboxylate ligand under hydrothermal conditions. X-ray crystallographic studies reveal that complexes (1) and (2) are isostructural, both of them exhibiting three-dimensional supramolecular architectures built by hydrogen bonds in which the coordinated water molecules serve as donors, while the O atoms of the carboxylate groups act as acceptors. Furthermore, (1) and (2) have been characterized by elemental, IR spectroscopic, powder X-ray diffraction (PXRD) and thermogravimetric analyses. The UV-Vis absorption spectrum of complex (1) has also been investigated.

  10. Synthesis and Crystal Structure of a Novd Nickel (Ⅱ) Coordination Polymer with Chiral Schiff-base%新型手性希夫碱镍配位聚合物的合成及其晶体结构

    Institute of Scientific and Technical Information of China (English)

    班风俊; 盛恩宏; 龚腾飞; 叶诚诚

    2012-01-01

    A novel chiral nickel ( II ) coordination polymer with Schiff-base, Ni2(salen)2 { salen = (R,R)-( - )-N, N'-bis[3-tert-butyl-5-(4-ethynylpyridyl) salicyl-idene]-1,2-diaminocyclohexane} (1) , was synthesized. The structure was characterized by single-crystal X-ray crystallography and elemental analysis. The 1 belongs to monoclinic, space group C2 with a =25.060(5) A, b = 13.508 (3) A, c = ll.938(2) A, α=90(3)°, β = 104.82(3)°, γ =90(3)°, V = 3 906.7(14) A3, Z = 4, Mr = 828.24, Dc = 1.429 g · cm-3, F(000) = 1808, μ = 1. 027 mm-1, GOF = 1.068, R1=-0.051 0, wR2 =0.128 9. 1 is constructed by intermolecular π---Π interaction and assembled into a 2D structure via CH---Π interactions between the cyclohexanes and benzene rings.%以手性对称的Shiff碱为配体,合成了手性镍配合物[Ni2(salen)2(1)],其结构经X-单晶射线衍射和元素分析表征.1属单斜晶系,C2空间群,晶胞参数a =25.060(5)(A),b=13.508(3)(A),c= 11.938(2)(A),α=90(3)°,β=104.82(3)°,γ=90(3)°,V=3906.7(14)(A)3,Z=4,Mr=828.24,Dc=1.429 g·cm-3,F(000)=1808,μ=1.027mm-1,GOF=1.068,R1=0.051 0,wR2=0.1289.在1的分子结构中,环己胺和苯环之间通过分子间CH…π作用形成二维结构.

  11. Wormlike aggregates from a supramolecular coordination polymer and a diblock copolymer

    NARCIS (Netherlands)

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

    2007-01-01

    The formation of wormlike micelles in mixed systems of a supramolecular coordination polymer Zn-L2EO4 and a diblock copolymer P2MVP41-b-PEO205 is investigated by light scattering and Cryo-TEM. By direct mixing at a stoichiometric charge ratio, the above mixtures proved to be capable of formation of

  12. Zinc(II) and Cadmium(II) coordination polymers constructed from phenylenediacetate ligands

    Energy Technology Data Exchange (ETDEWEB)

    Sezer, Güneş Günay [Vocational School of Health Services, Bartın University, Bartın (Turkey); Department of Chemistry, Eskişehir Osmangazi University, Eskişehir (Turkey); Yeşilel, Okan Zafer; Erer, Hakan [Department of Chemistry, Eskişehir Osmangazi University, Eskişehir (Turkey); Şahin, Onur [Scientific and Technological Research Application Center, Sinop University, Sinop (Turkey)

    2016-01-15

    ABSTRACT: A series of new coordination polymers {[Zn(μ-opda)(μ-bpa)]·2H_2O}{sub n} (1), [Zn(μ{sub 3}-ppda)(μ-bpa)]{sub n} (2), [Cd(μ{sub 3}-ppda)(μ-bpa)]{sub n} (3), [Cd(μ{sub 3}-mpda)(μ-bpa)]{sub n} (4) and [Cd(μ{sub 3}-mpda)(μ-bipy)]{sub n} (5), (o/m/ppda=1,2/1,3/1,4-phenylenediacetate, bpa=1,2-bi(4-pyridyl)ethane, bipy=4,4′-bipyridine) were synthesized. Their structures were characterized by elemental analysis, IR spectroscopy, single-crystal and powder X-ray diffraction. Furthermore, the effect of metal sources (zinc acetate and zinc oxide) and acidity of the solution on the structure of the coordination polymers was discussed for complexes 1 and 5, respectively. The single-crystal X-ray crystallographic studies revealed that complexes 1, 3, 4 and 5 are uninodal (4)-connected 2D frameworks and display sql topology with the point symbol of (4{sup 4}.6{sup 2}). Complex 2 is 3D coordination polymer and exhibits pcu topology with the point symbol of (4{sup 12}.6{sup 3}). In addition, the luminescent properties and thermal behavior of all complexes were also investigated. - Graphical abstract: Scheme 1. Topologies of Coordination Polymers Reported in This Paper.

  13. Natural Gas Purification Using a Porous Coordination Polymer with Water and Chemical Stability

    NARCIS (Netherlands)

    Duan, J.; Jin, W.; Krishna, R.

    2015-01-01

    Porous coordination polymers (PCPs), constructed by bridging the metals or clusters and organic linkers, can provide a functional pore environment for gas storage and separation. But the rational design for identifying PCPs with high efficiency and low energy cost remains a challenge. Here, we demon

  14. New Twists and Turns for Actinide Chemistry: Organometallic Infinite Coordination Polymers of Thorium Diazide.

    Science.gov (United States)

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

    2016-03-07

    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.

  15. Natural Gas Purification Using a Porous Coordination Polymer with Water and Chemical Stability

    NARCIS (Netherlands)

    Duan, J.; Jin, W.; Krishna, R.

    2015-01-01

    Porous coordination polymers (PCPs), constructed by bridging the metals or clusters and organic linkers, can provide a functional pore environment for gas storage and separation. But the rational design for identifying PCPs with high efficiency and low energy cost remains a challenge. Here, we demon

  16. The crystal structure, luminescence and nitrobenzene-sensing properties of a two-dimensional Mn(II) coordination polymer based on 2,6-bis(imidazol-1-yl)pyridine.

    Science.gov (United States)

    Wang, Yin-Lin; Long, Ling-Liang; Zhang, Jin-Fang

    2015-06-01

    A two-dimensional Mn(II) coordination polymer (CP), poly[bis[μ2-2,6-bis(imidazol-1-yl)pyridine-κ(2)N(3):N(3')]bis(thiocyanato-κN)manganese] [Mn(NCS)2(C11H9N5)2]n, (I), has been obtained by the self-assembly reaction of Mn(ClO4)2·6H2O, NH4SCN and bent 2,6-bis(imidazol-1-yl)pyridine (2,6-bip). CP (I) was characterized by FT-IR spectroscopy, elemental analysis and single-crystal X-ray diffraction. The crystal structure features a unique two-dimensional (4,4) network with one-dimensional channels. The luminescence and nitrobenzene-sensing properties were explored in a DMF suspension, revealing that CP (I) shows a strong luminescence emission and is highly sensitive for nitrobenzene detection.

  17. Thermo- and piezochromic properties of [Fe(hyptrz)]A{sub 2}·H{sub 2}O spin crossover 1D coordination polymer: Towards spin crossover based temperature and pressure sensors

    Energy Technology Data Exchange (ETDEWEB)

    Jureschi, Catalin-Maricel [Department of Electrical Engineering and Computer Science and Advanced Materials and Nanotechnology Laboratory (AMNOL), Stefan cel Mare University, University Street 13, Suceava 720229 (Romania); LISV, UVSQ, 78035 Versailles Cedex (France); Rusu, Ionela [Department of Electrical Engineering and Computer Science and Advanced Materials and Nanotechnology Laboratory (AMNOL), Stefan cel Mare University, University Street 13, Suceava 720229 (Romania); Codjovi, Epiphane [Groupe d’Etude de la Matière Condensée (GEMaC), CNRS-UMR 8635, UVSQ, 78035 Versailles Cedex (France); Linares, Jorge, E-mail: jorge.linares@uvsq.fr [Groupe d’Etude de la Matière Condensée (GEMaC), CNRS-UMR 8635, UVSQ, 78035 Versailles Cedex (France); Garcia, Yann [Institute of Condensed Matter and Nanosciences, Molecules, Solids, Reactivity (IMCN/MOST), Université Catholique de Louvain, Place L. Pasteur 1, 1348 Louvain-la-Neuve (Belgium); Rotaru, Aurelian, E-mail: rotaru@eed.usv.ro [Department of Electrical Engineering and Computer Science and Advanced Materials and Nanotechnology Laboratory (AMNOL), Stefan cel Mare University, University Street 13, Suceava 720229 (Romania)

    2014-09-15

    We have used reflectance measurements to investigate the effect of a hydrostatic pressure on the molecular 1D spin crossover coordination polymer [Fe(hyptrz)]A{sub 2}·H{sub 2}O (hyptrz=4-(3′-hydroxypropyl)-1,2,4-triazole and A=4-chloro-benzenesulfonate) Rev. Sci. Instrum. 80 (2009) 123901. Both thermal and pressure hysteresis have been recorded at different pressures and temperatures, respectively, in order to obtain valuable information about the optimal conditions of their use as wireless temperature and pressure sensors. The experimental analysis has been completed with a theoretical study and potential applications in terms of temperature and pressure wireless detection are discussed.

  18. Seawater-Assisted Self-Healing of Catechol Polymers via Hydrogen Bonding and Coordination Interactions.

    Science.gov (United States)

    Li, Jincai; Ejima, Hirotaka; Yoshie, Naoko

    2016-07-27

    It is highly desirable to prevent crack formation in polymeric materials at an early stage and to extend their lifespan, particularly when repairs to these materials would be difficult for humans. Here, we designed and synthesized catechol-functionalized polymers that can self-heal in seawater through hydrogen bonding and coordination. These bioinspired acrylate polymers are originally viscous materials, but after coordination with environmentally safe, common metal cations in seawater, namely, Ca(2+) and Mg(2+), the mechanical properties of the polymers were greatly enhanced from viscous to tough, hard materials. Reduced swelling in seawater compared with deionized water owing to the higher osmotic pressure resulted in greater toughness (∼5 MPa) and self-healing efficiencies (∼80%).

  19. A new one-dimensional Zn(II) coordination polymer based on 2-[(1H-imidazol-1-yl)methyl]-1H-benzimidazole and benzene-1,2-dicarboxylate.

    Science.gov (United States)

    Huang, Qiu-Ying; Liu, Wei; Yang, Yi; Meng, Xiang-Ru

    2015-11-01

    Multidentate N-heterocyclic compounds form a variety of metal complexes with many intriguing structures and interesting properties. The title coordination polymer, catena-poly[zinc(II)-bis{μ-2-[(1H-imidazol-1-yl)methyl]-1H-benzimidazole}-κ(2)N(3):N(3');N(3'):N(3)-zinc(II)-bis(μ-benzene-1,2-dicarboxylato)-κ(2)O(1):O(2);κ(3)O(1),O(1'):O(2)], [Zn2(C8H4O4)2(C11H10N4)2]n, has been synthesized by the reaction of Zn(NO3)2 with 2-[(1H-imidazol-1-yl)methyl]-1H-benzimidazole (imb) and benzene-1,2-dicarboxylic acid (H2bdic) under hydrothermal conditions. There are two crystallographically distinct imb ligands [imb(A) and imb(B)] in the structure which adopt very similar coordination geometries. The imb(A) ligand bridges two symmetry-related Zn1 ions, yielding a binuclear [(Zn1)2{imb(A)}2] unit, and the imb(B) ligand bridges two symmetry-related Zn2 ions resulting in a binuclear [(Zn2)2{imb(B)}2] unit. The above-mentioned binuclear units are further connected alternately by pairs of bridging bdic(2-) ligands, forming an infinite one-dimensional chain. These one-dimensional chains are further connected through N-H···O hydrogen bonds, leading to a two-dimensional layered structure. In addition, the title polymer exhibits good fluorescence properties in the solid state at room temperature.

  20. Fabrication of a PANI/CPs composite material: a feasible method to enhance the photocatalytic activity of coordination polymers.

    Science.gov (United States)

    Xu, Xin-Xin; Cui, Zhong-Ping; Qi, Ji; Liu, Xiao-Xia

    2013-03-21

    To improve the photocatalytic activity of a coordination polymer in the visible light region, polyaniline (PANI) was loaded onto its surface through a facile in situ chemical oxidation polymerization process. The resulting PANI loaded coordination polymer composite materials with excellent stability exhibit significantly higher photocatalytic activities than the pure coordination polymer photocatalyst on the degradation of methyl orange (MO) under visible light irradiation. This enhancement can be ascribed to the introduction of PANI on the surface of the coordination polymer, which leads to efficient separation of photogenerated electron-hole pairs as well as a significant expansion of the photoresponse region. Finally, we discussed the influence of acidity on the morphology and photocatalytic activity of the composite material. An optimal condition to obtain the PANI loaded coordination polymer composite material with excellent photocatalytic activity has been obtained.

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

    Energy Technology Data Exchange (ETDEWEB)

    Choi, Eun Young; Gao, Chunji; Lee, Suck Hyun; Kwon, O Pil [Ajou University, Suwon (Korea, Republic of)

    2012-04-15

    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{sub 2}){sub 6}CH{sub 3} or long -O(CH{sub 2}){sub 9}CH{sub 3} side chains, respectively, new BDC linkers with oxyethylene side chains of the same lengths, -(OCH{sub 2}CH{sub 2}){sub 2}CH{sub 3} and -(OCH{sub 2}CH{sub 2}){sub 3}CH{sub 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

  2. One dimensional coordination polymers: Synthesis, crystal structures and spectroscopic properties

    Science.gov (United States)

    Karaağaç, Dursun; Kürkçüoğlu, Güneş Süheyla; Şenyel, Mustafa; Şahin, Onur

    2016-11-01

    Two new one dimensional (1D) cyanide complexes, namely [M(4-aepy)2(H2O)2][Pt(CN)4], (4-aepy = 4-(2-aminoethyl)pyridine M = Cu(II) (1) or Zn(II) (2)), have been synthesized and characterized by vibrational (FT-IR and Raman) spectroscopy, single crystal X-ray diffraction, thermal and elemental analyses techniques. The crystallographic analyses reveal that 1 and 2 are isomorphous and isostructural, and crystallize in the monoclinic system and C2 space group. The Pt(II) ions are coordinated by four cyanide-carbon atoms in the square-planar geometry and the [Pt(CN)4]2- ions act as a counter ion. The M(II) ions display an N4O2 coordination sphere with a distorted octahedral geometry, the nitrogen donors belonging to four molecules of the organic 4-aepy that act as unidentate ligands and two oxygen atoms from aqua ligands. The crystal structures of 1 and 2 are similar each other and linked via intermolecular hydrogen bonding, Pt⋯π interactions to form 3D supramolecular network. Vibration assignments of all the observed bands are given and the spectral features also supported to the crystal structures of the complexes.

  3. Luminescent Europium(III) Coordination Zippers Linked with Thiophene-Based Bridges.

    Science.gov (United States)

    Hirai, Yuichi; Nakanishi, Takayuki; Kitagawa, Yuichi; Fushimi, Koji; Seki, Tomohiro; Ito, Hajime; Hasegawa, Yasuchika

    2016-09-19

    Novel Eu(III) coordination polymers [Eu(hfa)3 (dpt)]n (dpt: 2,5-bis(diphenylphosphoryl)thiophene) and [Eu(hfa)3 (dpedot)]n (dpedot: 2,5-bis(diphenylphosphoryl)ethylenedioxythiophene) with hydrogen-bonded zipper structures are reported. The coordination polymers are composed of Eu(III) ions, hexafluoroacetylacetonato ligands, and thiophene-based phosphine oxide bridges. The zig-zag orientation of single polymer chains induced the formation of densely packed coordination structures with multiple intermolecular interactions, resulting in thermal stability above 300 °C. They exhibit a high intrinsic emission quantum yield (ca. 80 %) due to their asymmetrical and low-vibrational coordination structures around Eu(III) ions. Furthermore, the characteristic alternative orientation of substituents also contributes to the dramatically high ligand-to-metal energy transfer efficiencies of up to 80 % in the solid state.

  4. Synthesis and Structural Characterization of a New 2D Coordination Polymer [Cu(pzta)2]n

    Institute of Scientific and Technical Information of China (English)

    HU,Xin; LIU,Cong; WANG,Yongjiang; GUO,Jixi

    2009-01-01

    A new copper(Ⅱ)tetrazolate coordination polymer[Cu(pzta)2]n (1)(pzta=5-pyrazinyltetrazolate)was prepared from the hydrothermal reaction of Cu(OAc)2,·H2O with NaN3 and pyrazinecarbonitrile(pzCN)in the presence of ethanol,and characterized by elemental analysis,IR,TGA and X-ray crystallography.The X-ray diffraction analysis of 1 shows that the compound crystallizes in the monoclinic system with space group P2(1)/c and Cu(Ⅱ)ion center is six-coordinated by four different pzta ligands.The complex 1 features a 2D tetrazole coordination polymer.The thermal analysis of 1 shows that the decomposition of the complex OCCURS in two regions.

  5. Anion-controlled assembly of silver-di(aminophenyl)sulfone coordination polymers: Syntheses, crystal structures, and solid state luminescence

    Energy Technology Data Exchange (ETDEWEB)

    Zhang, Qi-Long, E-mail: gzuqlzhang@126.com [Department of Chemistry, Guiyang Medical College, Guiyang 550004 (China); Hu, Peng [Department of Chemistry, Guiyang Medical College, Guiyang 550004 (China); Zhao, Yi [Key Laboratory of Macrocyclic and Supramolecular Chemistry, Guizhou University, Guiyang 550025 (China); Feng, Guang-Wei [Department of Chemistry, Guiyang Medical College, Guiyang 550004 (China); Zhang, Yun-Qian; Zhu, Bi-Xue; Tao, Zhu [Key Laboratory of Macrocyclic and Supramolecular Chemistry, Guizhou University, Guiyang 550025 (China)

    2014-02-15

    Five silver coordination polymers, namely, ([Ag(3,3′-daps){sub 2}]·BF{sub 4}){sub n} (1), ([Ag(3,3′-daps){sub 2}]·NO{sub 3}){sub n} (2), [Ag(3,3′-daps)(CF{sub 3}SO{sub 3})]{sub n} (3), ([Ag(4,4′-daps)]·CF{sub 3}SO{sub 3}){sub n} (4), and ([Ag(4,4′-daps)]·ClO{sub 4}){sub n} (5) (3,3′-daps=di(3′-aminodiphenyl)sulfone, and 4,4′-daps=di(4′-aminodiphenyl)sulfone) have been synthesized and structural characterized by elemental analyses, IR spectra, powder X-ray diffraction (PXRD) and single-crystal X-ray diffraction analyses. Complex 1 displays a 1D ladder-like chain with four-connected Ag ions and bridged 3,3′-daps. Complex 2 shows other 1D ladder chain modified by tentacles. Complex 3 is a 2D layer structure with both Ag ions and 3,3′-daps are 3-connected nodes. Complex 4 is another 1D ladder chain with three-connected Ag ions and 4,4′-daps. Complex 5 shows a 2D 4{sup 4}-sql net with Ag ions and 4,4′-daps as 4-connected nodes. Moreover, their solid state luminescence and thermal stabilities also have been investigated. - Graphical abstract: Pictogram: Synthetic procedures of the five anion controlled silver coordination polymers. We reported the synthetic procedures, structure, and luminescence property of the five anion controlled silver coordination polymers based on two novel di(aminophenyl)sulfone V-shaped ligands. Display Omitted - Highlights: • Five new silver coordination polymers were synthesized and characterized. • Two novel designed V-shaped di(aminophenyl)sulfone ligands were first introduced to coordination chemistry. • Anions play important roles in determining the five silver coordination polymers. • The structural diversity and photoluminescence property were also discussed.

  6. Preparation, Crystal Structure and Enthalpy Change of Formation of the Reaction in Liquid Phase of a New Three-Dimensional Mixed-Ligand Holmium(Ⅲ) Coordination Polymer Based on Strong π-π Stacking Interactions

    Institute of Scientific and Technical Information of China (English)

    REN,Yi-Xia; CHEN,San-Ping; GAO,Sheng-Li

    2007-01-01

    A new three-dimensional coordination polymer, [Ho(5-nip)(phen)(NO3)(DMF)] (5-nip=5-nitroisophthalic acid and phen=1,10-phenanthroline), was prepared and characterized by single crystal X-ray diffraction, elemental analysis, IR spectrum and DTG-DSC techniques. The results show that the title complex crystallizes in space group P2/m with a= 1.0906(3) nm, b=1.2804 (3) nm, c= 1.6987(4) nm,β=91.400(5)°, Z=4, Dc= 1.931 Mg/m3, F(000)=1352. Each Ho(Ⅲ) ion is nine-coordinated by one chelating bidentate and two monodentate bridging carboxylate groups, one chelating bidentate NO3- anion, one DMF molecule and one 1,10-phenanthroline molecule. The complex is constructed with one-dimensional ribbons featuring dinuclear units and the one-dimensional ribbons are further assembled into two-dimensional networks by strong π-π stacking interactions with the distance of 0.327 nm,then the networks are arranged into three-dimensional structure according to ABAB fashion. The complex exhibits high stability up to 600 ℃. Its enthalpy change of formation of the reaction in liquid-phase in solvent DMF was measured using an RD496-Ⅲ type microcalorimeter with a value of (-11.016±0.184) kJ·mol-1.

  7. Bio-Inspired Composite Interfaces: Controlling Hydrogel Mechanics via Polymer-Nanoparticle Coordination Bond Dynamics

    Science.gov (United States)

    Holten-Andersen, Niels

    2015-03-01

    In soft nanocomposite materials, the effective interaction between polymer molecules and inorganic nanoparticle surfaces plays a critical role in bulk mechanical properties. However, controlling these interfacial interactions remains a challenge. Inspired by the adhesive chemistry in mussel threads, we present a novel approach to control composite mechanics via polymer-particle interfacial dynamics; by incorporating iron oxide nanoparticles (Fe3O4 NPs) into a catechol-modified polymer network the resulting hydrogels are crosslinked via reversible coordination bonds at Fe3O4 NP surfaces thereby providing a dynamic gel network with robust self-healing properties. By studying the thermally activated composite network relaxation processes we have found that the polymer-NP binding energy can be controlled by engineering both the organic and inorganic side of the interface.

  8. Three one-dimensional coordination polymers based on 1,1'-bis(pyridin-4-ylmethyl)-2,2'-bi-1H-benzimidazole and HgX2 (X = Cl, Br and I).

    Science.gov (United States)

    Li, Ai-Guo; Liu, Qi-Kui; Li, Yan-An; Liu, Zhi-Xian; Dong, Yu-Bin

    2014-01-01

    A new 2,2'-bi-1H-benzimidazole bridging organic ligand, namely 1,1'-bis(pyridin-4-ylmethyl)-2,2'-bi-1H-benzimidazole, C26H20N6, L or (I), has been synthesized and used to create three new one-dimensional coordination polymers, viz. catena-poly[[dichloridomercury(II)]-μ-1,1'-bis(pyridin-4-ylmethyl)-2,2'-bi-1H-benzimidazole], [HgCl2(C26H20N6)]n, (II), and the bromido, [HgBr2(C26H20N6)]n, (III), and iodido, [HgI2(C26H20N6)]n, (IV), analogues. Free ligand L crystallizes with two symmetry-independent half-molecules in the asymmetric unit and each L molecule resides on a crytallographic inversion centre. In structures (II)-(IV), the L ligand is also positioned on a crystallographic inversion centre, whereas the Hg centre resides on a crystallographic twofold axis. Compound (I) adopts an anti conformation in the solid state and forms a two-dimensional network in the crystallographic bc plane via π-π and C-H...π interactions. The three Hg(II) coordination complexes, (II)-(IV), have one-dimensional zigzag chains composed of L and HgX2 (X = Cl, Br and I), and the Hg(II) centres are in a distorted tetrahedral [HgX2N2] coordination geometry. Complexes (III) and (IV) are isomorphous, whereas complex (II) displays an interesting conformational difference from the others, i.e. a twist in the flexible bridging ligand.

  9. 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

  10. 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

  11. From discrete molecule, to polymer, to MOF: mapping the coordination chemistry of Cd(II) using (113)Cd solid-state NMR.

    Science.gov (United States)

    Frost, Jamie M; Kobera, Libor; Pialat, Amélie; Zhang, Yixin; Southern, Scott A; Gabidullin, Bulat; Bryce, David L; Murugesu, Muralee

    2016-08-23

    Studies of three related Cd(II) systems (a discrete [Cd(II)2] unit, a one-dimensional [Cd(II)2]n coordination polymer and a Cd(II)-based MOF) all derived from the ligand 2,4,6-tris(2-pyrimidyl)-1,3,5-triazine, reveal an exceptionally rare example of (113)Cd-(113)Cd J coupling in the polymer that is detectable by solid-state NMR ((2)JCd-Cd = ∼65 Hz).

  12. Uranium(VI) coordination polymers with pyromellitate ligand: Unique 1D channel structures and diverse fluorescence

    Energy Technology Data Exchange (ETDEWEB)

    Zhang, Yingjie, E-mail: yzx@ansto.gov.au [Australian Nuclear Science and Technology Organization, Locked Bag 2001, Kirrawee DC, NSW 2232 (Australia); Bhadbhade, Mohan [Mark Wainwright Analytical Centre, University of New South Wales, Kensington, NSW 2052 (Australia); Karatchevtseva, Inna [Australian Nuclear Science and Technology Organization, Locked Bag 2001, Kirrawee DC, NSW 2232 (Australia); Price, Jason R. [Australian Synchrotron, 800 Blackburn Road, Clayton, VIC 3168 (Australia); Liu, Hao [Centre for Clean Energy Technology, School of Chemistry and Forensic Science, University of Technology Sydney, PO Box 123, Broadway, Sydney, NSW 2007 (Australia); Zhang, Zhaoming; Kong, Linggen [Australian Nuclear Science and Technology Organization, Locked Bag 2001, Kirrawee DC, NSW 2232 (Australia); Čejka, Jiří [Department of Mineralogy, National Museum, Václavské náměstí, 68, Prague 1, 115 79-CZ (Czech Republic); Lu, Kim; Lumpkin, Gregory R. [Australian Nuclear Science and Technology Organization, Locked Bag 2001, Kirrawee DC, NSW 2232 (Australia)

    2015-03-15

    Three new coordination polymers of uranium(VI) with pyromellitic acid (H{sub 4}btca) have been synthesized and structurally characterized. (ED)[(UO{sub 2})(btca)]·(DMSO)·3H{sub 2}O (1) (ED=ethylenediammonium; DMSO=dimethylsulfoxide) has a lamellar structure with intercalation of ED and DMSO. (NH{sub 4}){sub 2}[(UO{sub 2}){sub 6}O{sub 2}(OH){sub 6}(btca)]·~6H{sub 2}O (2) has a 3D framework built from 7-fold coordinated uranyl trinuclear units and btca ligands with 1D diamond-shaped channels (~8.5 Å×~8.6 Å). [(UO{sub 2}){sub 2}(H{sub 2}O)(btca)]·4H{sub 2}O (3) has a 3D network constructed by two types of 7-fold coordinated uranium polyhedron. The unique μ{sub 5}-coordination mode of btca in 3 enables the formation of 1D olive-shaped large channels (~4.5 Å×~19 Å). Vibrational modes, thermal stabilities and fluorescence properties have been investigated. - Graphical abstract: Table of content: three new uranium(VI) coordination polymers with pyromellitic acid (H{sub 4}btca) have been synthesized via room temperature and hydrothermal synthesis methods, and structurally characterized. Two to three dimensional (3D) frameworks are revealed. All 3D frameworks have unique 1D large channels. Their vibrational modes, thermal stabilities and photoluminescence properties have been investigated. - Highlights: • Three new coordination polymers of U(VI) with pyromellitic acid (H{sub 4}btca). • Structures from a 2D layer to 3D frameworks with unique 1D channels. • Unusual µ{sub 5}-(η{sub 1}:η{sub 2}:η{sub 1}:η{sub 2:}η{sub 1}) coordination mode of btca ligand. • Vibrational modes, thermal stabilities and luminescent properties reported.

  13. A Co(Ⅱ) 3,5-Diaminobenzoate Coordination Polymer

    Institute of Scientific and Technical Information of China (English)

    DAI Yu-Mei; TANG En; LI Zhao-Ji; WANG Xiao-Qin; YIN Pei-Xiu; YAO Yuan-Gen

    2006-01-01

    The title compound, [Co(C7N2H7O2)2]n·nH2O 1, was synthesized via the hydrothermal reaction of Co(Oac)2 with 3,5-diaminobenzoic acid and characterized by elemental analysis and infrared spectra. The crystal crystallizes in the monoclinic system, space group P21/c with a =7.456(3), b = 9.972(3), c = 10.391 (3) (A), β= 106.435(2)°, V = 741.0(4) (A)3, Z = 2, C14H16CoN4O5, Mr = 379.24, Dc = 1.700 g/cm3, F(000) = 390 and μ(MoKa) = 1.194 mm-1. The final R = 0.0324 and wR = 0.0886 for 1516 observed reflections with I>2σ(I) and R = 0.0337 and wR = 0.0899 for all data. X-ray diffraction studies reveal that the title compound has an interesting 3D microporous architecture with guest water molecules inside the channel. Each Co atom, adopting a distorted octahedral geometry, is coordinated by two O atoms from two 3,5-diaminobenzoate ligands and four N atoms from four symmetry-related 3,5-diaminobenzoate ligands.

  14. 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

  15. White Polymer Light-Emitting Diodes Based on Exciplex Electroluminescence from Polymer Blends and a Single Polymer.

    Science.gov (United States)

    Liang, Junfei; Zhao, Sen; Jiang, Xiao-Fang; Guo, Ting; Yip, Hin-Lap; Ying, Lei; Huang, Fei; Yang, Wei; Cao, Yong

    2016-03-01

    In this Article, we designed and synthesized a series of polyfluorene derivatives, which consist of the electron-rich 4,4'-(9-alkyl-carbazole-3,6-diyl)bis(N,N-diphenylaniline) (TPA-Cz) in the side chain and the electron-deficient dibenzothiophene-5,5-dioxide (SO) unit in the main chain. The resulting copolymer PF-T25 that did not comprise the SO unit exhibited blue light-emission with the Commission Internationale de L'Eclairage coordinates of (0.16, 0.10). However, by physically blending PF-T25 with a blue light-emitting SO-based oligomer, a novel low-energy emission correlated to exciplex emerged due to the appropriate energy level alignment of TPA-Cz and the SO-based oligomers, which showed extended exciton lifetime as confirmed by time-resolved photoluminescent spectroscopy. The low-energy emission was also identified in copolymers consisting of SO unit in the main chain, which can effectively compensate for the high-energy emission to produce binary white light-emission. Polymer light-emitting diodes based on the exciplex-type single greenish-white polymer exhibit the peak luminous efficiency of 2.34 cd A(-1) and the maximum brightness of 12 410 cd m(-2), with Commission Internationale de L'Eclairage color coordinates (0.27, 0.39). The device based on such polymer showed much better electroluminescent stability than those based on blending films. These observations indicated that developing a single polymer with the generated exciplex emission can be a novel and effective molecular design strategy toward highly stable and efficient white polymer light-emitting diodes.

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

    Energy Technology Data Exchange (ETDEWEB)

    Jin Jing; Han Xiao; Meng Qin; Li Dan; Chi Yuxian [School of Chemistry and Chemical Engineering, Liaoning Normal University, Dalian 116029 (China); Niu Shuyun, E-mail: syniu@sohu.com [School of Chemistry and Chemical Engineering, Liaoning Normal University, Dalian 116029 (China)

    2013-01-15

    Five Cd(II)/Zn(II) complexes [Cd(1,2-bdc)(pz){sub 2}(H{sub 2}O)]{sub n} (1), [Cd1Cd2(btec)(H{sub 2}O){sub 6}]{sub n} (2), [Cd(3,4-pdc) (H{sub 2}O)]{sub n} (3), [Zn(2,5-pdc)(H{sub 2}O){sub 4}]{center_dot}2H{sub 2}O (4) and {l_brace} [Zn(2,5-pdc)(H{sub 2}O){sub 2}]{center_dot}H{sub 2}O{r_brace} {sub n} (5) (H{sub 2}bdc=1,2-benzenedicarboxylic acid, pz=pyrazole, H{sub 4}btec=1,2,4,5-benzenetetracarboxylic acid, H{sub 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: Black-Right-Pointing-Pointer Five Cd/Zn complexes have been synthesized and characterized. Black-Right-Pointing-Pointer The SPS results indicate they possess obvious photoelectric conversion property. Black-Right-Pointing-Pointer The species and coordination environment of central metal ion affect SPS. Black-Right-Pointing-Pointer The species and property of ligands affect SPS

  17. Synthesis of cyanopyridine based conjugated polymer

    Directory of Open Access Journals (Sweden)

    B. Hemavathi

    2016-06-01

    Full Text Available This data file contains the detailed synthetic procedure for the synthesis of two new cyanopyridine based conjugated polymer P1 and P2 along with the synthesis of its monomers. The synthesised polymers can be used for electroluminescence and photovoltaic (PV application. The physical data of the polymers are provided in this data file along with the morphological data of the polymer thin films. The data provided here are in association with the research article entitled ‘Cyanopyridine based conjugated polymer-synthesis and characterisation’ (Hemavathi et al., 2015 [3].

  18. 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.

  19. Peptide-Based Polymer Therapeutics

    Directory of Open Access Journals (Sweden)

    Aroa Duro-Castano

    2014-02-01

    Full Text Available Polypeptides are envisaged to achieve a major impact on a number of different relevant areas such as biomedicine and biotechnology. Acquired knowledge and the increasing interest on amino acids, peptides and proteins is establishing a large panel of these biopolymers whose physical, chemical and biological properties are ruled by their controlled sequences and composition. Polymer therapeutics has helped to establish these polypeptide-based constructs as polymeric nanomedicines for different applications, such as disease treatment and diagnostics. Herein, we provide an overview of the advantages of these systems and the main methodologies for their synthesis, highlighting the different polypeptide architectures and the current research towards clinical applications.

  20. Six Zn(II) and Cd(II) coordination polymers assembled from a similar binuclear building unit: tunable structures and luminescence properties.

    Science.gov (United States)

    Zhang, Liyan; Rong, Lulu; Hu, Guoli; Jin, Suo; Jia, Wei-Guo; Liu, Ji; Yuan, Guozan

    2015-04-21

    Six Zn(ii) and Cd(ii) coordination polymers were constructed by treating a 2-substituted 8-hydroxyquinolinate ligand containing a pyridyl group with zinc or cadmium salts, and characterized by a variety of techniques. Interestingly, based on a similar binuclear Zn(ii) or Cd(ii) building unit, the supramolecular structures of the six coordination polymers () exhibit an unprecedented structural diversification due to the different choices of metal salts. and represent a novel 2D framework containing 1D infinite right- and left-handed helical chains. and are 2D coordination frameworks based on binuclear Cd(ii) building units. For and , the L ligands can bridge binuclear building units forming a 1D infinite chain. Interestingly, the adjacent Cd2O2 planes of the 1D chain in are in parallel with each other, while the dihedral angle between the two Zn2O2 planes in is 83.43°. Photoluminescence properties revealed that the six coordination polymers exhibit redshifted emission maximum compared with the free ligand HL, which can be ascribed to an increased conformational rigidity and the fabrication of coplanar binuclear building units M2L2 in . Coordination polymers also display distinct fluorescence lifetimes and quantum yields because of their different metal centers and supramolecular structures.

  1. Syntheses, structures, and properties of Co(II)/Zn(II) mixed-ligand coordination polymers based on 4-[(3,5-dinitrobenzoyl)amino]benzoic acid and 1,4-bis(1-imidazolyl) benzene

    Energy Technology Data Exchange (ETDEWEB)

    Yin, Fei; Chen, Jing; Liang, Yongfeng [Department of Chemistry, Zhejiang Sci-Tech University, Hangzhou, Zhejiang 310018 (China); Zou, Yang, E-mail: zouyang@zstu.edu.cn [Department of Chemistry, Zhejiang Sci-Tech University, Hangzhou, Zhejiang 310018 (China); Yinzhi, Jiang [Department of Chemistry, Zhejiang Sci-Tech University, Hangzhou, Zhejiang 310018 (China); Xie, Jingli, E-mail: jlxie@mail.zjxu.edu.cn [College of Biological, Chemical Sciences and Engineering, Jiaxing University, Jiaxing, Zhejiang 314001 (China)

    2015-05-15

    Two coordination polymers [Co(dnbab){sub 2}(bimb)](H{sub 2}O){sub 4} (1) and [Zn(dnbab){sub 2}(bimb)](H{sub 2}O){sub 5} (2) (Hdnbab=4-[(3,5-dinitrobenzoyl)amino]benzoic acid, bimb=1,4-bis(1-imidazolyl) benzene) have been solvothermally synthesized. Their structures have been determined by single-crystal X-ray diffraction analyses and further characterized by powder X-ray diffraction (PXRD) and thermogravimetric (TG) analyses. Complexes 1 and 2 are isostructures and each displays an one-dimensional (1D) zigzag chain, which further forms a 3D supramolecular architecture with 1-D channels via inter-chain π–π interactions and hydrogen bonds. Moreover, the magnetic properties of 1 and fluorescent properties of 2 have been investigated. - Graphical abstract: Two coordination supramolecular frameworks [Co(dnbab){sub 2}(bimb)](H{sub 2}O){sub 4}(1) and [Zn(dnbab){sub 2}(bimb)](H{sub 2}O){sub 5}(2) (Hdnbab=4-[(3,5-dinitrobenzoyl)amino]benzoic acid, bimb=1,4-bis(1-imidazolyl) benzene) have been synthesized and characterized by X-ray single-crystal diffraction. Their thermal, magnetic and fluorescent properties have also been studied. - Highlights: • Two isomorphic Co(II)/Zn(II) complexes with the mixed-ligands have been synthesized. • Hydrogen bonds and π–π stacking interactions directed the final 3-D architecture assembly. • Both Co(II) and Zn(II) complexes show good thermal stability. • Co complex exhibits antiferromagnetic interaction. • The fluorescent property of Zn(II) complex has been investigated in the solid state.

  2. Coordination Polymers towards Advanced Functions%向高功能发展的配位聚合物

    Institute of Scientific and Technical Information of China (English)

    杜淼; 卜显和

    2009-01-01

    The rational design and preparation of metal-organic coordination polymers with specific network structures and physicochemical properties by using the experience and method of crystal engineering has currently been a hot research topic in coordination chemistry, supramolecular chemistry, material chemistry and other related areas. As a new type of molecular-based crystalline material, coordination polymers (especially microporous coordination polymers) have displayed potential applications in many aspects such as guest exchange/separation, gas storage, chiral resolution, drug release, electroluminescence, selective catalysis, molecular recognition, and microporous devices. In this paper, the recent progress of such advanced multifunctional crystalline materials and their applications in adsorption, catalysis as well as optics, electrics, and magnetism are briefly reviewed.%运用晶体工程的经验和方法合理设计和制备具有特定网络结构和理化性能的配位聚合物是当前配位化学、超分子化学、材料化学及相关领域的研究热点之一.作为一类新型分子基晶体材料,配位聚合物(尤其是多孔配位聚合物)在客体交换与分离、气体储存、手性拆分、药物缓释、电致发光、选择性催化、分子识别及微孔器件等诸多方面均显示出潜在的应用前景.本文简要介绍了此类化合物作为具有复合性能的多功能晶体材料在吸附、催化及光、电、磁等方面应用的最新研究进展.

  3. 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.

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

    Science.gov (United States)

    Luo, Qianqian; Han, Ying; Lin, Hechun; Zhang, Yuanyuan; Duan, Chungang; Peng, Hui

    2017-03-01

    One dimensional coordination polymer Gd[(SO4)(NO3)(C2H6SO)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 SO42- ions to generate a 1-D chain, and all oxygen atoms in SO42- groups are connected to three nearest Gd atoms in μ3:η1:η1:η2 fashion. Gd, S and N from SO42- and NO3- 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 -ΔSm=28.8 J Kg-1 K-1 for ΔH=7 T.

  5. Synthesis, structure and masnetic properties of two new coordination polymers with carboxylate-substituted benzoimidazole lisands

    Institute of Scientific and Technical Information of China (English)

    HU BoWen; ZHAO JiongPeng; YANG Qian; ZHANG XiaoFeng; BU XianHe

    2009-01-01

    This paper reports two new coordination polymers formed by carboxylate-substituted benzoimidazole and formate ligands:[Mn(L)-(HCO2)]n (1) and [Co(L)·(HCO2)]n (2) (L = benzoimidazol-1-yl-acetate).Complexes 1 and 2 are isomorphous and adopt a new 3,6-connected three-nodal topology showing interesting magnetic properties:spin canted antiferromagnetism for Mn11 complex 1,but simple antiferromagnetic coupling for CoⅡ complex 2.

  6. Picogram sensing of trinitrophenol in aqueous medium through a water stable nanoscale coordination polymer.

    Science.gov (United States)

    Asha, K S; Vaisakhan, G S; Mandal, Sukhendu

    2016-06-01

    A water stable nanoscale coordination polymer (CP) can detect trinitrophenol (TNP) in an aqueous medium at a record-picogram level (∼1.66 pg cm(-2)) with a detection limit of 1.66 ppb. This is a simple and low-cost method for the detection of TNP in aqueous media in contact mode, taking advantage of the unique structural arrangement of the as-synthesized CP and the associated photophysical properties.

  7. Novel Zn(II) ladder-like coordination polymer constructed from designed ferrocenyl ligand

    Institute of Scientific and Technical Information of China (English)

    2008-01-01

    Reaction of Zn(NO3)2.6H2O with 3-(4-carboxylphenylamino)-1-ferrocenyl-2-butylen-1-one (HL) and 4,4'-bipyridine (4,4'-bipy) in methanol solution resulted in a novel ladder-like coordination polymer {[Zn2L2(μ2-L)2(4,4'-bipy)2].MeOH}n (1). Its crystal structure, thermal and electrochemical properties axe presented.

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

    Energy Technology Data Exchange (ETDEWEB)

    Si, Zhen-Xiu; Xu, Wei, E-mail: xuwei@nbu.edu.cn; Zheng, Yue-Qing, E-mail: yqzhengmc@163.com

    2016-07-15

    An uranium coordination polymer, namely [(UO{sub 2}(pydc)(H{sub 2}O)]·H{sub 2}O (1) (H{sub 2}pydc=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 UO{sub 2}{sup 2+} 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. - Graphical abstract: Complex 1 exhibits 1D chain coordination polymer in which UO{sub 2}{sup 2+} ions are bridged by 2,5-pyridinedicarboxylate ligand. Photoluminescence studies reveal that complex 1 exhibits characteristic emissions of uranyl centers. The compound is selective to degraded dye and displays good photocatalytic activities for the degradation of MB under Hg-lamp. Display Omitted - Highlights: • Complex 1 exhibits 1D chain coordination polymer. • Complex 1 could degrade methylene blue and Rhodamine B under Hg-lamp irradiation. • Luminescent property of 1 has been studied.

  9. A 2D [Fe-II-bistetrazole] coordination polymer exhibiting spin-crossover properties

    NARCIS (Netherlands)

    Quesada, Manuel; Prins, Ferry; Roubeau, Olivier; Gamez, Patrick; Teat, Simon J.; van Koningsbruggen, Petra J.; Haasnoot, Jaap G.; Reedijk, Jan

    2007-01-01

    The reaction of 1,3-bis(tetrazol-1-yl)-2-propanol (btzpol) with Fe(BF4)(2) center dot 6H(2)O in acetonitrile yields the remarkable 2D coordination polymer [Fe-II(btzpol)(1.8)(btzpol-OBF3)(1.2)](BF4)(0.8) center dot (H2O)(0.8)(CH3CN) (1). This compound has been structurally characterized using an X-r

  10. Synthesis, structure and magnetic properties of two new coordination polymers with carboxylate-substituted benzoimidazole ligands

    Institute of Scientific and Technical Information of China (English)

    2009-01-01

    This paper reports two new coordination polymers formed by carboxylate-substituted benzoimidazole and formate ligands: [Mn(L)·(HCO2)]n (1) and [Co(L)·(HCO2)]n (2) (L = benzoimidazol-1-yl-acetate). Com-plexes 1 and 2 are isomorphous and adopt a new 3,6-connected three-nodal topology showing inter-esting magnetic properties: spin canted antiferromagnetism for MnⅡ complex 1, but simple antiferro-magnetic coupling for CoⅡ complex 2.

  11. Infinite Coordination Polymer Nano- and Micro-Particles

    Science.gov (United States)

    2015-06-12

    potential applications is in part due to the fact that these structures , consisting of repeating ligands interconnected by metallic nodes, can be made...Figure 5: Representations of the crystal structure of NU-135. (a) Detail of pores, viewed along the ab plane. Lilac spheres indicate the...based linkers exhibit not only bending in the alkyne regions, but also twisting at the cobalt metal center. These structural considerations behave in

  12. Three 2 D copper(II)/cadmium(II) coordination polymers based on semi-rigid/flexible bis-pyridyl-bis-amide ligands and 5-aminoisophthalate: Syntheses, structures and properties

    Indian Academy of Sciences (India)

    Hongyan Lin; Huizhe Lu; Mao Le; Jian Luan; Xiuli Wang; Cuocheng Liu

    2015-07-01

    Three new transition metal coordination polymers [Cu(3-bpcb)0.5(5-AIP)]·2H2O (1), [Cd(3-bpcb)0.5(5-AIP)(H2O)]·H2O (2) and [Cd(3-bpsa)0.5(5-AIP)(H2O)]·2H2O (3) have been hydrothermally synthesized by self-assembly of 5-aminoisophthalic acid (5-H2 AIP), semi-rigid or flexible bis-pyridyl-bis-amide ligands [3-bpcb = N N′-bis(3-pyridinecarboxamide)-1,4-benzene, 3-bpsa = N,N′-bis(3-pyridyl)succinamide], and copper chloride or cadmium nitrate. X-ray diffraction analysis reveals that compounds 1 and 2 possess similar 2 D double-layered structures with (3,4)-connected (63)(65·8) topology, while compound 3 displays a 2 D layer with {62.10}{6} topology. The adjacent layers of 1–3 are finally extended into 3 D supramolecular frameworks by hydrogen bonding interactions. The bis-pyridyl-bis-amide ligands with different flexibilities play an important role in the construction of final topological structures for the title compounds. Further, the electrochemical behavior of the compound 1 and the fluorescent and photocatalytic properties of compounds 1–3 have been investigated.

  13. Crystal structure of a layered coordination polymer based on a 44 net containing Cd2+ ions and 1,5-bis­(pyridin-4-yl)pentane linkers

    Science.gov (United States)

    Harrison, William T. A.; Plater, M. John; deSilva, Ben M. deSilva; Foreman, Mark R. St J.

    2014-01-01

    The title compound, poly[[di­aqua­bis­[1,5-bis­(pyridin-4-yl)pentane-κ2 N:N′]cadmium] bis­(perchlorate) 1,5-bis­(pyridin-4-yl)pentane ethanol mono­solvate], [Cd(C15H18N2)2(H2O)2](ClO4)2·C15H18N2·C2H6O, is a layered coordination polymer built up from highly squashed 44 nets in which the octa­hedral trans-CdO2N4 nodes (Cd site symmetry -1) are linked by the bifunctional ligands, forming infinite (110) sheets. The cationic sheets are charge-balanced by inter­layer perchlorate ions. A free 1,5-bis­(pyridin-4-yl)pentane mol­ecule and an ethanol mol­ecule of crystallization are also found in the inter­sheet region. A number of O—H⋯O, O—H⋯N and C—H⋯O hydrogen bonds help to consolidate the layered structure. PMID:25249860

  14. Crystal structure of a layered coordination polymer based on a 4(4) net containing Cd(2+) ions and 1,5-bis-(pyridin-4-yl)pentane linkers.

    Science.gov (United States)

    Harrison, William T A; Plater, M John; deSilva, Ben M deSilva; Foreman, Mark R St J

    2014-08-01

    The title compound, poly[[di-aqua-bis-[1,5-bis-(pyridin-4-yl)pentane-κ(2) N:N']cadmium] bis-(perchlorate) 1,5-bis-(pyridin-4-yl)pentane ethanol mono-solvate], [Cd(C15H18N2)2(H2O)2](ClO4)2·C15H18N2·C2H6O, is a layered coordination polymer built up from highly squashed 4(4) nets in which the octa-hedral trans-CdO2N4 nodes (Cd site symmetry -1) are linked by the bifunctional ligands, forming infinite (110) sheets. The cationic sheets are charge-balanced by inter-layer perchlorate ions. A free 1,5-bis-(pyridin-4-yl)pentane mol-ecule and an ethanol mol-ecule of crystallization are also found in the inter-sheet region. A number of O-H⋯O, O-H⋯N and C-H⋯O hydrogen bonds help to consolidate the layered structure.

  15. 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.

  16. Diffusion-coupled molecular assembly: structuring of coordination polymers across multiple length scales.

    Science.gov (United States)

    Hirai, Kenji; Reboul, Julien; Morone, Nobuhiro; Heuser, John E; Furukawa, Shuhei; Kitagawa, Susumu

    2014-10-22

    Porous coordination polymers (PCPs) are an intriguing class of molecular-based materials because of the designability of framework scaffolds, pore sizes and pore surface functionalities. Besides the structural designability at the molecular scale, the structuring of PCPs into mesoscopic/macroscopic morphologies has attracted much attention due to the significance for the practical applications. The structuring of PCPs at the mesoscopic/macroscopic scale has been so far demonstrated by the spatial localization of coordination reactions on the surface of templates or at the phase boundaries. However, these methodologies have never been applied to the fabrication of solid-solution or multivariate metal-organic frameworks (MOFs), in which multiple components are homogeneously mixed. Herein, we demonstrate the structuring of a box-type superstructure comprising of a solid-solution PCP by integrating a bidirectional diffusion of multiple organic ligands into molecular assembly. The parent crystals of [Zn2(ndc)2(bpy)]n were placed in the DMF solution of additional organic component of H2bdc, and the temperature was rapidly elevated up to 80 °C (ndc = 1,4-naphthalenedicarboxylate, bpy = 4,4'-bipyridyl, bdc = 1,4-benzenedicarboxylate). The dissolution of the parent crystals induced the outward diffusion of components; contrariwise, the accumulation of the other organic ligand of H2bdc induced the inward diffusion toward the surface of the parent crystals. This bidirectional diffusion of multiple components spatially localized the recrystallization at the surface of cuboid parent crystals; therefore, the nanocrystals of a solid-solution PCP ([Zn2(bdc)1.5(ndc)0.5(bpy)]n) were organized into a mesoscopic box superstructure. Furthermore, we demonstrated that the box superstructures enhanced the mass transfer kinetics for the separation of hydrocarbons.

  17. Ultralong Persistent Room Temperature Phosphorescence of Metal Coordination Polymers Exhibiting Reversible pH-Responsive Emission.

    Science.gov (United States)

    Yang, Yongsheng; Wang, Ke-Zhi; Yan, Dongpeng

    2016-06-22

    Ultra-long-persistent room temperature phosphorescence (RTP) materials have attracted much attention and present various applications in illumination, displays, and the bioimaging field; however, the persistent RTP is generally from the inorganic phosphor materials to date. Herein, we show that the metal coordination polymers (CPs) could be new types of emerging long-lived RTP materials for potential sensor applications. First, two kinds of Cd-based CPs, Cd(m-BDC)(H2O) (1) and Cd(m-BDC)(BIM) (2) (m-BDC = 1,3-benzenedicarboxylic acid; BIM = benzimidazole), were obtained through a hydrothermal process, and the samples were found to exhibit two-dimensional layered structures, which are stabilized by interlayer C-H···π interaction and π···π interaction, respectively. The CPs show unexpected second-time-scale ultra-long-persistent RTP after the removal of UV excitation, and this persistent emission can be detected easily on a time scale of 0-10 s. The CPs also feature a tunable luminescence decay lifetime by adjusting their coordination situation and packing fashion of ligands. Theoretical calculation further indicates that the introduction of the second ligand could highly influence the electronic structure and intermolecular electron transfer toward tailoring the RTP of the CP materials. Moreover, CP 2 exhibits well-defined pH- and temperature-dependent phosphorescence responses. Therefore, this work provides a facile way to develop new type of CPs with steady-state and dynamic tuning of the RTP properties from both experimental and theoretical perspectives, which have potential applications in the areas of displays, pH/temperature sensors, and phosphorescence logic gates. On account of suitable incorporation of inorganic and organic building blocks, it can be expected that the ultra-long-persistent RTP CPs can be extended to other similar systems due to the highly tunable structures and facile synthesis routes.

  18. Fe-nitrilotriacetic acid coordination polymer nanowires: an effective sensing platform for fluorescence-enhanced nucleic acid detection

    Science.gov (United States)

    Zhou, Yunchun; Liu, Qian; Sun, Xuping; Kong, Rongmei

    2017-02-01

    The determination of specific nucleic acid sequences is key in identifying disease-causing pathogens and genetic diseases. In this paper we report the utilization of Fe-nitrilotriacetic acid coordination polymer nanowires as an effective nanoquencher for fluorescence-enhanced nucleic acid detection. The detection is fast and the whole process can be completed within 15 min. This nanosensor shows a low detection limit of 0.2 nM with selectivity down to single-base mismatch. This work provides us with an attractive sensing platform for applications.

  19. Ultrasonic motors with polymer-based vibrators.

    Science.gov (United States)

    Wu, Jiang; Mizuno, Yosuke; Tabaru, Marie; Nakamura, Kentaro

    2015-12-01

    With their characteristics of low density and elastic moduli, polymers are promising materials for making ultrasonic motors (USMs) with high energy density. Although it has been believed for a long time that polymers are too lossy to be applied to high-amplitude vibrators, there are several new polymers that exhibit excellent vibration characteristics. First, we measure the damping coefficients of some functional polymers to explore the applicability of polymers as vibrators for USMs. Second, to investigate the vibration characteristics, we fabricate bimorph vibrators using several kinds of polymers that have low attenuation. Third, a bending mode USM is fabricated with a polymer rod and four piezoelectric plates bonded on the rod as a typical example of a USM. Through an experimental investigation of the motor performance, it was found that the polymer-based USMs exhibited higher rotation velocity than the aluminum-based USM under a light preload, although the maximum torque of the polymer-based USMs was smaller than the aluminum-based USM. Among the tested polymers, polyphenylenesulfide was a prospective material for USMs under light preloads because of the high amplitude and lightweight of polyphenylenesulfide.

  20. Synthesis and Characterization of Nanosized Uranyl Coordination Polymers derived from Terephthalic acid and Azoles

    Directory of Open Access Journals (Sweden)

    Maged S.Al-Fakeh

    2016-05-01

    Full Text Available The structure of the complexes [UO2(TPA(Azole(H2O].xH2O, TPA = 1,4-benzenedicarboxylic acid and azoles = 2-aminobenzothiazole, 2-aminothiazole, 2-amino-4-methylthiazole and 2-mercaptobenzothiazole has been prepared and characterized. The structure of the complexes has been assigned based on elemental analysis, IR, electronic spectral studies, magnetic measurement, molar conductance, Scanning electron microscope (S.E.M, X-ray powder diffraction techniques investigations and thermogravimetric analysis complete the characterization of the compound. Thermogravimetry(TG, derivative thermogravimetry (DTG and differential thermal analysis (DTA have been used to study the thermal decomposition of the complexes. The kinetic parameters have been calculated making use of the Coats-Redfern and Horowitz-Metzger. The scanning electron microscope SEM photographs and particle size calculations from the powder XRD data indicate the average size of the prepared UO2(II (28-56 nm supramolecular coordination polymers in the nanoscale range. The biological screening of the compounds was also tested.

  1. 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.

  2. 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.

  3. 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.

  4. Synthesis, crystal structure and Thermogravimetry of ortho-phthalic acid bridged coordination polymer of Copper(II)

    Indian Academy of Sciences (India)

    BABITA SARMA; SAURAV BHARALI; DIGANTA KUMAR DAS

    2016-06-01

    Coordination polymer of Cu(II) bridged by o-phthalic acid alone is not known. The reaction of$CuCl_{2}.2H_{2}O$ with (2-butoxycarbonyl)benzoic acid yielded three dimensional coordination polymer bridged byo-phthalic acid. X-ray crystal structure shows structure with monoclinic P21/c space group. o-Phthalic acidmolecules act as bridge between two Cu(II), one carboxylate binds to one Cu(II) as bidentate while the othercarboxylate binds to another Cu(II) as monodentate. The four planar co-ordination positions of Cu(II) aresatisfied by two chelated carboxylates while fifth and sixth co-ordination positions are satisfied by monodentatecarboxylates. EPR and TGA of the coordination polymer are also reported.

  5. Design and its limitations in the construction of bi- and poly-nuclear coordination complexes and coordination polymers (aka MOFs): a personal view.

    Science.gov (United States)

    Robson, R

    2008-10-14

    This article, presented from a personal point of view, is concerned with the design of ligands intended to give specifically either binuclear or tetranuclear metal complexes or coordination polymers. No attempt is made to provide a comprehensive coverage of these topics, the focus being mainly upon results from our laboratory. Some emphasis is placed upon aspects of the historical development of the deliberate construction of coordination polymers (aka MOFs)--materials promising useful applications, the study of which continues to expand exponentially. Some of our recent research is described in which the carbonate ion and the tetracyanoquinodimethane dianion are used as bridging ligands to generate targeted coordination polymers. It is intended that Dalton Perspectives be easily comprehensible to non-specialists in the field; an average second year university chemistry student should be easily able to understand the present contribution.

  6. Facile fabrication and adsorption property of a nano/microporous coordination polymer with controllable size and morphology.

    Science.gov (United States)

    Liu, Qing; Jin, Li-Na; Sun, Wei-Yin

    2012-09-11

    A porous coordination polymer [Cu(3)(btc)(2)] with controllable size and morphology from nanocube to microoctahedron was readily synthesized in an ethanol-water mixture at room temperature by adjusting the concentration of the surfactant and the polymer shows size- and morphology-dependent sorption properties.

  7. New Biodegradable Peptide-based Polymer Constructs

    NARCIS (Netherlands)

    van Dijk, M.

    2009-01-01

    Peptide-based polymers are of increasing interest, since they can be applied for a variety of purposes such as drug delivery devices, scaffolds for tissue engineering and -repair, and as novel biomaterials. Peptide-based polymers are common in nature and often exhibit special characteristics.

  8. New Biodegradable Peptide-based Polymer Constructs

    NARCIS (Netherlands)

    van Dijk, M.

    2009-01-01

    Peptide-based polymers are of increasing interest, since they can be applied for a variety of purposes such as drug delivery devices, scaffolds for tissue engineering and -repair, and as novel biomaterials. Peptide-based polymers are common in nature and often exhibit special characteristics. Howeve

  9. New Biodegradable Peptide-based Polymer Constructs

    NARCIS (Netherlands)

    van Dijk, M.

    2009-01-01

    Peptide-based polymers are of increasing interest, since they can be applied for a variety of purposes such as drug delivery devices, scaffolds for tissue engineering and -repair, and as novel biomaterials. Peptide-based polymers are common in nature and often exhibit special characteristics. Howeve

  10. Electrothermal Coordination in Cable Based Transmission Grids

    DEFF Research Database (Denmark)

    Olsen, Rasmus Schmidt; Holbøll, Joachim; Gudmundsdottir, Unnur Stella

    2013-01-01

    Electrothermal coordination (ETC) is introduced for cable based transmission grids. ETC is the term covering operation and planning of transmission systems based on temperature, instead of current. ETC consists of one part covering the load conditions of the system and one covering the thermal...... to be beneficial for both operator and system planner. It is shown how the thermal behavior can be monitored in real-time during normal dynamic load and during emergencies. In that way, ETC enables cables to be loaded above their normal rating, while maintaining high reliability of the system, which potentially...

  11. Synthesis, spectral characterization and thermal aspects of coordination polymers of some transition metal ions with adipoyl bis(isonicotinoylhydrazone)

    Science.gov (United States)

    Haque, Mahejabeen Azizul; Paliwal, L. J.

    2017-04-01

    A series of metal coordination polymers of Mn(II), Fe(II), Co(II), Ni(II), Cu(II), and Zn(II), obtained by the reaction of metal acetate with newly synthesized adipoyl bis(isonicotinoylhydrazone) (ADBI) have been investigated. The ligand has been characterized by 1H NMR, 13C NMR, FTIR, and ESI mass spectra. Structural and spectroscopic characterization of the coordination polymers have been carried out using elemental analysis, XRD, SEM, infrared and diffused reflectance spectra, magnetic susceptibility measurements and thermogravimetric analytical techniques. Each metal ion is coordinated to the ligand through oxygen of carbonyl group and the nitrogen of azomethine group of ligand forming a stable 5-membered heterocyclic ring. The synthesized ligand coordinates in an octadentate manner. Magnetic and diffused reflectance spectral studies reveal octahedral geometry of Co(II), Cu(II), Fe(II) and Ni(II) coordination polymers and tetrahedral geometry of Mn(II) and Zn(II) coordination polymers. The thermal stability and decomposition steps of all coordination polymers have been studied using TG, DTG and DTA techniques. Moreover, the kinetic parameters such as activation energy (Ea*), order of reaction (n), Arrhenius factor (A), change in entropy (ΔS*), change in enthalpy (ΔH*) and free energy change (ΔG*) were evaluated at each stage of decomposition curve using Coats-Redfern method.

  12. Synthesis and Crystal Structure of a New Cadmium(Ⅱ) Coordination Polymer with Ethylenediaminetetraacetic Acid

    Institute of Scientific and Technical Information of China (English)

    ZHENG Jian-Mei; WU Mei-Feng; ZHENG Fa-Kun; LIU Hua

    2012-01-01

    A new cadmium(Ⅱ) coordination polymer,namely,[KCd2(edta)I]n(1,H4edta = ethylenediaminetetraacetic acid),has been prepared and structurally characterized by single-crystal X-ray diffraction.Crystallographic data for 1:C10H12Cd2IKN2O8,Mr = 679.02,monoclinic,space group P21/n,a = 9.870(5),b = 8.989(4),c = 19.082(10) ,β = 104.581(10)o,V = 1638.5(13) 3,Z = 4,Dc = 2.753 g/cm3,μ = 4.776 mm-1,F(000) = 1272,the final R = 0.0473 and wR = 0.1311 for 2846 observed reflections with I 〉 2σ(I).Polymer 1 features a 2-D layered structure,in which each edta4-ligand chelates/bridges five adjacent six-/seven-coordinated Cd(Ⅱ) centers with all ten donors(eight oxygen and two nitrogen) involved with coordination.Additional iodide I-ions as counterions are bound to the Cd(Ⅱ) centers in a terminal mode and the potassium K+ ions are located in the layers and surrounded by O and I atoms from neighboring environment.The thermal stability of 1 has been discussed.

  13. Water-Resistant and Transparent Plastic Films from Functionalizable Organic Polymers: Coordination Polymers as Templates for Solid-State [2+2]-Photopolymerization.

    Science.gov (United States)

    Garai, Mousumi; Biradha, Kumar

    2017-01-05

    An organic polymer containing cyclobutanes and amides as backbones and pyridyl groups as sidearms was synthesized by single-crystal-to-single-crystal (SCSC) [2+2]-photopolymerization in the coordination polymers (CPs) of diene. The diene molecule was photo-inactive in its crystals and formed a triply intertwined 1D-helical CP with Cd(NO3 )2 and Cu(NO3 )2 salts. The 1D-CP was transformed into a coordination polymer of organic polymers containing threefold interpenetrated 3D-networks of CdSO4 topology through a [2+2]-reaction in SCSC manner upon irradiation. The organic polymer was separated from its CPs and found to have an unusually high degree of polymerization for this type of reaction. Furthermore, the organic polymer was amenable for N-alkylation reactions such as methylation, propylation, and decylation. The formate salts of the organic polymer and the methylated polymer were shown to form plastic films with a combination of properties such as high transparency, tensile strengths, gas permeability, thermal stability, water-resistance, and resistance to other organic solvents. The methylated polymer was also able to capture chromate ions and anionic dyes from aqueous solutions.

  14. Polymer based nanocomposites with tailorable optical properties

    Science.gov (United States)

    Colombo, Annalisa; Simonutti, Roberto

    2014-09-01

    Transparent polymers are extensively used in everyday life, from windows to computer displays, from food packaging to lenses. A possible approach for modulating their optical properties (refractive index, transparency, color and luminescence) is to change the chemical structure of the polymer, however this option is in many cases economically prohibitive. Our approach, instead, relies in the use of standard polymers with the supplement of specific nanostructured additives able to tune the final property of the material. Among others, the cases of luminescent solar concentrators based on poly(methylmethacrylate) containing luminescent quantum dots and highly transparent polymer nanocomposites with high refractive index will be presented.

  15. Coordination polymers built from 1,4-bis(imidazol-1-ylmethyl)benzene: from crystalline to amorphous.

    Science.gov (United States)

    Adarsh, N N; Novio, Fernando; Ruiz-Molina, Daniel

    2016-07-28

    The supramolecular chemistry of the bis-imidazole ligand 1,4-bis(imidazol-1-ylmethyl)benzene, popularly known as bix, has been explored by various researchers in order to synthesize functional coordination polymers (CPs). The flexibility of the bix ligand, its unpredictable conformation and its coordination behaviour with transition metal ions have resulted in a huge number of structurally diverse and functionally intriguing CPs. In this perspective review we discuss the progress in CPs of bix between 1997 and today. More precisely, this review emphasizes the developments in functional supramolecular coordination polymers built from the bix ligand, from crystalline materials to amorphous nanomaterials.

  16. 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.

  17. Soy-Based Polymers and Their Applications

    Science.gov (United States)

    Polymers from natural resources have attracted important attention in the last few years because of increasing social emphasis on issues concerning the environment, waste disposal, and the depletion of non-renewable resources that has stimulated research on renewable materials. Soy-based polymers f...

  18. 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.

  19. Efficient fixation of CO2 by a zinc-coordinated conjugated microporous polymer.

    Science.gov (United States)

    Xie, Yong; Wang, Ting-Ting; Yang, Rui-Xia; Huang, Nian-Yu; Zou, Kun; Deng, Wei-Qiao

    2014-08-01

    Zinc-coordinated conjugated microporous polymers (Zn-CMPs), prepared by linking salen zinc and 1,3,5-triethynylbenzene, exhibit extraordinary activities (turnover frequencies of up to 11600 h(-1) ), broad substrate scope, and group tolerance for the synthesis of functional organic carbonates by coupling epoxides with CO2 at 120 °C and 3.0 MPa without the use of additional solvents. The catalytic activity of Zn-CMP is comparable to those of homogeneous catalysts and superior to those of other heterogeneous catalysts. This catalyst could be reused more than ten times without a significant decrease in performance.

  20. A New 3D Coordination Polymer of Bismuth with Nicotinic Acid N-Oxide

    Directory of Open Access Journals (Sweden)

    Farzin Marandi

    2013-01-01

    Full Text Available The new three-dimensional coordination polymer {[Bi(NNO2(NO3]·1.5H2O}n (1, NNO− = nicotinate N-oxide was synthesized and characterized by elemental analysis, IR and 1H-NMR spectroscopy, as well as single-crystal X-ray diffraction analysis. 1 crystallizes in the monoclinic space group C2/c. The crystal structure consists of a rectangular-shaped grid constructed with NNO linkers. Cavities of a diameter of 7.9–8.3 Å2 are filled with disordered water molecules. The thermal stability of the compound was evaluated by thermogravimetric analysis.

  1. Counter anion dependent gradual spin transition in a 1D cobalt(ii) coordination polymer.

    Science.gov (United States)

    Roy, Subhasis; Choubey, Somnath; Bhar, Kishalay; Sikdar, Nivedita; Costa, José Sánchez; Mitra, Partha; Ghosh, Barindra Kumar

    2015-05-07

    One Co(ii) SCO coordination polymer [Co(enbzpy)(μ1,5-dca)]n(PF6)n (·PF6) has been isolated and characterised structurally and magnetostructurally. The properties of ·PF6 are compared with the reported perchlorate analogue [Co(enbzpy)(μ1,5-dca)]n(ClO4)n (·ClO4). The gradual spin transition in ·PF6 in contrast to an abrupt spin transition with a hysteresis loop in ·ClO4 has been analysed in terms of structural factors.

  2. Synthesis and characterization of 1D iron(II) spin crossover coordination polymers with hysteresis.

    Science.gov (United States)

    Bauer, Wolfgang; Lochenie, Charles; Weber, Birgit

    2014-02-07

    Purposeful ligand design was used for the synthesis of eight new 1D iron(II) spin crossover coordination polymers aiming for cooperative spin transitions with hysteresis. The results from magnetic measurements and X-ray structure analysis show that the combination of rigid linkers and a hydrogen bond network between the 1D chains is a promising tool to reach this goal. Five of the eight new samples show a cooperative spin transition with hysteresis with up to 43 K wide hysteresis loops.

  3. A Novel 3D Zn-La Heterometallic Coordination Polymer Involving in situ Glycinate Ligand Synthesis

    Institute of Scientific and Technical Information of China (English)

    SONG Wen-Donga; LI Shi-Jie; GUO Jian; TONG Shao-Wei; JI Li-Li; MIAO Dong-Liang; AN Jing-Bo; NG Seik Weng

    2012-01-01

    One novel 3D 3d-4f coordination polymer, [LaZn(glc)(ox)2(H20)2]n (1, glc = glycinate, ox = oxalate), was obtained by the in situ synthesis of glycinate from the reaction of tetrazole-l-acetic acid, sodium oxalate, zinc nitrate and lanthanide oxide in the presence of a trace quantity of nitric acid under hydrothermal conditions. Compound 1 is of monoclinic, space group P21/n with a = 0.99601(9), b = 1.14592(10), c = 1.19107(10) nm and β = 108.7150(10)°. 1 exhibits an unusual 3D heterometallic coordination framework constructed by heterometallic dinuclear LaZn subunits and mixed ox and glc linkers with a uninodal 6-connected vine {33.43.58.6} net.

  4. Hysteretic Spin Crossover in Two-Dimensional (2D) Hofmann-Type Coordination Polymers.

    Science.gov (United States)

    Liu, Wei; Wang, Lu; Su, Yu-Jun; Chen, Yan-Cong; Tucek, Jiri; Zboril, Radek; Ni, Zhao-Ping; Tong, Ming-Liang

    2015-09-08

    Three new two-dimensional (2D) Hofmann-type coordination polymers with general formula [Fe(3-NH2py)2M(CN)4] (3-NH2py = 3-aminopyridine, M = Ni (1), Pd (2), Pt (3)) have been synthesized. Magnetic susceptibility measurements show that they exhibited cooperative spin crossover (SCO) with remarkable hysteretic behaviors. Their hysteresis widths are 25, 37, and 30 K for 1-3, respectively. The single-crystal structure of 1 suggest that the pseudo-octahedral Fe sites are equatorially bridged by [M(CN)4](2-) to form 2D grids and axially coordinated by 3-NH2py ligands. The intermolecular interactions between layers (the offset face-to-face π···π interactions, hydrogen bonds, and weak N(amino)···Ni(II) contacts) together with the covalent bonds bridged by [M(CN)4](2-) units are responsible to the significant cooperativity.

  5. Series of mixed uranyl-lanthanide (Ce, Nd) organic coordination polymers with aromatic polycarboxylates linkers.

    Science.gov (United States)

    Mihalcea, Ionut; Volkringer, Christophe; Henry, Natacha; Loiseau, Thierry

    2012-09-17

    Three series of mixed uranyl-lanthanide (Ce or Nd) carboxylate coordination polymers have been successfully synthesized by means of a hydrothermal route using either conventional or microwave heating methods. These compounds have been prepared from mixtures of uranyl nitrate, lanthanide nitrate together with phthalic acid (1,2), pyromellitic acid (3,4), or mellitic acid (5,6) in aqueous solution. The X-ray diffraction (XRD) single-crystal revealed that the phthalate complex (UO(2))(4)O(2)Ln(H(2)O)(7)(1,2-bdc)(4)·NH(4)·xH(2)O (Ln = Ce(1), Nd(2); x = 1 for 1, x = 0 for 2), is based on the connection of tetranuclear uranyl-centered building blocks linked to discrete monomeric units LnO(2)(H(2)O)(7) via the organic species to generate infinite chains, intercalated by free ammonium cations. The pyromellitate phase (UO(2))(3)Ln(2)(H(2)O)(12)(btec)(3)·5H(2)O (Ce(3), Nd(4)) contains layers of monomeric uranyl-centered hexagonal and pentagonal bipyramids linked via the carboxylate arms of the organic molecules. The three-dimensionality of the structure is ensured by the connection of remaining free carboxylate groups with isolated monomeric units LnO(2)(H(2)O)(7). The network of the third series (UO(2))(2)(OH)Ln(H(2)O)(7)(mel)·5H(2)O (Ce(5), Nd(6)) is built up from dinuclear uranyl units forming layers through connection with the mellitate ligands, which are further linked to each other through discrete monomers LnO(3)(H(2)O)(6). The thermal decomposition of the various coordination complexes led to the formation of mixed uranium-lanthanide oxide, with the fluorite-type structure at 1500 °C (for 1, 2) or 1400 °C for 3-6. Expected U/Ln ratio from the crystal structures were observed for compounds 1-6.

  6. 1D coordination polymers with polychalcogenides as linkers between metal atoms

    Energy Technology Data Exchange (ETDEWEB)

    Kysliak, Oleksandr; Beck, Johannes, E-mail: j.beck@uni-bonn.de

    2013-07-15

    The reactions of zinc metal with elemental selenium and selenium/sulfur mixtures in liquid ammonia or methylamine under solvothermal conditions in closed glass ampoules at 50 °C lead within some days specifically to [Zn(NH{sub 3}){sub 2}Se{sub 4}]{sub n} (1), [Zn(MeNH{sub 2}){sub 2}Se{sub 4}]{sub n} (2), [Zn(NH{sub 3}){sub 2}Se{sub 2.23}S{sub 1.77}]{sub n} (3). From MnCl{sub 2}, Rb{sub 2}Se and excess Se in n-butylamine [Mn({sup n}BuNH{sub 2}){sub 4}Se{sub 6}]{sub n} (4) is obtained after prolonged reaction time at ambient temperature. The compounds are sensitive towards air and loss of NH{sub 3} or the amine ligands. The crystal structures were determined by single crystal diffraction at low temperatures. As a common structural feature, all compounds represent 1D coordination polymers with polychalcogenide chains as linkers between the metal atoms and consist of infinite [M–Ch{sub m}–]{sub n} chains (M=Zn, Mn; Ch{sub m}=Se{sub 4}, (S/Se){sub 4}, Se{sub 6}). The Zn central atoms in 1–3 have tetrahedral coordination with two amine ligands, the Mn atoms in 4 have octahedral coordination with four amine ligands and cis position of the two Se atoms. Raman spectra of 1–3 show the stretching mode vibrations of the Ch{sub 4} groups. The observation of S–S, S–Se, and Se–Se vibration bands in the spectrum of 3 indicates the presence of mixed S/Se polyanions. An optical band gap of 1.86(5) eV was determined for 2 by diffuse reflectance spectroscopy. - Graphical abstract: The reaction of Zn and Se in liquid methylamine yields dark red [Zn(NH{sub 2}CH{sub 3})Se{sub 4}], a 1D coordination polymer consisting of helical Zn–Se{sub 4}–Zn– chains. - Highlights: • A series of 1D coordination polymers consisting of metal amine complexes concatenated by polychalcogenide ions is presented. • Syntheses were performed as solvothermal reactions in liquid ammonia, liquid methylamine and n-butylamine. • Crystal structures are dominated by helices [M–Ch{sub m

  7. Lanthanide contraction effect on crystal structures of lanthanide coordination polymers with cyclohexanocucurbit[6]uril ligand

    Science.gov (United States)

    Zheng, Li-Mei; Liu, Jing-Xin

    2017-01-01

    A series of compounds based on the macrocyclic ligand cyclohexanocucurbit[6]uril (Cy6Q[6]) with formulas {Ln(H2O)6Cy6Q[6]}·2(CdCl4)·H3O·xH2O [isomorphous with Ln=La (1), Ce (2), Pr (3) and Nd (4), x=11 (1), 11 (2), 10 (3) and 11 (4)], {Sm(H2O)5Cy6Q[6]}·2(CdCl4)·H3O·10H2O (5) and {Ln(H2O)5(NO3)@Cy6Q[6]}·2(CdCl4)·2H3O·xH2O [isomorphous with Ln=Gd (6), Tb (7) and Dy (8), x=8 (6), 6 (7) and 6 (8)], have been successfully synthesized by the self-assembly of Cy6Q[6] with the corresponding lanthanide nitrate under hydrochloric acid aqueous solution in the presence of CdCl2. Single-crystal X-ray diffraction analyses revealed that compounds 1-8 all crystallize in monoclinic space group P21/c, and display 1D coordination polymer structures. The lanthanide contraction effect on the structures of 1-8 has also been investigated and discussed in detail. In contrast, the reaction of Cy6Q[6] with the Ho(NO)3, Tm(NO)3, Yb(NO)3 under the same conditions resulted in the compounds 9-11 with formulas Cy6Q[6]·2(CdCl4)·2H3O·xH2O [isomorphous with x=10 (9), 10 (10), and 9 (11)], in which no lanthanide cations are observed. The structural difference of these compounds indicates that the Cy6Q[6] may be used in the separation of lanthanide cations.

  8. 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

  9. Supramolecular networking of macrocycles based on exo-coordination: from discrete to continuous frameworks.

    Science.gov (United States)

    Park, Sunhong; Lee, So Young; Park, Ki-Min; Lee, Shim Sung

    2012-03-20

    Macrocyclic ligands typically show high selectivity for specific metal ions and small molecules, and these features make such molecules attractive candidates for nanoscale chemical sensing applications. Crown ethers are macrocyclic structures with polyether linkages where the oxygen donors are often separated by an ethylene unit (-O-CH(2)-CH(2)-O-). Because the oxygen lone pairs in crown-type macrocycles are directed inward, the preorganized macrocyclic cavity tends to form complexes where metals coordinate inside the cavity (endo-coordination). However, sulfur-containing macrocycles often demonstrate metal coordination outside of the cavity (exo-coordination). This coordination behavior results from the different torsion arrangements adopted by the X-CH(2)-CH(2)-X atom sequence (X = O, gauche; X = S, anti) in these molecules. Exo-coordination is synthetically attractive because it would provide a means of connecting macrocyclic building blocks in diverse arrangements. In fact, exo-coordination could allow the construction of more elaborate network assemblies than are possible using conventional endocyclic coordination (which gives metal-in-cavity products). Exo-coordination can also serve as a tool for crystal engineering through the use of diverse controlling factors. Although challenges remain in the development of exo-coordination-based synthetic approaches and, in particular, for the architectural control of supramolecular coordination platforms, we have established several strategies for the rational synthesis of new metallosupramolecules. In this Account, we describe our recent studies of the assembly of metallosupramolecules and coordination polymers based on sulfur-containing macrocycles that employ simple and versatile exo-coordination procedures. Initially, we focus on the unusual topological products such as sandwich (1:2, metal-to-ligand), club sandwich (2:3), and cyclic oligomeric complexes as discrete network systems. The primary structures we

  10. Preparation of PbS and PbO nanopowders from new Pb(II)(saccharine) coordination polymers

    Energy Technology Data Exchange (ETDEWEB)

    Aslani, Alireza, E-mail: a.aslani110@yahoo.com [Nanobiotechnology Research Center, Baqiyatallah University Medical of Science, PO BOX 1994x81, Tehran (Iran, Islamic Republic of); Department of Chemistry, University of Lorestan, Lorestan-Khoramabad 68135-465 (Iran, Islamic Republic of); Musevi, Seyid Javad, E-mail: Erkin_musevi@hotmail.com [Department of Chemistry, Shahid Beheshti Technical and Vocational University, Urmia (Iran, Islamic Republic of); Şahin, Ertan, E-mail: Ertan@atauni.edu.tr [Department of Chemistry, Faculty of Science, Ataturk University, Erzurum 25240 (Turkey); Yilmaz, Veysel T., E-mail: vtyilmaz@uludag.edu.tr [Department of Chemistry, Faculty of Arts and Sciences, Uludag University, 16059 Bursa (Turkey)

    2014-11-01

    Highlights: • The complex of compounds “[Pb(H{sub 2}O)(μ-OAc)(μ-sac)]{sub n}” are synthesized at nano and bulk size structurally diverse and show interesting three-dimensional coordination polymers. • Reduction of the particle size of the coordination polymers to a few dozen nanometers results in lower thermal stability when compared to the single crystalline samples. • This study demonstrates that the metal–organic framework may be suitable precursors for the preparation of nanoscale materials with interesting morphologies. - Abstract: Nanopowders and single crystal of new Pb(II) three-dimensional coordination polymer, [Pb(H{sub 2}O)(μ-OAc)(μ-sac)]{sub n} “PASAC” were synthesized by a sonochemical and branched tube methods (Yılmaz et al., Z. Anorg. Allg. Chem. 629 (2003) 172). The new nano-structures of Pb(II) coordination polymer were characterized by X-ray crystallography analysis, scanning electron microscopy (SEM), X-ray powder diffraction (XRD), surface analysis (BET), and IR spectroscopy. The crystal structure of these compounds consists of three-dimensional polymeric units. The thermal stability of compounds was studied by thermal gravimetric analysis (TGA) and differential thermal analyses (DTA). PbS and PbO nano-structures were obtained by calcinations of the nano-structures of this coordination polymer at 600 °C.

  11. Practical applications of the geographic coordinate data base in Arkansas

    Science.gov (United States)

    Mickie Warwick; Don C. Bragg

    2005-01-01

    Though not intended for these applications, the General Land Office (GLO) survey notes are a primary source of historical, ecological, and cultural information, making it imperative that their spatial coordinates be as reliable as possible. The Geographic Coordinate Data Base (GCDB) is a statistically-based coordinate fitting program that uses the GLO notes and other...

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

    Science.gov (United States)

    Zhao, Hui; Sun, Xiao-Xia; Hu, Huai-Ming; An, Ran; Yang, Meng-Lin; Xue, Ganglin

    2017-01-01

    Nine new lanthanide coordination polymers, namely, [Ln(Hsfpip)(ox)0.5(H2O)]n·2n(H2O) ((Ln=Eu (1), Tb (2), Dy (3), Ho (4), Er (5), Yb (6), Y(7)), [Ln(H2sfpip)(ox)(H2O)4]n·2n(H2O) (Ln=Nd (8) Sm (9)), [H2ox=oxalic acid, H3sfpip=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 H3sfpip resulted in two types of structures. Compounds 1-7 are obtained at pH 5.0 and exhibit 3D tfz-d networks with ox2- 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.

  13. Electrical bistability around room temperature in an unprecedented one-dimensional coordination magnetic polymer.

    Science.gov (United States)

    Amo-Ochoa, Pilar; Delgado, Esther; Gómez-García, Carlos J; Hernández, Diego; Hernández, Elisa; Martin, Avelino; Zamora, Félix

    2013-05-20

    The synthesis, crystal structure, and physical properties of an unprecedented one-dimensional (1D) coordination polymer containing [Fe2(S2C6H2Cl2)4](2-) entities bridged by dicationic [K2(μ-H2O)2(THF)4](2+) units are described. The magnetic properties show that the title compound presents pairwise Fe-Fe antiferromagnetic interactions that can be well reproduced with a S = 1/2 dimer model with an exchange coupling, J = -23 cm(-1). The electrical conductivity measurements show that the title compound is a semiconductor with an activation energy of about 290 meV and two different transitions, both with large hysteresis of about 60 and 30 K at 260-320 K and 350-380 K, respectively. These two transitions are assumed to be due to slight structural changes in the cation-anion interactions. Differential Scanning Calorimetry confirms the presence of both transitions. This compound represents the first sample of a coordination polymer showing electrical bistability.

  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. Spectroscopic properties of a series of Co(II) coordination polymers and the influence of Co(II) coordination environment on photoelectric property

    Science.gov (United States)

    Jin, Jing; Gong, Yuanyuan; Li, Lei; Han, Xiao; Meng, Qin; Liu, Yonghua; Niu, Shuyun

    2015-02-01

    Four Co(II) coordination polymers, [Co(suc)]n1, [Co(pdc)]n2, {[Co7(suc)4(OH)6(H2O)3] · 8H2O}n3, {[Co(bdc)(phen)(H2O)] · H2O}n4 (H2suc = succinic acid, H2pdc = pyridine-3,4-dicarboxylic acid, H2bdc = 1,2-benzenedicarboxylic acid, phen = 1,10-phenanthroline) were hydrothermally synthesized and characterized by X-ray single-crystal diffraction, surface photovoltage spectroscopy (SPS), electrical conductivity, thermogravimetric analysis (TG), ultraviolet visible and near-infrared absorption spectrum (UV-Vis-NIR), infrared spectrum (IR), and elemental analysis. The structural analyses indicate that the coordination numbers of the Co(II) ions are 4, 5, 6 and 6 for the polymers 1-4, respectively. And polymers 1 and 2 exhibit 3D structure formed by suc2- and pdc2- anions bridging Co(II) ions, respectively. Polymer 3 exhibits a 2D structure with suc2- anions bridging seven-nuclear [Co7(OH)6(H2O)3]3- unit and polymer 4 is a 1D structure bridged by bdc2- anions. The surface photoelectric properties of the cobalt polymers were mainly studied by SPS. The results of SPS reveal that all polymers possess certain photoelectric conversion property in the range of 300-800 nm. The influences of the structure, coordination micro-environment of central metal ion and structural dimensionality on response bands of SPS were discussed.

  16. Assembly of 4-, 6- and 8-connected Cd(II) pseudo-polymorphic coordination polymers: Synthesis, solvent-dependent structural variation and properties

    Energy Technology Data Exchange (ETDEWEB)

    Li, Zhao-Hao [College of Chemistry and Chemical Engineering, and Henan Key Laboratory of Function-Oriented Porous Materials, Luoyang Normal University, Luoyang 471934 (China); Xue, Li-Ping, E-mail: lpxue@163.com [College of Food and Drug, Luoyang Normal University, Luoyang 471934 (China); Miao, Shao-Bin [College of Chemistry and Chemical Engineering, and Henan Key Laboratory of Function-Oriented Porous Materials, Luoyang Normal University, Luoyang 471934 (China); Zhao, Bang-Tun, E-mail: zbt@lynu.edu.cn [College of Chemistry and Chemical Engineering, and Henan Key Laboratory of Function-Oriented Porous Materials, Luoyang Normal University, Luoyang 471934 (China)

    2016-08-15

    The reaction of Cd(NO{sub 3}){sub 2}·4H{sub 2}O, 2,5-thiophenedicarboxylic acid (H{sub 2}tdc) and 1,2-bis(imidazol-1′-yl)methane (bimm) by modulating solvent systems yielded three highly connected pseudo-polymorphic coordination polymers based on different dinuclear [Cd{sub 2}(CO{sub 2}){sub 2}] subunits bridged by carboxylate groups. Single crystal structural analyses reveal structural variation from 4-connected 2D sql layer, 6-connected 2-fold interpenetrated 3D pcu to 8-connected 3D bcu-type network in compounds 1–3. The structural dissimilarity in the structures dependent on the coordination environments of Cd(II) ions and linking modes of mixed ligand influenced by different solvent systems during the synthesis process. Moreover, thermogravimetric and photoluminescence behaviors of 1–3 were also investigated for the first time, and all the complexes emit blue luminescence in the solid state. - Graphical abstract: Key Topic. Different solvent systems modulated three Cd(II) pseudo-polymorphic coordination polymers based on thiophene-2,5-dicarboxylate and 1,2-bis(imidazol-1′-yl)methane mixed ligands. Display Omitted - Highlights: • Three solvent-dependent Cd(II) pseudo-polymorphic coordination polymers have been synthesized. • Structural variation from 4-connected 2D layer, 6-connected 2-fold interpenetrated 3D net to 8-connected 3D net. • All complexes emit blue luminescence.

  17. Alternative DNA base pairing through metal coordination.

    Science.gov (United States)

    Clever, Guido H; Shionoya, Mitsuhiko

    2012-01-01

    Base-pairing in the naturally occurring DNA and RNA oligonucleotide duplexes is based on π-stacking, hydrogen bonding, and shape complementarity between the nucleobases adenine, thymine, guanine, and cytosine as well as on the hydrophobic-hydrophilic balance in aqueous media. This complex system of multiple supramolecular interactions is the product of a long-term evolutionary process and thus highly optimized to serve its biological functions such as information storage and processing. After the successful implementation of automated DNA synthesis, chemists have begun to introduce artificial modifications inside the core of the DNA double helix in order to study various aspects of base pairing, generate new base pairs orthogonal to the natural ones, and equip the biopolymer with entirely new functions. The idea to replace the hydrogen bonding interactions with metal coordination between ligand-like nucleosides and suitable transition metal ions culminated in the development of a plethora of artificial base-pairing systems termed "metal base-pairs" which were shown to strongly enhance the DNA duplex stability. Furthermore, they show great potential for the use of DNA as a molecular wire in nanoscale electronic architectures. Although single electrons have proven to be transmitted by natural DNA over a distance of several base pairs, the high ohmic resistance of unmodified oligonucleotides was identified as a serious obstacle. By exchanging some or all of the Watson-Crick base pairs in DNA with metal complexes, this problem may be solved. In the future, these research efforts are supposed to lead to DNA-like materials with superior conductivity for nano-electronic applications. Other fields of potential application such as DNA-based supramolecular architecture and catalysis may be strongly influenced by these developments as well. This text is meant to illustrate the basic concepts of metal-base pairing and give an outline over recent developments in this field.

  18. Starch-based completely biodegradable polymer materials

    Directory of Open Access Journals (Sweden)

    2009-06-01

    Full Text Available Starch is a natural polymer which possesses many unique properties and some shortcoming simultaneously. Some synthetic polymers are biodegradable and can be tailor-made easily. Therefore, by combining the individual advantages of starch and synthetic polymers, starch-based completely biodegradable polymers (SCBP are potential for applications in biomedical and environmental fields. Therefore it received great attention and was extensively investigated. In this paper, the structure and characteristics of starch and some synthetic degradable polymers are briefly introduced. Then, the recent progress about the preparation of SCBP via physical blending and chemical modification is reviewed and discussed. At last, some examples have been presented to elucidate that SCBP are promising materials for various applications and their development is a good solution for reducing the consumption of petroleum resources and environmental problem.

  19. Straw-based coordinate muon chamber

    CERN Document Server

    Peshekhonov, V; Myalkovskiy, V; Russakovich, N; Zhukov, I

    2012-01-01

    The article considers a prototype module with sensitive dimensions of 2 x 0.5 m2 based on 2 m long straw tubes which preserves its geometrical dimensions up to the pressure of 4 bar independently of the ambient temperature and humidity. The suggested technique provides a possibility of constructing relatively low-cost planar modules by using straw tubes as long as needed for constructing large area detectors at colliders or other field experiments by assembling them in a common coordinate detector with a user-specified acceptance. The distinguishing feature of a detector is its good radiation hardness, low radiation thickness and a possibility of optimizing the detector operation mode in a large range of gas pressure.

  20. DNA damage induced by bare and loaded microporous coordination polymers from their ground and electronic excited states.

    Science.gov (United States)

    Yañuk, Juan G; Alomar, María L; Gonzalez, M Micaela; Simon, Francisco; Erra-Balsells, Rosa; Rafti, Matías; Cabrerizo, Franco M

    2015-05-21

    We report on interactions of cell free double-stranded DNA (dsDNA) with a selected subgroup of Microporous Coordination Polymers (MCPs). In particular, we have studied the influence of different metal ion constituents and chemically modified linkers using a set of five benzene carboxylate-based MCPs. Our results suggest that the DNA moiety can be structurally modified in two different ways: by direct MCPs-dsDNA interaction and/or through photosensitized processes. The extent of the observed damage was found to be strongly dependent on the charge density of the material. The potential use of the MCPs tested as inert carriers of photosensitizers was demonstrated by analyzing the interaction between dsDNA and harmine-loaded Cr-based materials, both in the absence of light and upon UVA irradiation.

  1. 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.

  2. Electrochemical Li-Ion Intercalation in Octacyanotungstate-Bridged Coordination Polymer with Evidence of Three Magnetic Regimes.

    Science.gov (United States)

    Long, Jérôme; Asakura, Daisuke; Okubo, Masashi; Yamada, Atsuo; Guari, Yannick; Larionova, Joulia

    2016-08-01

    Discovery of novel compounds capable of electrochemical ion intercalation is a primary step toward development of advanced electrochemical devices such as batteries. Although cyano-bridged coordination polymers including Prussian blue analogues have been intensively investigated as ion intercalation materials, the solid-state electrochemistry of the octacyanotungstate-bridged coordination polymer has not been investigated. Here, we demonstrate that an octacyanotungstate-bridged coordination polymer Tb(H2O)5[W(CN)8] operates as a Li(+)-ion intercalation electrode material. The detailed magnetic measurements reveal that the tunable amount of intercalated Li(+) ion in the solid-state redox reaction between paramagnetic [W(V)(CN)8](3-) and diamagnetic [W(IV)(CN)8](4-) in the framework enables the electrochemical control of different magnetic regimes. While the initial ferromagnetic long-range ordering is irreversibly lost upon lithium insertion, electrochemical switching between paramagnetic and short-range ordering regimes can be achieved.

  3. Friction and wear in polymer-based materials

    CERN Document Server

    Bely, V A; Petrokovets, M I

    1982-01-01

    Friction and Wear in Polymer-Based Materials discusses friction and wear problems in polymer-based materials. The book is organized into three parts. The chapters in Part I cover the basic laws of friction and wear in polymer-based materials. Topics covered include frictional interaction during metal-polymer contact and the influence of operating conditions on wear in polymers. The chapters in Part II discuss the structure and frictional properties of polymer-based materials; the mechanism of frictional transfer when a polymer comes into contact with polymers, metals, and other materials; and

  4. Recent developments in Inorganic polymers: A Review with focus on Si-Al based inorganic polymers

    Directory of Open Access Journals (Sweden)

    Shrray Srivastava

    2015-12-01

    Full Text Available Inorganic polymers are a unique classification of polymers. They contain inorganic atoms in the main chain. Hybrids with organic polymers as well as those chains that contain metals as pendant groups are considered in a special sub-classification as organo-metallic polymers. The networks containing only inorganic elements in main chain are called inorganic polymers. The silicone rubber is the most commercial inorganic polymer. The organo-metallic and inorganic polymers have a different set of applications. The current paper is a review of current applications of polymers with inorganic back-bone networks, especially focusing on Si and Al based inorganic polymeric materials.

  5. Gas Sensors Based on Electrodeposited Polymers

    Directory of Open Access Journals (Sweden)

    Boris Lakard

    2015-07-01

    Full Text Available Electrochemically deposited polymers, also called “synthetic metals”, have emerged as potential candidates for chemical sensing due to their interesting and tunable chemical, electrical, and structural properties. In particular, most of these polymers (including polypyrrole, polyaniline, polythiophene and their derivatives can be used as the sensitive layer of conductimetric gas sensors because of their conducting properties. An important advantage of polymer-based gas sensors is their efficiency at room temperature. This characteristic is interesting since most of the commercially-available sensors, usually based on metal oxides, work at high temperatures (300–400 °C. Consequently, polymer-based gas sensors are playing a growing role in the improvement of public health and environment control because they can lead to gas sensors operating with rapid detection, high sensitivity, small size, and specificity in atmospheric conditions. In this review, the recent advances in electrodeposited polymer-based gas sensors are summarized and discussed. It is shown that the sensing characteristics of electrodeposited polymers can be improved by chemical functionalization, nanostructuration, or mixing with other functional materials to form composites or hybrid materials.

  6. Leucine zipper motif inspiration: a two-dimensional leucine Velcro-like array in peptide coordination polymers generates hydrophobicity.

    Science.gov (United States)

    Rodríguez-Hermida, Sabina; Evangelio, Emi; Rubio-Martínez, Marta; Imaz, Inhar; Verdaguer, Albert; Juanhuix, Jordi; Maspoch, Daniel

    2017-08-29

    Here, we show that the well-known hydrophobic leucine (Leu) zipper motif (also known as the coiled-coil or Leu scissors motif), typically found in proteins, can be used as a source of inspiration in coordination polymers built from Leu-containing dipeptides or tripeptides. We demonstrate that this motif can be extended to form Velcro-like layers of Leu, and that the hydrophobicity of these layers is transferred to coordination polymers, thereby enabling the development of a new type of hydrophobic materials.

  7. 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.

  8. Proton dynamics of two-dimensional oxalate-bridged coordination polymers.

    Science.gov (United States)

    Miyatsu, Satoshi; Kofu, Maiko; Nagoe, Atsushi; Yamada, Takeshi; Sadakiyo, Masaaki; Yamada, Teppei; Kitagawa, Hiroshi; Tyagi, Madhusudan; García Sakai, Victoria; Yamamuro, Osamu

    2014-08-28

    A two-dimensional porous coordination polymer (NH4)2{HOOC(CH2)4COOH}[Zn2(C2O4)3] (abbreviated as (NH4)2(adp)[Zn2(ox)3] (adp = adipic acid, ox = oxalate)), which accommodates water molecules between the [Zn2(ox)3] layers, is highly remarked as a new type of crystalline proton conductor. In order to investigate its phase behavior and the proton conducting mechanism, we have performed adiabatic calorimetry, neutron diffraction, and quasi-elastic neutron scattering experiments on a fully hydrated sample (NH4)2(adp)[Zn2(ox)3]·3H2O with the highest proton conductivity (8 × 10(-3) S cm(-1), 25 °C, 98% RH). Its isostructural derivative K2(adp)[Zn2(ox)3]·3H2O was also measured to investigate the role of ammonium ions. (NH4)2(adp)[Zn2(ox)3]·3H2O and K2(adp)[Zn2(ox)3]·3H2O exhibit higher order transitions at 86 K and 138 K, respectively. From the magnitude of the transition entropy, the former is of an order-disorder type while the latter is of a displacive type. (NH4)2(adp)[Zn2(ox)3]·3H2O has four Debye-type relaxations and K2(adp)[Zn2(ox)3]·3H2O has two similar relaxations above each transition temperature. The two relaxations of (NH4)2(adp)[Zn2(ox)3]·3H2O with very small activation energies (ΔEa < 5 kJ mol(-1)) are due to the rotational motions of ammonium ions and play important roles in the proton conduction mechanism. It was also found that the protons in (NH4)2(adp)[Zn2(ox)3]·3H2O are carried through a Grotthuss mechanism. We present a discussion on the proton conducting mechanism based on the present structural and dynamical information.

  9. Functional tetrametallic linker modules for coordination polymers and metal-organic frameworks.

    Science.gov (United States)

    Johansson, Frank B; Bond, Andrew D; McKenzie, Christine J

    2007-03-19

    potential construction of 1-D and 2-D coordination polymers/metal-organic frameworks (MOFs) capable of reversible O2 binding.

  10. 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.

  11. Glass Formation of a Coordination Polymer Crystal for Enhanced Proton Conductivity and Material Flexibility.

    Science.gov (United States)

    Chen, Wenqian; Horike, Satoshi; Umeyama, Daiki; Ogiwara, Naoki; Itakura, Tomoya; Tassel, Cédric; Goto, Yoshihiro; Kageyama, Hiroshi; Kitagawa, Susumu

    2016-04-18

    The glassy state of a two-dimensional (2D) Cd(2+) coordination polymer crystal was prepared by a solvent-free mechanical milling process. The glassy state retains the 2D structure of the crystalline material, albeit with significant distortion, as characterized by synchrotron X-ray analyses and solid-state multinuclear NMR spectroscopy. It transforms to its original crystal structure upon heating. Thus, reversible crystal-to-glass transformation is possible using our new processes. The glass state displays superior properties compared to the crystalline state; specifically, it shows anhydrous proton conductivity and a dielectric constant two orders of magnitude greater than the crystalline material. It also shows material flexibility and transparency.

  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. Trapping of a spatial transient state during the framework transformation of a porous coordination polymer.

    Science.gov (United States)

    Kondo, Mio; Furukawa, Shuhei; Hirai, Kenji; Tsuruoka, Takaaki; Reboul, Julien; Uehara, Hiromitsu; Diring, Stéphane; Sakata, Yoko; Sakata, Osami; Kitagawa, Susumu

    2014-04-01

    Structural transformability accompanied by molecular accommodation is a distinguished feature of porous coordination polymers (PCPs) among porous materials. Conventional X-ray crystallography allows for the determination of each structural phase emerged during transformation. However, the propagation mechanism of transformation through an entire crystal still remains in question. Here we elucidate the structural nature of the spatial transient state, in which two different but correlated framework structures, an original phase and a deformed phase, simultaneously exist in one crystal. The deformed phase is distinctively generated only at the crystal surface region by introducing large guest molecules, while the remaining part of crystal containing small molecules maintains the original phase. By means of grazing incidence diffraction techniques we determine that the framework is sheared with sharing one edge of the original primitive cubic structure, leading to the formation of crystal domains with four mirror image relationships.

  14. Syntheses, Structures and Photoluminescence of Two New Europium(Ⅲ) Coordination Polymers

    Institute of Scientific and Technical Information of China (English)

    ZHU Hai—Yun

    2012-01-01

    Two new europium (Ⅲ) coordination polymers formulated as Eu2(H2O)2(ox)4 ]· (C5H6N)2 ·2H 2 O(1) and Eu 2(ad)3(H2O)4 ]·0.25H2O (2) (H2ox = oxalic acid, H2ad = adipic acid) have been synthesized from the self-assembly of lanthanide ions Eu 3+ with flexible oxalic and adipic acid ligands, respectively. Structural analyses revealed that complex 1 exhibits three-dimensional metalorganic frameworks, and 2 has intricate two-dimensional interpenetrated metal-organic networks. In addition, the photoluminescent properties of complexes 1 and 2 were discussed in detail, which shows strong red emission, corresponding to 5 D0 → 7 F 2 transition of Eu3+ ions.

  15. Syntheses, Structures and Photoluminescence of Two New Europium(III) Coordination Polymers

    Institute of Scientific and Technical Information of China (English)

    LI Min; HUANG Qun-Zeng; FENG Yu-Quan; SHI Heng-Zhen

    2012-01-01

    Two new europium (Ⅲ) coordination polymers formulated as Eu2(H20)a(ox)4]· (CsH6N)2-2H20 (1) and Eu2(ad)3(H20)4]'0.25H20 (2) (H20x = oxalic acid, H2ad = adipic acid) have been synthesized from the self-assembly of lanthanide ions Eu^3+ with flexible oxalic and adipic acid ligands, respectively. Structural analyses revealed that complex 1 exhibits three-dimensional metalorganic frameworks, and 2 has intricate two-dimensional interpenetrated metal-organic networks. In addition, the photoluminescent properties of complexes 1 and 2 were discussed in detail, which shows strong red emission, corresponding to ^5Do →^7F? transition of Eu^3+ ions.

  16. Linear alkaline earth metal phosphinate coordination polymers: synthesis and structural characterization.

    Science.gov (United States)

    Rood, Jeffrey A; Huttenstine, Ashley L; Schmidt, Zachery A; White, Michael R; Oliver, Allen G

    2014-06-01

    Reaction of alkaline earth metal salts with diphenylphosphinic acid in dimethylformamide solvent afforded four coordination polymers: [Mg3(O2PPh2)6(DMF)2]·2DMF (I), [Ca(O2PPh2)2(DMF)2] (II), [Sr(O2PPh2)2(DMF)2] (III) and [Ba(O2PPh2)2(DMF)2] (IV) (where DMF is N,N-dimethylformamide). Single-crystal X-ray diffraction revealed that all four compounds produce linear chain structures in the solid state, with the Ca, Sr and Ba forming isostructural crystals. The bulk materials were characterized by FT-IR and (1)H NMR spectroscopy and elemental analyses.

  17. Synthesis and Characterization of Metal-B-diketonate Coordination Complexes and Polymers

    Directory of Open Access Journals (Sweden)

    Mohammed A. Al-Anber

    2013-10-01

    Full Text Available A mononuclear [M(tba2(H2O2] (3: M = Mn, 4: M = Ni, 5: M = Zn; tba = deprotonated of 1 complexes have been prepared by the reaction of 3-benzoyl-1.1.1-trifluoro-acetone (H-tba: 1 with M(OAc2.nH2O (M = Mn, Ni, Zn; OAc = O2CMe in a 2:1 molar ratio. Complexes 3 - 5 can be extended to form a coordination polymers of general formula [M(tba2(4,4'-bipy]n (6: M = Mn, 7: M = Ni, 8: M = Zn; tba = 3-benzoyl-1.1.1-trifluoro-acetone; 4,4'-bipy = 4,4’-bipyridine by bridging the central metal atom with 4,4’-bipyridine (4,4'-bipy. The reaction progress was controlled via FTIR, UV-Vis spectroscopy and elemental analysis.

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

    Science.gov (United States)

    Kajiro, Hiroshi; Kondo, Atsushi; Kaneko, Katsumi; Kanoh, Hirofumi

    2010-01-01

    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. PMID:21152303

  19. 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.

  20. Carboxyl group (-CO2 H) functionalized coordination polymer nanoparticles as efficient platforms for drug delivery.

    Science.gov (United States)

    Novio, Fernando; Lorenzo, Julia; Nador, Fabiana; Wnuk, Karolina; Ruiz-Molina, Daniel

    2014-11-17

    Functionalization of nanoparticles can significantly influence their properties and potential applications. Although researchers can now functionalize metal, metal oxide, and organic polymer nanoparticles with a high degree of precision, controlled surface functionalization of nanoscale coordination polymer particles (CPPs) has remained a significant challenge. The lack of methodology is perhaps one of the greatest roadblocks to the advancement of CPPs into high added-value drug delivery applications. Here, we report having achieved this goal through a stepwise formation and functionalization protocol. We fabricated robust nanoparticles with enhanced thermal and colloidal stabilities by incorporation of carboxyl groups and these surface carboxyl groups could be subsequently functionalized through well-known peptide coupling reactions. The set of chemistries that we employed as proof-of-concept enabled a plethora of new functional improvements for the application of CPPs as drug delivery carriers, including enhanced colloidal stabilities and the incorporation of additional functional groups such as polyethylene glycol (PEG) or fluorescent dyes that enabled tracking of their cellular uptake. Finally, we ascertained the cytotoxicity of the new CPP nanoparticles loaded with camptothecin to human breast adenocarcinoma (MCF-7). Efflux measurements show that the encapsulation of camptothecin enhances the potency of the drug 6.5-fold and increases the drug retention within the cell.

  1. Structure and magnetic properties of heterometallic coordination carboxylate polymers with cobalt and lithium atoms

    Energy Technology Data Exchange (ETDEWEB)

    Evstifeev, I. E.; Kiskin, M. A., E-mail: mkiskin@igic.ras.ru [Russian Academy of Sciences, Kurnakov Institute of General and Inorganic Chemistry (Russian Federation); Bogomyakov, A. S. [Russian Academy of Sciences, International Tomography Center, Siberian Branch (Russian Federation); Sidorov, A. A.; Novotortsev, V. M.; Eremenko, I. L. [Russian Academy of Sciences, Kurnakov Institute of General and Inorganic Chemistry (Russian Federation)

    2011-09-15

    Reactions between lithium pivalate and cobalt coordination polymers [Co{sub 5}(OH{sub 2})(OH)(Piv){sub 9})L{sup 1}){sub 4}]{sub n} (I) and [Co{sub 2}(OH{sub 2})(Piv){sub 4}(L{sup 2}){sub 2}]{sub n} (II), where Piv-is the pivalate anion, L{sup 1} is pyrazine, and L{sup 2} is pyrimidine, result in new heterometallic polymers {l_brace}[Li{sub 2}Co{sub 2}(Piv){sub 6}(L{sup 1}){sub 2}]{sub 2}MeCN{r_brace}{sub n} (III), {l_brace}[Li{sub 2}Co{sub 2}(Piv){sub 6}(L{sup 2})]{sub 0.5}MeCN{r_brace}{sub n} (IV), and [Li{sub 2}Co{sub 2}(Piv){sub 6}(L{sup 2}){sub 2}]{sub n} (V). The resulting compounds contain tetra-nuclear {l_brace}Li{sub 2}Co{sub 2}(Piv){sub 6}{r_brace} fragments connected by neutral bridging ligands (pyrazine or pyrimidine) into layer structures. Crystal structures III-V are determined, and the magnetic properties of III and IV are studied.

  2. Synthesis and characterization of two one-dimensional lanthanide coordination polymers

    Energy Technology Data Exchange (ETDEWEB)

    Yin Mingcai; Sun Jutang

    2004-11-03

    Two lanthanide coordination polymers [Eu(H{sub 2}sal)(Hsal)(sal){center_dot}H{sub 2}O]{sub n} (1) and {l_brace}[Tb(FUR){sub 3}(H{sub 2}O){sub 2}]{center_dot}DMF{r_brace}{sub n} (2) (H{sub 2}sal, salicylic acid; Hsal{sup -}, o-HOC{sub 6}H{sub 4}CO{sub 2}{sup -}; HFUR, {alpha}-furancarboxylic acid; DMF, N,N-dimethylformamide) were synthesized and characterized by elemental analysis, TG, IR, and luminescence spectra. The crystal structures were determined by X-ray single crystal analysis. Both complexes are one-dimensional polymers. Probably the luminescence quenching of complex 1 is assigned to its special one-dimensional ribbon structure. The vibration energy level caused by the one-dimensional ribbon and located between {sup 5}D{sub 0} and {sup 7}F{sub j} maybe is the main reason. Complex 2 displays intense green luminescence under the excitation of UV light. The emission bands at 486, 541, 584, and 618 nm are attributed to the characteristic {sup 5}D{sub 4}{yields}{sup 7}F{sub j} (j = 6, 5, 4, 3) transitions of Tb(III) ions, respectively.

  3. Magnetic and Photochromic Properties of a Manganese(II) Metal-Zwitterionic Coordination Polymer.

    Science.gov (United States)

    Gong, Teng; Yang, Xiao; Sui, Qi; Qi, Yan; Xi, Fu-Gui; Gao, En-Qing

    2016-01-04

    The solvothermal reaction of Mn(ClO4)2, NaN3, and a rigid viologen-tethered tetracarboxylic acid (1,1'-bis(3,5-dicarboxyphenyl)-4,4'-bipyridinium chloride, [H4L]Cl2) led to a coordination polymer of formula [Mn4(L)(N3)6(H2O)2]n. X-ray analysis revealed a 3D coordination structure. The Mn(II) ions are connected by mixed azide and carboxylate bridges to give 2D layers, which are pillared by the viologen tether of the zwitterionic ligand. Magnetic analyses suggested that the compound features antiferromagnetism and field-induced metamagnetism. The compound also shows photochromic and photomagnetic properties. The long-range magnetic ordering is owed to the spin-canting structure of the Mn(II)-azide-carboxylate layer; the photochromism involves the formation of viologen radicals via photoinduced electron transfer, and the photomagnetism is related to the interactions between the metal ion and the photogenerated radicals. The study demonstrates a strategy for the design of new multifunctional materials with photoresponsive properties.

  4. Hydrothermal Synthesis, Crystal Structure, Spectrum and Electrochemical Analysis of the Copper(Ⅱ) Coordination Polymer

    Institute of Scientific and Technical Information of China (English)

    LI Chang-Hong; LI Wei; LI Yu-Lin; KUANG Yun-Fei

    2012-01-01

    The three-dimensional framework copper(Ⅱ) coordination polymer with basic copper carbonate and 3-(pyridin-2-yl)-1,2,4-triazole has been hydrothermally synthesized. It crystallizes in monoclinic space group P21/c, with a = 1.20860(3), b = 1.29581(2), c = 1.67863(3) nm, β = 116.0280(2)°, C21H12Cu3N12, Mr = 623.05, V = 2.36230(9) nm3, Dc = 1.752 g/cm3, Z = 4, F(000) = 1236, GOOF = 1.037, the final R = 0.0408 and wR = 0.1141. Every unit cell contains three copper atoms and three 3-(pyridin-2-yl)-1,2,4-triazole ligands. Every central Cu(Ⅱ) ion is coordinated by four nitrogen atoms of the 3-(pyridin-2-yl)-1,2,4-triazole ligands, forming a distorted tetrahedron. The title complex exhibits an intense photoluminescence at room temperature with the maximum emission at 392 nm. The cyclic voltametric behavior of the complex shows that the electron transfer in electrolysis reaction is irreversible.

  5. Polymer Based Biosensors for Medical Applications

    DEFF Research Database (Denmark)

    Cherré, Solène; Rozlosnik, Noemi

    2015-01-01

    The objective of this chapter is to give an overview about the newest developments in biosensors made of polymers for medical applications. Biosensors are devices that can recognize and detect a target with high selectivity. They are widely used in many fields such as medical diagnostic, environm......The objective of this chapter is to give an overview about the newest developments in biosensors made of polymers for medical applications. Biosensors are devices that can recognize and detect a target with high selectivity. They are widely used in many fields such as medical diagnostic...... and be available for use by everybody. To fulfil these purposes, polymers represent very appropriate materials. Many nano- and microfabrication methods for polymers are available, allowing a fast and cheap production of devices. This chapter will present the general concept of a biosensor in a first part....... The second part will focus on conducting polymers, used as electrode material in devices based on electrochemical detection. A third part will describe the molecularly imprinted technology, where the target is replicated in 3D negative form into the polymer....

  6. 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.

  7. Nucleotide/Tb³⁺ coordination polymer nanoparticles as luminescent sensor and scavenger for nitrite ion.

    Science.gov (United States)

    Qi, Zewan; You, Qi; Chen, Yang

    2016-01-01

    Newly emerged metal organic coordination polymers have aroused the great interest in designing tailored functional materials. In this study, multiple functional components, luminescent Tb(3+) ion, nucleobase and antenna molecule, were integrated in a single material and prepared into a responsive nanoparticle for nitrite. The terbium coordination polymer nanoparticles made of this kind of material have the dual functions of recognition and transduction and obey a preset sensing mechanism without a post-functionalization of common materials. As the result of the tailored, the terbium coordination polymer nanoparticles are highly sensitive and selective to nitrite by means of Dexter energy transfer between Tb(3+) ion and nitrite, and can be used for the scavenger for nitrite in aqueous solution. The detection limit, dynamic range and removal capacity of U-Tb-OBBA CPNPs for nitrite are 0.3 µM, 0.3-470 µM and 4.44 mg per gram of particles, respectively. Metal organic coordination polymers show an attractive potential in constructing smart sensing materials.

  8. 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.

  9. The exceptionally rich coordination chemistry generated by Schiff-base ligands derived from o-vanillin.

    Science.gov (United States)

    Andruh, Marius

    2015-10-14

    Ortho-vanillin became very popular in coordination chemistry because of its Schiff bases, which generate a rich variety of complexes, ranging from oligonuclear species to coordination polymers. Some of these organic molecules are particularly useful in metallosupramolecular chemistry for assembling homo- and heterometallic helicates. The Schiff bases obtained using aminoalcohols open the door to the synthesis of homo- and heterometallic clusters with various nuclearities and surprising topologies of the metal centers. Several relevant structural types are reviewed. The heterobinuclear 3d-3d' and 3d-4f complexes are valuable building-blocks for the synthesis of heterotrimetallic systems. Beyond the richness of this chemistry, the complexes obtained from o-vanillin-based Schiff ligands show interesting properties: magnetism, luminescence, chirality, catalysis, cytotoxicity, and ferroelectricity. This paper reviews recent data that illustrate a very fertile and dynamic research field in coordination chemistry and materials science.

  10. Copper(II) coordination polymers: tunable structures and a different activation effect of hydrogen peroxide for the degradation of methyl orange under visible light irradiation.

    Science.gov (United States)

    Liu, Lu; Wu, Dongqing; Zhao, Bei; Han, Xiao; Wu, Jie; Hou, Hongwei; Fan, Yaoting

    2015-01-21

    By tuning the synthesis conditions, based on a conformation-sensitive ligand, 1,4-bis(1,2,4-triazole-1-methylene)-2,3,5,6-tetramethyl benzene (btmx) and Cu(NO3)2·3H2O/CuCl2·2H2O, we have obtained three Cu(ii) coordination polymers with diverse structures, namely, {[Cu(btmx)2(H2O)]·2NO3}n (), {[Cu(btmx)2(Cl)2]·5H2O}n () and [Cu(btmx)(Cl)2]n (). Complex exhibits a novel 2D → 3D interpenetrating structure with a point symbol of 6(3). Complex features an irregular 2D grid with (4(4)·6(2)) topology. The structure of complex is a 1D double chain structure. The ultraviolet-visible absorption spectra and TG curves of these complexes are also presented and discussed. Moreover, under visible light, the coordination polymers , , and display a different activation effect of hydrogen peroxide (H2O2) for the photocatalytic decomposition of methyl orange (MO), which indicates that the coordination polymers may have bright prospects in the field of photocatalytic degradation of dyes.

  11. [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.

  12. 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.

  13. Reo: A Channel-based Coordination Model for Component Composition

    NARCIS (Netherlands)

    Arbab, F.

    2004-01-01

    In this paper, we present Reo, which forms a paradigm for composition of software components based on the notion of mobile channels. Reo is a channel-based exogenous coordination model in which complex coordinators, called connectors, are compositionally built out of simpler ones. The simplest conne

  14. A channel-based coordination model for component composition

    NARCIS (Netherlands)

    Arbab, F.

    2002-01-01

    In this paper, we present $P epsilon omega$, a paradigm for composition of software components based on the notion of mobile channels. $P repsilon omega$ is a channel-based exogenous coordination model wherein complex coordinators, called {em connectors are compositionally built out of simpler ones.

  15. Biodegradation studies of rosin-based polymers.

    Science.gov (United States)

    Satturwar, P M; Mandaogade, P M; Darwhekar, G N; Fulzele, S V; Joshi, S B; Dorle, A K

    2003-07-01

    This study was designed to investigate two rosin-based polymers (R-1 and R-2) for their in vitro and in vivo biodegradation behavior. The in vitro hydrolytic degradation was carried out in buffer solutions of pH 4.4, 7.4, and 10.4 at 37 degrees C. Enzymatic degradation was studied using enzymes lipase, pancreatine, and pectinase. Free films of the two polymers were subcutaneously implanted in rabbits for the in vivo biodegradation. The extent of degradation was determined quantitatively by weight loss and was followed qualitatively by scanning electron microscopy. The extent and the rate of degradation was better in vivo than in vitro. The polymers showed poor enzymatic degradation and a highly pH-dependent hydrolytic degradation.

  16. Different dimensional coordination polymers with 4,4'-oxybis(benzoate): Syntheses, structures and properties

    Energy Technology Data Exchange (ETDEWEB)

    Lun, Huijie [Henan Key Laboratory of Polyoxometalate, Institute of Molecular and Crystal Engineering, College of Chemistry and Chemical Engineering, Henan University, Kaifeng, Henan, 475004 (China); Li, Yamin, E-mail: liyamin@henu.edu.cn [State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou, Fujian 350002 (China); Zhang, Xudong [State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou, Fujian 350002 (China); Yang, Jing-He; Xiao, Changyu [Henan Key Laboratory of Polyoxometalate, Institute of Molecular and Crystal Engineering, College of Chemistry and Chemical Engineering, Henan University, Kaifeng, Henan, 475004 (China); Xu, Yanqing [School of Chemistry, Key Laboratory of Cluster Science, Ministry of Education of China, Beijing Institute of Technology, Beijing 100081 (China); Li, Junrui [Henan Key Laboratory of Polyoxometalate, Institute of Molecular and Crystal Engineering, College of Chemistry and Chemical Engineering, Henan University, Kaifeng, Henan, 475004 (China)

    2014-07-01

    Five transition-metal coordination polymers, namely, [Zn{sub 7}Cl{sub 6}(oba){sub 4}]{sub n} (1), [Cd{sub 7}Cl{sub 6}(oba){sub 4}]{sub n} (2), [Zn(oba)(H{sub 2}O)]{sub n} (3), [Ag{sub 2}(oba)]{sub n} (4) and [Co(oba)(H{sub 2}O){sub 2}]{sub n} (5) (H{sub 2}oba=4,4′-oxydibenzoic acid), have been achieved under hydrothermal conditions and structurally characterized by IR, elemental analyses, X-ray single-crystal diffraction and TGA. The X-ray single-crystal diffraction reveals that compounds 1 and 2 are isomorphism, featuring pillared-layer 3D motifs, in which the 2D inorganic layers (Zn{sub 6}Cl{sub 7}){sub n} (or (Cd{sub 6}Cl{sub 7}){sub n}) are connected by oba{sup 2−} pillars. Compound 3 exhibits 1D stair-like chain and extends to a 3D network by two different interchain O–H–O hydrogen bonding interactions while compound 4 features wave chains and stretches to 2D layer by interchain Ag–O weak contacts. Compound 5 shows 2D network in which Co-chains are pillared by oba{sup 2−} ligand and then forms a 3D network by four different O–H–O hydrogen bonding interactions. Furthermore, 1–4 exhibit luminescent properties at a solid state and 5 shows antiferromagnetic behavior. - Graphical abstract: Five new transition-metal coordination complexes 1–5 have been synthesized and characterized by single-crystal X-ray diffractions, IR spectra, elemental analyses, thermogravimetric analyses (TGA), photoluminescent spectra and magnetic measurement. - Highlights: • Compound 1 exhibits a pillared-layer 3D network. • The photoluminescent properties of 1–4 have been measured. • Compound 5 exhibits antiferromagnetic behavior.

  17. Coordinating control of multiple rigid bodies based on motion primitives

    Institute of Scientific and Technical Information of China (English)

    Fan Wu; Zhi-Yong Geng

    2012-01-01

    This paper studies the problem of coordinated motion generation for a group of rigid bodies.Two classes of coordinated motion primitives,relative equilibria and maneuvers,are given as building blocks for generating coordinated motions.In a motion-primitive based planning framework,a control method is proposed for the robust execution of a coordinated motion plan in the presence of perturbations,The control method combines the relative equilibria stabilization with maneuver design,and results in a closeloop motion planning framework.The performance of the control method has been illustrated through a numerical simulation.

  18. Metal-Organic Framework-Polymer Composite as a Highly Efficient Sorbent for Sulfonamide Adsorption and Desorption: Effect of Coordinatively Unsaturated Metal Site and Topology.

    Science.gov (United States)

    Shih, Yung-Han; Wang, Kuen-Yun; Singco, Brenda; Lin, Chia-Her; Huang, Hsi-Ya

    2016-11-08

    In this study, we first demonstrated the effect of two types of metal-organic framework-polymer (MOF-polymer) monoliths on in-tube solid-phase microextraction (IT-SPME) of sulfonamides. Sulfonamides were successfully adsorbed onto MIL-101(Cr)-polymer but were difficult to elute due to these sulfonamides could interact via Lewis acid-base interaction with the presence of Cr(III) coordinatively unsaturated metal sites (CUS). Moreover, the cage-type topology of MIL-101(Cr) that could produce multiple pathways thus complicates the desorption of the test analytes from the sorbent. Contrastingly, MIL-53(Al)-polymer provided weaker Al(III) CUS, and its one-dimensional channel pore structure could provide an unhindered pathway for sulfonamides transfer during elution. After optimizing the IT-SPME condition such as MOF content, pH of sample matrix, column length, extraction flow rate, and elution volume, the calculated extraction recovery of sulfonamides in MIL-53(Al)-polymer as analyzed by microemulsion electrokinetic chromatography (MEEKC) were in the range of 40%-90% with relative standard deviations (RSDs) below 5% and a reusability of at least 30 times.

  19. A series of Zn-4f heterometallic coordination polymers and a zinc complex containing a flexible mixed donor dicarboxylate ligand.

    Science.gov (United States)

    Feng, Xun; Feng, Yu-Quan; Liu, Lang; Wang, Li-Ya; Song, Hong-Liang; Ng, Seik-Weng

    2013-06-01

    A new zinc compound, together with a corresponding series of Zn-4f heterometallic coordination polymers, namely, [Zn(H2PBDA)(PBDA)]n (1), {[Ln2(PBDA)2·2H2O] [Zn2(PBDA)2Cl2]}n [H2PBDA = 3-(pyridin-3-yl-oxy) benzene-1,2-dicarboxylic acid, and Ln = Pr(2), Nd(3), Eu(4), Gd(5), Dy(6), Ho(7), Er(8)] have been hydrothermally synthesized and characterized systematically. Polymers 2-8 feature two-dimensional (2D) 4,4 networks, containing the original 1D heterometallic double stranded chains composed of [Ln2Zn2(PBDA)2] entities. The extensive hydrogen bonding and π-π stacking interactions were observed to stabilize the extended architectures. The luminescence emission spectra of the polymers vary depending on the lanthanide(III) ion present. Informative magnetic susceptibility measurements show that the same carboxylate bridging fashion of the PBDA ligand results in the different magnetic properties occurring within the heterometallic coordination polymers. In addition, polymer 6 exhibits an interesting slow magnetic relaxation behavior at lower temperatures.

  20. A role based coordination model in agent systems

    Institute of Scientific and Technical Information of China (English)

    ZHANG Ya-ying; YOU Jin-yuan

    2005-01-01

    Coordination technology addresses the construction of open, flexible systems from active and independent software agents in concurrent and distributed systems. In most open distributed applications, multiple agents need interaction and communication to achieve their overall goal. Coordination technologies for the Internet typically are concerned with enabling interaction among agents and helping them cooperate with each other.At the same time, access control should also be considered to constrain interaction to make it harmless. Access control should be regarded as the security counterpart of coordination. At present, the combination of coordination and access control remains an open problem. Thus, we propose a role based coordination model with policy enforcement in agent application systems. In this model, coordination is combined with access control so as to fully characterize the interactions in agent systems. A set of agents interacting with each other for a common global system task constitutes a coordination group. Role based access control is applied in this model to prevent unauthorized accesses. Coordination policy is enforced in a distributed manner so that the model can be applied to the open distributed systems such as Intemet. An Internet online auction system is presented as a case study to illustrate the proposed coordination model and finally the performance analysis of the model is introduced.

  1. Synthesis, crystal structure and catalytic behavior of homo- and heteronuclear coordination polymers [M(tdc)(bpy)] (M2+ = Fe2+, Co2+, Zn2+, Cd2+; tdc2- = 2,5-thiophenedicarboxylate).

    Science.gov (United States)

    Kettner, Florian; Worch, Christian; Moellmer, Jens; Gläser, Roger; Staudt, Reiner; Krautscheid, Harald

    2013-08-05

    A series of isostructural 3D coordination polymers (3)∞[M(tdc)(bpy)] (M(2+) = Zn(2+), Cd(2+), Co(2+), Fe(2+); tdc(2-) = 2,5-thiophenedicarboxylate; bpy = 4,4'-bipyridine) was synthesized and characterized by X-ray diffraction, thermal analysis, and gas adsorption measurements. The materials show high thermal stability up to approximately 400 °C and a solvent induced phase transition. Single crystal X-ray structure determination was successfully performed for all compounds after the phase transition. In the zinc-based coordination polymer, various amounts of a second type of metal ions such as Co(2+) or Fe(2+) could be incorporated. Furthermore, the catalytic behavior of the homo- and heteronuclear 3D coordination polymers in an oxidation model reaction was investigated.

  2. Highly sensitive biosensors based on water-soluble conjugated polymers

    Institute of Scientific and Technical Information of China (English)

    XU Hui; WU Haiping; FAN Chunhai; LI Wenxin; ZHANG Zhizhou; HE Lin

    2004-01-01

    Conjugated, conductive polymers are a kind of important organic macromolecules, which has found applications in a variety of areas. The application of conjugated polymers in developing fluorescent biosensors represents the merge of polymer sciences and biological sciences. Conjugated polymers are very good light harvesters as well as fluorescent polymers, and they are also "molecular wires". Through elaborate designs, these important features, i.e. efficient light harvesting and electron/energy transfer, can be used as signal amplification in fluorescent biosensors. This might significantly improve the sensitivity of conjugated polymer-based biosensors. In this article, we reviewed the application of conjugated polymers, via either electron transfer or energy transfer, to detections of gene targets, antibodies or enzymes. We also reviewed recent efforts in conjugated polymer-based solid-state sensor designs as well as chip-based multiple target detection. Possible directions in this conjugated polymer-based biosensor area are also discussed.

  3. Single-ion-magnet behavior in a two-dimensional coordination polymer constructed from Co(II) nodes and a pyridylhydrazone derivative.

    Science.gov (United States)

    Liu, Xiangyu; Sun, Lin; Zhou, Huiliang; Cen, Peipei; Jin, Xiaoyong; Xie, Gang; Chen, Sanping; Hu, Qilin

    2015-09-21

    A novel two-dimensional (2D) coordination polymer, [Co(ppad)2]n (1), resulted from the assembly of Co(II) ions based on a versatile ligand termed N(3)-(3-pyridoyl)-3-pyridinecarboxamidrazone. Alternating/direct-current magnetic studies of compound 1 indicate that the spatially separated high-spin Co(II) ions act as single-ion magnets (SIMs). The present work represents the first case of a 2D Co(II)-based SIM composed of a monocomponent organic spacer.

  4. Integration of porous coordination polymers and gold nanorods into core-shell mesoscopic composites toward light-induced molecular release.

    Science.gov (United States)

    Khaletskaya, Kira; Reboul, Julien; Meilikhov, Mikhail; Nakahama, Masashi; Diring, Stéphane; Tsujimoto, Masahiko; Isoda, Seiji; Kim, Franklin; Kamei, Ken-ichiro; Fischer, Roland A; Kitagawa, Susumu; Furukawa, Shuhei

    2013-07-31

    Besides conventional approaches for regulating in-coming molecules for gas storage, separation, or molecular sensing, the control of molecular release from the pores is a prerequisite for extending the range of their application, such as drug delivery. Herein, we report the fabrication of a new porous coordination polymer (PCP)-based composite consisting of a gold nanorod (GNR) used as an optical switch and PCP crystals for controlled molecular release using light irradiation as an external trigger. The delicate core-shell structures of this new platform, composed of an individual GNR core and an aluminum-based PCP shell, were achieved by the selective deposition of an aluminum precursor onto the surface of GNR followed by the replication of the precursor into aluminum-based PCPs. The mesoscopic structure was characterized by electron microscopy, energy dispersive X-ray elemental mapping, and sorption experiments. Combination at the nanoscale of the high storage capacity of PCPs with the photothermal properties of GNRs resulted in the implementation of unique motion-induced molecular release, triggered by the highly efficient conversion of optical energy into heat that occurs when the GNRs are irradiated into their plasmon band. Temporal control of the molecular release was demonstrated with anthracene as a guest molecule and fluorescent probe by means of fluorescence spectroscopy.

  5. Hydrothermal Synthesis, Crystal Structure and Electrochemical Behavior of 2d Hybrid Coordination Polymer

    Science.gov (United States)

    Fan, Weiqiang; Zhu, Lin; Shi, Weidong; Chen, Fuxiao; Bai, Hongye; Song, Shuyan; Yan, Yongsheng

    2013-06-01

    A novel metal-organic coordination polymer [Cu(phen)(L)0.5(H2O)]n (H4L = (N,N‧-5,5‧-bis(isophthalic acid)-p-xylylenediamine, and phen = 1,10-phenanthroline) has been hydrothermally synthesized and characterized by elemental analysis, IR, TGA, and single-crystal X-ray diffraction. The crystallographic data show that the title compound crystallizes in monoclinic space group P21/n with a = 10.682(2), b = 15.682(3), c = 11.909(2) Å, β = 91.39(3)°, V = 1994.3(7) Å3, C24H17CuN3O5, Mr = 490.95, Dc = 1.635 g/cm3, F(000) = 1004, Z = 4, μ(MoKα) = 1.141 mm-1, the final R = 0.0418 and wR = 0.0983 for 3578 observed reflections (I > 2σ(I)). The structural analyses reveal that the title compound exhibits shows a 2D layer structure, which are further linked by hydrogen bonding interactions to form a three-dimensional supramolecular network. In addition, the thermal stability and electrochemical behavior of title compound has been studied. CCDC: 900413.

  6. Coordination chemistry of mercury(ii) with 2-pyridylnitrones: monomers to polymers.

    Science.gov (United States)

    Azizpoor Fard, Mahmood; Behnia, Ava; Puddephatt, Richard J

    2017-03-14

    The coordination chemistry of mercury(ii) halides, HgX2, X = Cl, Br, I, with N-methyl-α-(2-pyridyl)nitrone, L1, and N-t-butyl-α-(2-pyridyl)nitrone, L2, is reported. The structures of 1 : 1 complexes [HgX2L], X = Cl, L = L1; X = Br, L = L2, 2 : 1 complexes [(HgX2)2L], X = Br or I, L = L1; X = Cl or I, L = L2, and a unique compound [(HgBr2)5(L2)3] have been determined. In the 1 : 1 and 1 : 2 complexes, the ligand L1 adopts the anti conformation, and is either monodentate or bridging, while the ligand L2 adopts the syn conformation and acts as a chelate ligand. In the compound [(HgBr2)5(L2)3] the ligand L2 is present in both syn-chelate and anti-bridging bonding modes. Secondary intermolecular bonding, involving OHg or XHg interactions, can lead to association of the molecular compounds to form polymers of several kinds. In solution, the complexes are labile and the crystalline products do not necessarily reflect the reaction stoichiometry.

  7. Spectroscopic properties and the catalytic activity of new organo-lead supramolecular coordination polymer containing quinoxaline

    Science.gov (United States)

    Etaiw, Safaa El-din H.; Abdou, Safaa N.

    2015-01-01

    The 3D-supramolecular coordination polymer (SCP) 3∞[ Cu2(CN)3(Me3Pb)(qox)], 1, as the first example of the CuCN SCP containing the (Me3Pb) fragment, was explored to investigate its catalytic and photo-catalytic activities. The structure of 1 contains two chemically identical but crystallographically different [Cu2(CN)3ṡMe3Pbṡqox]2 units with four Cu(I) sites assuming distorted TP-3 geometry. Two non-linear chains of equal abundance are formed producing corrugated parallel chains which are connected laterally by quinoxaline creating 2D-layers which are arranged parallel in an (AB⋯AB⋯AB)n fashion forming 3D-network. IR, mass, electronic absorption and fluorescence spectra are also investigated. The SCP 1 is diamagnetic and exhibits good catalytic and photo-catalytic activities for the degradation of methylene blue (MB). The reaction is first order with respect to MB dye. The irradiation of the reaction with UV-light enhanced the rate of MB mineralization. The efficiency of recycled the 1 and the mechanism of degradation of MB dye were investigated.

  8. Natural gas purification using a porous coordination polymer with water and chemical stability.

    Science.gov (United States)

    Duan, Jingui; Jin, Wanqin; Krishna, Rajamani

    2015-05-04

    Porous coordination polymers (PCPs), constructed by bridging the metals or clusters and organic linkers, can provide a functional pore environment for gas storage and separation. But the rational design for identifying PCPs with high efficiency and low energy cost remains a challenge. Here, we demonstrate a new PCP, [(Cu4Cl)(BTBA)8·(CH3)2NH2)·(H2O)12]·xGuest (PCP-33⊃guest), which shows high potential for purification of natural gas, separation of C2H2/CO2 mixtures, and selective removal of C2H2 from C2H2/C2H4 mixtures at ambient temperature. The lower binding energy of the framework toward these light hydrocarbons indicates the reduced net costs for material regeneration, and meanwhile, the good water and chemical stability of it, in particular at pH = 2 and 60 °C, shows high potential usage under some harsh conditions. In addition, the adsorption process and effective site for separation was unravelled by in situ infrared spectroscopy studies.

  9. 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.

  10. 40 CFR 721.10036 - Acetaldehyde based polymer (generic).

    Science.gov (United States)

    2010-07-01

    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Acetaldehyde based polymer (generic... Specific Chemical Substances § 721.10036 Acetaldehyde based polymer (generic). (a) Chemical substance and... based polymer (PMN P-02-406) is subject to reporting under this section for the significant new uses...

  11. Protein-based supramolecular polymers: progress and prospect.

    Science.gov (United States)

    Luo, Quan; Dong, Zeyuan; Hou, Chunxi; Liu, Junqiu

    2014-09-11

    Proteins are naturally evolved macromolecules with highly sophisticated structures and diverse properties. The design and controlled self-assembly of proteins into polymeric architectures via supramolecular interactions offers unique advantages in understanding the spontaneously self-organisational process and fabrication of various bioactive materials. This feature article highlights recent advances and future trends in supramolecular polymers that are directly assembled from the building blocks of proteins. Non-covalent interactions capable of inducing polymerization include aromatic π-π stacking, host-guest interactions, metal coordination, and interprotein interactions combined with site-selective protein modification to explore the dynamic and specific unidirectional aggregation behaviours among protein units. We also discuss some extended supramolecular protein polymers achieved by rational design and fine-tuning the protein-protein interactions, which may help to inspire future design of more complicated polymeric protein assemblies. The protein-based supramolecular polymer system provides a versatile platform for functionalization and thereby shows great potential in the development of novel biomaterials with controlled structures and properties.

  12. Crystal structure of a helical silver(I coordination polymer based on an unsymmetrical dipyridyl ligand: catena-poly[[silver(I-μ-N-(pyridin-4-ylmethylpyridine-3-amine-κ2N:N′] tetrafluoridoborate methanol hemisolvate

    Directory of Open Access Journals (Sweden)

    Suk-Hee Moon

    2015-11-01

    Full Text Available The asymmetric unit of the title compound, {[AgL]·BF4·0.5CH3OH}n, L = N-(pyridin-4-ylmethylpyridine-3-amine, C11H11N3, contains one AgI ion, one ligand L, one tetrafluoridoborate anion disordered over two orientations in a 0.669 (13:0.331 (13 ratio and one half of a methanol solvent molecule situated on an inversion center. Each AgI ion is coordinated by two N atoms from two L ligands in a distorted linear geometry [N—Ag—N = 174.70 (19°]. Each L ligand bridges two AgI ions, thus forming polymeric helical chains propagating in [010]. In the crystal, Ag...Ag [3.3369 (10 Å] and π–π interactions between the aromatic rings [centroid-to-centroid distance = 3.676 (4 Å] link these chains into layers parallel to (10-1. Ag...F and weak N(C—H...F interactions further consolidate the crystal packing.

  13. Ultrasonic-assisted synthesis and structural characterization of two new nano-structured Hg(II) coordination polymers.

    Science.gov (United States)

    Ghasempour, Hosein; Azhdari Tehrani, Alireza; Morsali, Ali

    2015-11-01

    Two new Hg(II) coordination polymers containing N,N'-Bis-pyridin-3-ylmethylene-naphtalene-1,5-diamine ligand were synthesized by conventional and sonochemical methods, characterized by spectroscopic techniques (FT-IR and elemental analysis), and their X-ray crystallographic structures were determined. The crystal packing and supramolecular features of these coordination polymers were studied using geometrical analysis and Hirshfeld surface analysis. The crystal structure analysis revealed that H⋯H contacts, C-H⋯π and C-H⋯X (X = Cl for 1 and X = Br for 2) hydrogen bonding interactions are strong enough to govern the supramolecular architecture. The BFDH analysis helps us to compare the predicted morphology to that obtained under ultrasonication. This study may provide further insight into discovering the role of weak intermolecular interactions in the context of nano-supramolecular assembly.

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

    Science.gov (United States)

    Perez, Emilie; Andre, Marie-Laure; Navarro Amador, Ricardo; Hyvrard, François; Borrini, Julien; Carboni, Michaël; Meyer, Daniel

    2016-11-05

    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. Copyright © 2016 Elsevier B.V. All rights reserved.

  15. Synthesis, crystal structure and luminescent properties of one coordination polymer of cadmium(II) with mixed thiocyanate and hexamethylenetetramine ligands.

    Science.gov (United States)

    Bai, Yan; Shang, Wei-Li; Dang, Dong-Bin; Sun, Ji-De; Gao, Hui

    2009-03-01

    A novel Cd(II) coordination polymer [Cd(SCN)(2)(hmt)(1/2)(H(2)O)](2).H(2)O (hmt=hexamethylenetetramine) has been synthesized and characterized by IR, elemental analysis, TG technique and X-ray crystallography. Cd(II) atom has an distorted octahedral environment with an N(3)S(2)O donor set. Every six Cd(II) centers are linked by hmt and thiocyanato bridges to form a planar 2D coordination polymer containing hexagonal metallocyclic rings [Cd(6)(SCN)(8)(hmt)(2)]. A 2D layer structure is held together with its neighboring ones via a set of hydrogen-bonding interactions to form a 3D supramolecular structure. The luminescent properties of the title complex in the solid state were investigated.

  16. Synthesis and photo-/electro-catalytic properties of a 3D POMOF material based on an interpenetrated copper coordination polymer linked by in situ dual ligands and Dawson-type phosphotungstates.

    Science.gov (United States)

    Fan, Ling-Yu; Yu, Kai; Lv, Jing-Hua; Zhang, He; Su, Zhan-Hua; Wang, Lu; Wang, Chun-Mei; Zhou, Bai-Bin

    2017-08-08

    A novel 3D polyoxometalate metal organic framework (POMOF), [{CuCu (H2O)5(pzc)10(pz)6}{P2W18O62}2]·4H2O (1) (Hpzc = pyrazine-2-carboxylic acid, pz = pyrazine) has been hydrothermally synthesized and characterized by IR, TG, XRD, UV-vis and elemental analyses. In compound 1, the pzc and pz ligands are generated through in situ transformation from pyrazine-2,3-dicarboxylic acid (pzdc) to remove one or two CO2 molecules. The ligands with four coordination modes connect nine crystallographically independent Cu atoms to form a super-big circle unit. Each ring unit is connected to the adjacent six rings via an edge-sharing way to form a 2-D Cu/pz/pzc MOF layer, which is further extended along two spatial directions by two kinds of insert modes to generate an interpenetrating and staggered 3-D metal organic network. The {P2W18} clusters as nine-node inorganic guest molecules are grafted on the Cu/pz/pzc framework forming a complex 3D POMOF with a new topology {4·6·8(3)·10}2 {4·6·8}2 {4·6(2)·8(2)·10}2{4·6(3)·8(2)}2{4·8(5)}2{4(2)·6(2)·8(2)}2{4(2)·6(3)·8}{4(3)·6(7)·8(13)·10(10)·12(3)}2 {4}6{6·8(2)}2{6(2)·8}2 {6(4)·8·10}{6}2{8}4. Additionally, compound 1 exhibits good electrocatalytic activity for the reduction of H2O2 and effective photocatalytic degradation ability for three azo dyes under UV irradiation.

  17. 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

  18. Synthesis, spectral, X-ray diffraction and thermal studies of new ZnII-pyrazine coordination polymers

    Science.gov (United States)

    Marandi, Farzin

    2014-02-01

    Two new zinc(II) coordination polymers with a β-diketone and N-donor ancillary ligands, [Zn(pyz)(ttfa)2]n (1) and [Zn(pyz)(btfa)2]n (2), (Httfa = 2-thenoyltrifluoroacetone, Hbtfa = benzoyltrifluoroacetone and pyz = pyrazine), have been prepared and characterized by elemental analysis, IR, 1H NMR and 13C NMR spectroscopy, and studied by thermal gravimetric analysis as well as single crystal X-ray diffraction. The crystal and molecular structures of 1 and 2 have been solved by X-ray diffraction and they turned out to be one-dimensional polymers with linear dispositions of the metal atoms. These one-dimensional polymers are further connected to form a 3D supramolecular network by CH⋯π (only in 1), CH⋯F, π-π and interesting H⋯H (only in 2) interactions.

  19. In-Situ Composition and Luminescence of Europium and Terbium Coordination Polymers/PEMA Hybrid Thick Films

    Institute of Scientific and Technical Information of China (English)

    YAN Bing; WANG Qianming

    2005-01-01

    Europium and terbium coordination polymers of pyridine- 3-carboxylic acid were in-situ composed with ethyl methacrylate ( EMA ). With the polymerization of EMA monomer and the formation of europium and terbium coordination polymers of pyridine- 3-carboxylic acid, the transparent hybrid thick films composed of [Eu( NIC)3 ]n ( [ Tb( NIC)3 ]n ) and poly ethyl methacrylate ( PEMA ) have been prepared. The luminescence properties and energy transfer of these polymeric composites were studied with absorption spectra, fluorescent excitation and emission spectra in detail. All the hybrid thick films composed of terbium coordination polymer show the characteristic strong green emission of terbium ions, which implies the same energy transfer mechanism as the pure complex and the hybrid composite film is a suitable substrate for the luminescence of terbium ions. In the range of composing concentration of luminescent species (0.01,0.025,0.05,0.1 mmol/15 mL EMA ) , emission intensities increase with the increasing of corresponding composing concentration and the concentration quenching effect does not take place.

  20. The new one-dimensional coordination polymer catena-poly[[diaquasodium(I)]-μ-oxalato-[diaquairon(III)]-μ-oxalato].

    Science.gov (United States)

    Benhacine, Mohamed Al Amine; Hamadène, Malika; Bouacida, Sofiane; Merazig, Hocine

    2016-03-01

    The oxalate dianion is one of the most studied ligands and is capable of bridging two or more metal centres and creating inorganic polymers based on the assembly of metal polyhedra with a wide variety of one-, two- or three-dimensional extended structures. Yellow single crystals of a new mixed-metal oxalate, namely catena-poly[[diaquasodium(I)]-μ-oxalato-κ(4)O(1),O(2):O(1'),O(2')-[diaquairon(III)]-μ-oxalato-κ(4)O(1),O(2):O(1'),O(2')], [NaFe(C2O4)2(H2O)4]n, have been synthesized and the crystal structure elucidated by X-ray diffraction analysis. The compound crystallizes in the noncentrosymmetric space group I41 (Z = 4). The asymmetric unit contains one Na(I) and one Fe(III) atom lying on a fourfold symmetry axis, one μ2-bridging oxalate ligand and two aqua ligands. Each metal atom is surrounded by two chelating oxalate ligands and two equivalent water molecules. The structure consists of infinite one-dimensional chains of alternating FeO4(H2OW1)2 and NaO4(H2OW2)2 octahedra, bridged by oxalate ligands, parallel to the [100] and [010] directions, respectively. Because of the cis configuration and the μ2-coordination mode of the oxalate ligands, the chains run in a zigzag manner. This arrangement facilitates the formation of hydrogen bonds between neighbouring chains involving the H2O and oxalate ligands, leading to a two-dimensional framework. The structure of this new one-dimensional coordination polymer is shown to be unique among the A(I)M(III)(C2O4)2(H2O)n series. In addition, the absorption bands in the IR and UV-Visible regions and their assignments are in good agreement with the local symmetry of the oxalate ligand and the irregular environment of iron(III). The final product of the thermal decomposition of this precursor is the well-known ternary oxide NaFeO2.

  1. Stereochemically Distinct Cyclotetrasiloxanes Containing 3-Pyridyl Moieties and Their Functional Coordination Polymers.

    Science.gov (United States)

    Deshmukh, Mahesh S; Vijayakanth, Thangavel; Boomishankar, Ramamoorthy

    2016-03-21

    Synthesis of new cyclotetrasiloxane scaffolds containing peripherally functionalized 3-pyridyl moieties, [MeSiO(CH═CH(3)Py)]4 (L(1)) and [MeSiO(CH2CH2(3)Py)]4 (L(2)), and their reactivity studies with certain d(10) metal ions are reported. The ligand L(1) is obtained by the Heck-coupling reaction of tetramethyl tetravinyl tetrasiloxane (D4(vi)) and 3-bromopyridine in the presence of the Pd(0) catalysts. The as-synthesized ligand L(1) shows the presence of three stereoisomers, cis-trans-cis (L(1A)), cis-cis-trans (L(1B)), and all-trans (L(1C)), which are quantitatively separated by column chromatography. Subsequent reduction of L(1A), L(1B), and L(1C) with triethylsilane in the presence of catalytic amounts of Pd/C leads to the formation of the ligands L(2A), L(2B), and L(2C) with retention of stereochemistry due to the precursor moieties. Treatment of ZnI2 with L(1A) gives a one-dimensional coordination framework [(L(1A))4(ZnI2)2]∞, 1. These 1D-chains are further connected by π-π stacking interactions between the pyridyl groups of the adjacent chains leading to the formation of a three-dimensional network with the topology of a PtS net. The reaction of silver nitrate with ligand L(1B) gives a chain like one-dimensional cationic coordination polymer {[(L(1B))4Ag2]·2NO3·H2O·CH3OH }∞, 2, consisting of two different kinds of 32-membered macrocycles. Treatment of the all-trans ligand L(2C) with copper(I) iodide salt results in the formation of a cubane-type Cu4I4 cluster MOF [(L(2C))4Cu4I4]∞, 3, in a two-dimensional 4-connected uninodal sql/Shubnikov tetragonal plane net topology represented by the Schläfli symbol {4(4).6(2)}. This MOF displays a thermochromic luminescence behavior due to Cu4I4 clusters showing an orange emission at 298 K and a blue emission at 77 K.

  2. Quantification of Aromaticity Based on Interaction Coordinates: A New Proposal.

    Science.gov (United States)

    Pandey, Sarvesh Kumar; Manogaran, Dhivya; Manogaran, Sadasivam; Schaefer, Henry F

    2016-05-12

    Attempts to establish degrees of aromaticity in molecules are legion. In the present study, we begin with a fictitious fragment arising from only those atoms contributing to the aromatic ring and having a force field projected from the original system. For example, in benzene, we adopt a fictitious C6 fragment with a force field projected from the full benzene force field. When one bond or angle is stretched and kept fixed, followed by a partial optimization for all other internal coordinates, structures change from their respective equilibria. These changes are the responses of all other internal coordinates for constraining the bond or angle by unit displacements and relaxing the forces on all other internal coordinates. The "interaction coordinate" derived from the redundant internal coordinate compliance constants measures how a bond (its electron density) responds for constrained optimization when another bond or angle is stretched by a specified unit (its electron density is perturbed by a finite amount). The sum of interaction coordinates (responses) of all bonded neighbors for all internal coordinates of the fictitious fragment is a measure of the strength of the σ and π electron interactions leading to aromatic stability. This sum, based on interaction coordinates, appears to be successful as an aromaticity index for a range of chemical systems. Since the concept involves analyzing a fragment rather than the whole molecule, this idea is more general and is likely to lead to new insights.

  3. Geometric deviation modeling by kinematic matrix based on Lagrangian coordinate

    Science.gov (United States)

    Liu, Weidong; Hu, Yueming; Liu, Yu; Dai, Wanyi

    2015-09-01

    Typical representation of dimension and geometric accuracy is limited to the self-representation of dimension and geometric deviation based on geometry variation thinking, yet the interactivity affection of geometric variation and gesture variation of multi-rigid body is not included. In this paper, a kinematic matrix model based on Lagrangian coordinate is introduced, with the purpose of unified model for geometric variation and gesture variation and their interactive and integrated analysis. Kinematic model with joint, local base and movable base is built. The ideal feature of functional geometry is treated as the base body; the fitting feature of functional geometry is treated as the adjacent movable body; the local base of the kinematic model is fixed onto the ideal geometry, and the movable base of the kinematic model is fixed onto the fitting geometry. Furthermore, the geometric deviation is treated as relative location or rotation variation between the movable base and the local base, and it's expressed by the Lagrangian coordinate. Moreover, kinematic matrix based on Lagrangian coordinate for different types of geometry tolerance zones is constructed, and total freedom for each kinematic model is discussed. Finally, the Lagrangian coordinate library, kinematic matrix library for geometric deviation modeling is illustrated, and an example of block and piston fits is introduced. Dimension and geometric tolerances of the shaft and hole fitting feature are constructed by kinematic matrix and Lagrangian coordinate, and the results indicate that the proposed kinematic matrix is capable and robust in dimension and geometric tolerances modeling.

  4. Synthesis of nanostructured materials by using metal-cyanide coordination polymers and their lithium storage properties.

    Science.gov (United States)

    Nie, Ping; Shen, Laifa; Luo, Haifeng; Li, Hongsen; Xu, Guiyin; Zhang, Xiaogang

    2013-11-21

    Herein, we demonstrate a novel and simple two-step process for preparing LiCoO2 nanocrystals by using a Prussian blue analogue Co3[Co(CN)6]2 as a precursor. The resultant LiCoO2 nanoparticles possess single crystalline nature and good uniformity with an average size of ca. 360 nm. The unique nanostructure of LiCoO2 provides relatively shorter Li(+) diffusion pathways, thus facilitating the fast kinetics of electrochemical reactions. As a consequence, high reversible capacity, excellent cycling stability and rate capability are achieved with these nanocrystals as cathodes for lithium storage. The LiCoO2 nanocrystals deliver specific capacities of 154.5, 135.8, 119, and 100.3 mA h g(-1) at 0.2, 0.4, 1, and 2 C rates, respectively. Even at a high current density of 4 C, a reversible capacity of 87 mA h g(-1) could be maintained. Importantly, a capacity retention of 83.4% after 100 cycles is achieved at a constant discharge rate of 1 C. Furthermore, owing to facile control of the morphology and size of Prussian blue analogues by varying process parameters, as well as the tailored design of multi-component metal-cyanide hybrid coordination polymers, with which we have successfully prepared porous Fe2O3@NixCo3-xO4 nanocubes, one of the potential anode materials for lithium-ion batteries, such a simple and scalable approach could also be applied to the synthesis of other nanomaterials for energy storage devices.

  5. Syntheses,Structures and Properties of Lanthanide Coordination Polymers Constructed from Mixed Acid

    Institute of Scientific and Technical Information of China (English)

    孙长艳; 吕琼; 张慧燕; 李文军; 常志东; 郑向军

    2012-01-01

    Two new coordination polymers,[Ln(oba)(ox)0.5(H2O)2]n(Ln = Ho(1),Eu(2);H2oba = 4,4?-oxybis(benzoic acid),H2ox = oxalic acid) have been synthesized under hydrothermal conditions.According to single-crystal X-ray diffraction analyses,complex 1 crystallizes in the monoclinic system,space group P21/c with a = 13.783(2),b =10.0120(15),c = 12.1974(18) ,β = 105.217(2)°,V = 1624.2(4) 3,C15H12O9Ho,Mr = 501.18,Z = 4,Dc = 2.050 g/cm3,F(000) = 964,μ = 4.919 mm-1,λ(MoKα) = 0.71073 ?,GOOF = 1.124,the final R = 0.0239 and wR = 0.0570 for 3310 independent reflections with Rint = 0.0298.Complexes 2 and 1 are isostructural.Oba and ox ligands bridge the Ln(III) ions into 2D layers with(4,4) topology,which are further interlinked into a 3D supramolecular network by hydrogen bonds.TG curves of the two complexes are studied to examine their thermal stabilities.Additionally,complex 2 shows red fluorescence in the solid state at room temperature.

  6. Thermodynamically metastable thiocyanato coordination polymer that shows slow relaxations of the magnetization.

    Science.gov (United States)

    Werner, Julia; Rams, Michał; Tomkowicz, Zbigniew; Runčevski, Tomče; Dinnebier, Robert E; Suckert, Stefan; Näther, Christian

    2015-03-16

    Reaction of cobalt thiocyanate with 4-acetylpyridine leads to the formation of [Co(NCS)2(4-acetylpyridine)2]n (3/I). In its crystal structure the Co cations are connected by pairs of μ-1,3-bridging thiocyanato ligands into dimers that are further connected into layers by single anionic ligands. DTA-TG measurements of Co(NCS)2(4-acetyl-pyridine)4 (1) led to the formation of 3/I. In contrast, when the hydrate Co(NCS)2(4-acetyl-pyridine)2(H2O)2 (2) is decomposed, a mixture of 3/I and a thermodynamically metastable form 3/II is obtained. Further investigations reveal that thermal annealing of 2 leads to the formation of 3/II, that contains only traces of the stable form 3/I. DSC and temperature dependent X-ray powder diffraction (XRPD) measurements prove that 3/II transforms into 3/I on heating. The crystal structure of 3/II was determined ab initio from XRPD data. In its crystal structure the Co cations are linked by pairs of bridging thiocyanato anions into a 1D coordination polymer, and thus, 3/II is an isomer of 3/I. Magnetic measurements disclose that the stable form 3/I only shows paramagnetism without any magnetic anomaly down to 2 K. In contrast, the metastable form 3/II shows ferromagnetic behavior. The phase transition into ordered state at Tc = 3.8 K was confirmed by specific heat measurements. Alternating current susceptibility measurements show frequency dependent maxima in χ' and χ″, which is indicative for a slow relaxation of the magnetization.

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

    Science.gov (United States)

    Wu, Yu; Lu, Lu; Feng, Jianshen; Li, Yulong; Sun, Yanchun; Ma, Aiqing

    2017-01-01

    The reaction of Cu(NO3)2·3H2O/Ni(NO3)2·6H2O with 4‧-(4-(3,5-dicarboxylphenoxy)phenyl)-4,2‧:6‧,4‧‧-terpyridine (H2dbp) gave [Cu0.5(Hdbp)]n (1) and [Ni(dbp)(H2O)]n (2), while the reactions of Co(NO3)2·6H2O with H2dbp in the presence of 4,4‧-bipy and 2,2‧-bpy generated [Co(dbp)(4,4‧-bipy)]n (3) and {[Co(dbp)(2,2‧-bipy)]n·H2O} (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 (4.620.83)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.

  8. Syntheses, Structures, and Properties of Five Coordination Polymers Involving Phthalic Acid

    Institute of Scientific and Technical Information of China (English)

    WU Li-li; HE Rong; WEI Zhen; SONG Hui-hua

    2011-01-01

    Five new coordination polymers Cu(phen)(H2O)(phth)·CH3OH(1),[Cu(2,2'-bipy)(H2O)](phth).3.5H2O(2),Zn(phen)(phth)(H2O).1.125H2O(3) and [M(4,4'-bipy)(H2O)2](phth).2H2O[M=Zn(4),Mn(5)](H2phth=phthalic acid,bipy=bipyridine,phen=l,10-phenanthroline) have been synthesized from the amino acid derivatives(phthalyl-I-valine,H2L) and structurally characterized.H2L was hydrolyzed into phth2- group during the reaction,but the strucure feature was different from that of the complex directly synthesized from H2phth in the reported literature,revealing that H2L played an important role in composing the novel compounds.Compounds 1,2 and 3 are all 1D chains,but the differences are that compound 1 is further hydrogen-bonded into 2D networks,and compound 2 is further extended into 3D supramolecular network through π-π stacking and hydrogen-bonding interactions.However,compound 3 is a 1D helix chain structure and further links into 2D networks through π-π stacking.Compounds 4 and 5 are isostructural and exhibit the same 2D layers,which are further connected by hydrogen-bonding interactions to form 3D supramolecular network.Antiferromagnetic superexchange was observed for compounds 1,2 and 5.

  9. Study of proton conductivity of a 2D flexible MOF and a 1D coordination polymer at higher temperature.

    Science.gov (United States)

    Sanda, Suresh; Biswas, Soumava; Konar, Sanjit

    2015-02-16

    We report the proton conduction properties of a 2D flexible MOF and a 1D coordination polymer having the molecular formulas {[Zn(C10H2O8)0.5(C10S2N2H8)]·5H2O]}n (1) and {[Zn(C10H2O8)0.5(C10S2N2H8)]·2H2O]}n (2), respectively. Compounds 1 and 2 show high conductivity values of 2.55 × 10(-7) and 4.39 × 10(-4) S cm(-1) at 80 °C and 95% RH. The conductivity value of compound 1 is in the range of those for previously reported flexible MOFs, and compound 2 shows the highest proton conductivity among the carboxylate-based 1D CPs. The dimensionality and the internal hydrogen bonding connectivity play a vital role in the resultant conductivity. Variable-temperature experiments of both compounds at high humidity reveal that the conductivity values increase with increasing temperature, whereas the variable humidity studies signify the influence of relative humidity on high-temperature proton conductivity. The time-dependent measurements for both compounds demonstrate their ability to retain conductivity up to 10 h.

  10. Coordination polymer derived cobalt embedded in nitrogen-doped carbon nanotubes for efficient electrocatalysis of oxygen evolution reaction

    Science.gov (United States)

    Cong, Jingkun; Li, Changqing; Zhao, Tao; Wu, Jin; Zhang, Rui; Ren, Wenjing; Wang, Shunli; Gao, Junkuo; Liu, Yi; Yao, Juming

    2017-09-01

    In this paper, we reported the fabrication of Co-embedded nitrogen-doped carbon nanotube (Co-NCNT) by using Co-melamine coordination polymer (CP) as precursor. The sample was well characterized via SEM, TEM, XRD, XPS and BET methods. The Co-NCNT shows excellent and stable catalytic performance for OER. The overpotential of Co-NCNT at 10 mA cm-2 is 370 mV (vs RHE). The current density of Co-NCNT could reach 100 mA cm-2 at overpotential of 520 mV, which showed much better performance than RuO2, while the largest current density of RuO2 could reach is only 44 mA cm-2. The Tafel slope of Co-NCNT is 56 mV dec-1, which is smaller than that of commercial RuO2 (58 mV dec-1). The results indicate that metal-melamine based CPs or MOFs can be promising precursors for the preparation of efficient metal-embedded nitrogen-doped carbon materials for electrocatalysis.

  11. Highly selective and sensitive detection of metal ions and nitroaromatic compounds by an anionic europium(iii) coordination polymer.

    Science.gov (United States)

    Feyisa Bogale, Raji; Ye, Junwei; Sun, Yuan; Sun, Tongxin; Zhang, Siqi; Rauf, Abdul; Hang, Cheng; Tian, Peng; Ning, Guiling

    2016-07-01

    A luminescent Eu(iii)-based coordination polymer, {[Eu(H2O)5(BTEC)][H(C5H6N2)]·3H2O} () has been synthesized under hydrothermal conditions using 1,2,4,5-benzenetetracarboxylic acid (H4BTEC) as a linker. Compound possesses an anionic zig-zag chain constructed from the BTEC ligands and [EuO4(H2O)5] nodes. The protonated 4-aminopyridine groups as guests are located between chains. exhibits the characteristic sharp emission bands of Eu(3+) at 578, 593, 615, 652 and 693 nm upon excitation at 290 nm. The strong emission of could be quenched effectively by trace amounts of Fe(3+) ions even in the presence of other metal ions including Al(3+), Ca(2+), Cd(2+), Co(2+), Cr(3+), Cu(2+), Fe(2+), K(+), Mg(2+), Mn(2+), Pd(2+) and Zn(2+). Similarly, also exhibits superior selectivity and sensitivity towards 4-nitrophenol (4-NP) compared with other competing interfering analytes, such as 2,4,6-trinitrophenol, 2,6-dinitrotolune, 4-nitrotoluene, nitrobenzene, 1,3-dinitrobenzene, o-xylene, nitromethane, nitropropane, phenol, 4-bromophenol and bromobenzene, through a fluorescence quenching mechanism. The possible fluorescence quenching mechanisms are discussed. Moreover, could be used as a visual fluorescent test paper for selectively detecting trace amounts of Fe(3+) and 4-NP.

  12. 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

    2015-01-01

    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 Zn(2+) 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.

  13. New oxalate-propagated layered Mn2+/Fe2+-4,4‧-sulfoyldiphthalhydrazidate coordination polymers

    Science.gov (United States)

    Jin, Juan; Yan, Wen-Fu; Yang, Qing-Feng; Yu, Xiao-Yang; Sun, Li-Xiang; Xu, Ji-Qing; Chen, Zi-Ao; Li, Chuan-Zhao

    2017-01-01

    Based on the hydrothermal in situ acylation reaction of 4,4‧-sulfoyldiphthalic anhydride (sdpha) with N2H4ṡH2O, two isostructural oxalate-propagated Mn2+/Fe2+-diacylhydrazidate coordination polymers, [M3(sdpth)2(ox)(H2O)2]ṡ2H2O (M2+ = Mn2+1, Fe2+2; sdpth = 4,4‧-sulfoyldiphthalhydrazidate, 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 both compounds, ox ligands act as the second linkers, extending the metal-diacylhydrazidate chains into a 2-D layer. Via Nsbnd H⋯O interactions, compounds 1 and 2 self-assemble into 3-D supramolecular networks. The magnetic analyses indicate that there are antiferromagnetic interactions between magnetic centers in compounds 1 and 2. The photoluminescence properties of compounds 1 and 2 were also investigated in an aqueous solution.

  14. Synthetic Architecture of MgO/C Nanocomposite from Hierarchical-Structured Coordination Polymer toward Enhanced CO2 Capture.

    Science.gov (United States)

    Li, Ping; Liu, Wen; Dennis, John S; Zeng, Hua Chun

    2017-03-22

    Highly efficient, durable, and earth-abundant solid sorbents are of paramount importance for practical carbon capture, storage, and utilization. Here, we report a novel and facile two-step strategy to synthesize a group of hierarchically structured porous MgO/C nanocomposites using flowerlike Mg-containing coordination polymer as a precursor. The new nanocomposites exhibit superb CO2 capture performance with sorption capacity up to 30.9 wt % (at 27 °C, 1 bar CO2), fast sorption kinetics, and long cycling life. Importantly, the achieved capacity is >14 times higher than that of commercial MgO, and favorably exceeds the highest value recorded to date for MgO-based sorbents under similar operating conditions. On the basis of the morphological and textural property analysis, together with CO2 sorption mechanism study using CO2-TPD and DRIFT techniques, the outstanding performance in CO2 uptake originates from unique features of this type of sorbent materials, which include hierarchical architecture, porous building blocks of nanosheets, high specific surface area (ca. 300 m(2)/g), evenly dispersed MgO nanocrystallites (ca. 3 nm) providing abundant active sites, and the in situ generated carbon matrix that acts as a stabilizer to prevent the growth and agglomeration of MgO crystallites. The nanocomposite system developed in this work shows good potential for future low-cost CO2 abatement and utilization.

  15. Synthesis and Crystal Structure of a One-Dimensional Coordination Polymer Containing Unusual Na2Cu2 Tetrametallacyclic Units

    Institute of Scientific and Technical Information of China (English)

    GAO,En-Qing(高恩庆); SUN,Hai-Ying(孙海英); LIAO,Dai-Zheng(廖代正); JIANG,Zong-Hui(姜宗慧); YAN Shi-Ping(阎世平)

    2002-01-01

    A unique coordination polymer, {[CuLNa(ClO4)]@ H2O}n (1), was isolated from the solution containing sodium perchlorate and the neutral macrocyclic oxamidocopper(Ⅱ) complex [CuL] (H2L = 2,3-dioxo-5,6:13,14-dibenzo-7,12-bis(ethoxycarbonyl)-1, 4, 8, 11-tetraazacyclotetradeca-7, 11-diene). The complex is composed of [Na2Cu2] tetrametallavycles bridged by perchlorate ions to form infinite one-dimensional chains which are stacked via π-π interactions and weak coordination bonds to result in a two-dimensional supramolecular network. The perclorate ions were found to coordinate to sodium atoms in the unusual bridging chelating tridentate mode of μ2-(O:O′,O").

  16. Polymer gratings based on photopolymerization for low-order distributed feedback polymer lasers

    Institute of Scientific and Technical Information of China (English)

    Xuanke Zhao; Qingwu Zhao; Qinghua Zhang

    2008-01-01

    Novel polymer distributed feedback(DFB)gratings are fabricated based on photopolymerization to reduce lasing threshold of polymer lasers.A photopolymer formulation sensitive to 355-nm ultraviolet(UV)light is proposed for the fabrication of polymer gratings and it can be used to form polymer films by spin-coating process.A very low surface-relief depth ranging from 12.5 to about 1.0 nm has been demonstrated with a refractive-index modulation of about 0.012.The experimental results indicate that such polymer gratings have promising potentials for the fabrication of low-order DFB organic semiconductor lasers.

  17. Assembly of 4-, 6- and 8-connected Cd(II) pseudo-polymorphic coordination polymers: Synthesis, solvent-dependent structural variation and properties

    Science.gov (United States)

    Li, Zhao-Hao; Xue, Li-Ping; Miao, Shao-Bin; Zhao, Bang-Tun

    2016-08-01

    The reaction of Cd(NO3)2·4H2O, 2,5-thiophenedicarboxylic acid (H2tdc) and 1,2-bis(imidazol-1‧-yl)methane (bimm) by modulating solvent systems yielded three highly connected pseudo-polymorphic coordination polymers based on different dinuclear [Cd2(CO2)2] subunits bridged by carboxylate groups. Single crystal structural analyses reveal structural variation from 4-connected 2D sql layer, 6-connected 2-fold interpenetrated 3D pcu to 8-connected 3D bcu-type network in compounds 1-3. The structural dissimilarity in the structures dependent on the coordination environments of Cd(II) ions and linking modes of mixed ligand influenced by different solvent systems during the synthesis process. Moreover, thermogravimetric and photoluminescence behaviors of 1-3 were also investigated for the first time, and all the complexes emit blue luminescence in the solid state.

  18. Influence of the steric effect of flexible isomeric phenylenediacetic acids on the resultant lead(II) coordination polymers

    Energy Technology Data Exchange (ETDEWEB)

    Wu, Yunlong; Zhao, Yanqing; Yang, Guo-Ping, E-mail: ygp@nwu.edu.cn; Guo, Yanjun; Wang, Yao-Yu, E-mail: wyaoyu@nwu.edu.cn; Shi, Qi-Zhen

    2015-03-15

    To study the steric effect of the flexible dicarboxylate ligands on the resultant formations of coordination polymers (CPs), four new Pb{sup II} CPs [Pb(1,2-pda)(H{sub 2}O)]{sub n} (1), [Pb(1,3-pda)]{sub n}·nH{sub 2}O (2), [Pb{sub 2}(1,4-pda){sub 2}(H{sub 2}O)]{sub n}·2nH{sub 2}O (3a and 3b) have been produced by the isomeric phenylenediacetic acids (H{sub 2}pda). The X-ray crystallography study reveals that CP 1 is a two-dimensional (2D) 4-connected sql (4{sup 4}.6{sup 2}) network via the weak Pb···O interactions built on 1D chain-like structure. CP 2 crystallizes in orthorhombic system with chiral space group P2{sub 1}2{sub 1}2{sub 1}, showing a 4-connected sra (4{sup 2}.6{sup 3}.8) framework where a left-handed helical motif is formed by Pb{sup II} ions and trans-1,3-pda ligands. More interestingly, CPs 3a and 3b are two true 3D polymorphs and have the different morphology. Topologically, the framework of 3a exhibits a 4-connected lon 6{sup 6} motif, while that of 3b is a (4,6)-connected fsh (4{sup 3}.6{sup 3}){sub 2}(4{sup 6}.6{sup 6}.8{sup 3}) net. It is found that the three isomeric pda anions display the various coordination fashions in four CPs. The different structural arrangements show that the steric effect of the isomeric H{sub 2}pda tectons has a positive role in directing the final products of Pb{sup II} CPs. Also, the fluorescent properties of the CPs were studied in the solid state at room temperature. - Graphical abstract: Four new Pb{sup II}-based CPs have been produced by the isomeric phenylenediacetic acids (H{sub 2}pda). The different structural arrangements show that the steric effect of the isomeric H{sub 2}pda tectons has a positive role in directing the final products of Pb{sup II} CPs. Also, the fluorescent properties of the CPs were studied in the solid state at room temperature. - Highlights: • Four Pb{sup II}-based coordination polymers were produced by phenylenediacetic acids. • The crystal and topological structures of the

  19. Ligand-controlled assembly of Cd(II) coordination polymers based on mixed ligands of naphthalene-dicarboxylate and dipyrido[3,2-d:2‧,3‧-f]quinoxaline: From 0D+1D cocrystal, 2D rectangular network (4,4), to 3D PtS-type architecture

    Science.gov (United States)

    Liu, Guocheng; Chen, Yongqiang; Wang, Xiuli; Chen, Baokuan; Lin, Hongyan

    2009-03-01

    Three novel Cd(II) coordination polymers, namely, [Cd(Dpq)(1,8-NDC)(H 2O) 2][Cd(Dpq)(1,8-NDC)]·2H 2O ( 1), [Cd(Dpq)(1,4-NDC)(H 2O)] ( 2), and [Cd(Dpq)(2,6-NDC)] ( 3) have been obtained from hydrothermal reactions of cadmium(II) nitrate with the mixed ligands dipyrido [3,2-d:2',3'-f]quinoxaline (Dpq) and three structurally related naphthalene-dicarboxylate ligands [1,8-naphthalene-dicarboxylic acid (1,8-H 2NDC), 1,4-naphthalene-dicarboxylic acid (1,4-H 2NDC), and 2,6-naphthalene-dicarboxylic acid (2,6-H 2NDC)]. Single-crystal X-ray diffraction analysis reveals that the three polymers exhibit novel structures due to different naphthalene-dicarboxylic acid. Compound 1 is a novel cocrystal of left- and right-handed helical chains and binuclear complexes and ultimately packed into a 3D supramolecular structure through hydrogen bonds and π- π stacking interactions. Compound 2 shows a 2D rectangular network (4,4) bridged by 1,4-NDC with two kinds of coordination modes and ultimately packed into a 3D supramolecular structure through inter-layer π- π stacking interactions. Compound 3 is a new 3D coordination polymer with distorted PtS-type network. In addition, the title compounds exhibit blue/green emission in solid state at room temperature.

  20. 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

    Indian Academy of Sciences (India)

    HONGYAN LIN; JUNJUN SUN; GUOCHENG LIU; XIANG WANG; PANWEN CHEN

    2017-01-01

    Three new Ni(II) coordination polymers exhibiting different 1D and 2D framework structures have been hydrothermally synthesized: [Ni(L ¹)(1,3-BDC)(H ₂O) ₃]•H ₂O (1), [Ni(L ¹)(1,3,5-HBTC)(H ₂O) ₃] (2), [Ni ₃ (L ²)3(1,3,5-BTC) ₂ (H ₂O)8]•12H ₂ ₂O (3) [L ¹ = N,N_-bis(pyridin-3-yl)cyclohexane-1,4-dicarboxamide, L ² = N,N’-bis(3-pyridyl)octandiamide, 1,3-H ₂BDC = 1,3-benzenedicarboxylic acid, 1,3,5-H3BTC = 1,3,5- benzenetricarboxylic acid]. X-ray single crystal diffraction analyses revealed that polymer 1 is a 2D interlaced layer based on the 1D [Ni(L ¹)(1,3-BDC)(H ₂O) ₃] meso-helical chains. Polymer 2 is a 1D wave-shaped chain derived from the 1D [Ni(L ¹)]n chain and monodentate coordinated 1,3,5-HBTC anions. Polymer 3 possesses an interesting 2D layer containing the trinuclear [Ni ₃ (1,3,5-BTC) ₂] substructural unit and 1D zigzag [Ni(L ²)]n chain, representing a 3,4-connected {6•8 ²} ₂{6 ² •8 ² • 10• 12} topology. Finally, the adjacent 1D chains or the 2D layers are connected through hydrogen bonding interactions to construct 3D supramolecular networks. Further, the thermal stability, solid state fluorescent property and photocatalytic activity of 1–3 have been investigated.

  1. Hydrogen-bonded porous coordination polymers: structural transformation, sorption properties, and particle size from kinetic studies.

    Science.gov (United States)

    Uemura, Kazuhiro; Saito, Kazuya; Kitagawa, Susumu; Kita, Hidetoshi

    2006-12-20

    Three new coordination polymers, [CoCl2(4-pmna)2]n (1), {[Co(NCS)2(4-pmna)2].2Me2CO}n (2 superset 2Me2CO), and {[Co(4-pmna)2(H2O)2](NO3)2.2CH3OH}n (3 superset 2H2O.2MeOH) (4-pmna = N-(pyridin-4-ylmethyl)nicotinamide), have been synthesized and characterized using single-crystal X-ray diffraction. The cobalt(II) atoms are bridged by 4-pmna ligands in all three compounds to form double-stranded one-dimensional "repeated rhomboid-type" chains with rectangular-shaped cavities. In 1, each chain slips and obstructs the neighboring cavities so that there are no guest-incorporated pores. Both 2 superset 2Me2CO and 3 superset 2H2O.2MeOH do not have such a staggered arrangement and have pores that can be filled with a guest molecule. Compound 3 superset 2H2O.2MeOH traps guest molecules with multiple hydrogen bonds and shows a reversible structural rearrangement during adsorption and desorption. The new crystalline compound, 3, is stabilized by forming hydrogen bonds with the amide moieties of the 4-pmna ligands and was characterized using infrared spectroscopy. The clathration enthalpy of the reaction 3 + 2H2O(l) + 2MeOH(l) 3 superset 2H2O.2MeOH (approximately 35 kJ/mol) was estimated from differential scanning calorimetry data by considering the vaporization enthalpies of H2O and MeOH. The desorption process of 3 superset 2H2O.2MeOH --> 3 follows a single zero-order reaction mechanism under isothermal conditions. The activation energy of ca. 100 kJ/mol was obtained by plotting the logarithm of the reaction time for the same reacted fraction versus the reciprocal of the temperature. Moreover, the distribution of the one-dimensional channels in 3 superset 2H2O.2MeOH was estimated using the observation that the reaction rate is directly proportional to the total sectional area.

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

    Science.gov (United States)

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

    2016-07-01

    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)]·2H2O}n (1), {[Zn(bib)(atbip)]·H2O}n (2), [Zn(bib)(2,2‧-tda)]}n (3) and {[Zn(bib)(5-tbipa)]·EtOH}n (4), (H2atibdc=5-amino-2,4,6-triiodoisophthalic acid, H2atbip=5-amino-2,4,6-tribromoisophthalic acid, 2,2‧-H2tad=2,2‧-thiodiacetic acid, 5-H2tbipa=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 (E1=209.658 kJ·mol-1, E2=250.037 kJ mol-1, E3=225.300 kJ mol-1, E4=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. ΔHd>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 kinetics.

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

    Energy Technology Data Exchange (ETDEWEB)

    He, Tian [Key Laboratory of Synthetic and Natural Functional Molecule Chemistry of the Ministry of Education, College of Chemistry and Materials Science, Northwest University, Xi’an 710069 (China); Yue, Ke-Fen, E-mail: ykflyy@nwu.edu.cn [Key Laboratory of Synthetic and Natural Functional Molecule Chemistry of the Ministry of Education, College of Chemistry and Materials Science, Northwest University, Xi’an 710069 (China); Zhao, Yi-xing; Chen, San-Ping [Key Laboratory of Synthetic and Natural Functional Molecule Chemistry of the Ministry of Education, College of Chemistry and Materials Science, Northwest University, Xi’an 710069 (China); Zhou, Chun-sheng, E-mail: slzhoucs@126.com.cn [Shaanxi Key Laboratory of Comprehensive Utilization of Tailings Resources, College of Chemical Engineering and Modern Materials, Shangluo University, Shangluo 726000 (China); Yan, Ni [Key Laboratory of Synthetic and Natural Functional Molecule Chemistry of the Ministry of Education, College of Chemistry and Materials Science, Northwest University, Xi’an 710069 (China)

    2016-07-15

    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_2O}{sub n} (1), {[Zn(bib)(atbip)]·H_2O}{sub n} (2), {[Zn(bib)(2,2′-tda)]}{sub n} (3) and {[Zn(bib)(5-tbipa)]·EtOH}{sub n} (4), (H{sub 2}atibdc=5-amino-2,4,6-triiodoisophthalic acid, H{sub 2}atbip=5-amino-2,4,6-tribromoisophthalic acid, 2,2′-H{sub 2}tad=2,2′-thiodiacetic acid, 5-H{sub 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{sub 1}=209.658 kJ·mol{sup −1}, E{sub 2}=250.037 kJ mol{sup −1}, E{sub 3}=225.300 kJ mol{sup −1}, E{sub 4}=186.529 kJ·mol{sup −1}) demonstrates that the reaction rate of the melting decomposition is slow. The thermodynamic parameters (ΔH{sup ‡}, ΔG{sup ‡} and ΔS{sup ‡}) at the peak temperatures of the DTG curves were also calculated. ΔG{sup ‡}>0 indicates that the skeleton collapse is not spontaneous. ΔH{sub d}>0 suggests that the skeleton collapse is endothermic, corresponding to the intense endothermic peak of the DSC

  4. 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.

  5. Non-centrosymmetric coordination polymers based on thallium and acetylenedicarboxylate

    Science.gov (United States)

    Ahlers, Ruth; Ruschewitz, Uwe

    2009-06-01

    Single crystals of anhydrous thallium acetylenedicarboxylate (Tl 2(C 4O 4), 1) and thallium acetylenedicarboxylate oxalate (Tl 4(C 4O 4)(C 2O 4), 2) precipitated from aqueous solutions containing thallium(I)-acetate and the respective organic acids. Both compounds crystallize in non-centrosymmetric space groups ( 1: P2 12 12 1; 2: C2) and contain stereochemically active lone pairs at Tl(I). The crystal structures of 1 and 2 show some similarities. Tl atoms are organized in corrugated layers, which are connected by the respective carboxylate anions. Upon heating 1 decomposes at 195 °C to form elemental pyrophorous thallium powder. 2 starts decomposing at approx. 150 °C forming elemental thallium next to another compound, which could not be identified up to now. TlHADC was also synthesized, but its crystal structure could not be solved either from powder or single crystal diffraction data. Upon heating it decomposes to form 1.

  6. Solvothermal Synthesis, Crystal Structure and Luminescent Property of a Dy(Ⅲ) Coordination Polymer Constructed by 1,2,4,5-Benzenetetracarboxylic Acid

    Institute of Scientific and Technical Information of China (English)

    BAI Wei-Wei; ZHU Ning; HAN Li-Min; tONG Hai-Long; GAOYuan-Yuan; SUO Quan-Ling

    2012-01-01

    A three-dimensional coordination polymer {[Dy(H2btec)2/4(btec)3/6(H2O)]·2H2O} n has been synthesized through the reaction of DyCl3·6H2O and 1,2,4,5-benzenetetracarboxylic acid by solvothermal technique, and the crystal structure was determined by X-ray diffraction. The Dy(Ⅲ) coordination polymer crystallizes in monoclinic, space group P21/n with a=10.7063(1), b=7.1491(1), c=17.1197(3), α=90, β=97.10, γ=90°, V=1300.31(3)3 , C10H9DyO11 , Dc=2.389g/cm3 , Z=4, F(000)=892, the final R=0.0165 and wR=0.0448 for I 〉 2σ(I). The title coordination polymer possesses a three-dimensional framework consisting of nine-coordinate Dy(Ⅲ) centers and two kinds of coordination modes for the 1,2,4,5-benzenetetracarboxylic acid ligands. Every btec4- ligand (deprotonated four protons from 1,2,4,5-benzenetetracarboxylic acid) in the title coordination polymer can clamp three Dy atoms like forceps, which could make the Dy atoms closer in the area of metal-metal interaction. The 3-D framework of the coordination polymer has many channels occupied by the free guest water molecules, and the hydrogen bonds between the coordinated carboxylic groups and guest water molecules could stabilize the crystal structure of the title coordination polymer. In addition, the luminescence properties were also studied.

  7. Supramolecular polymers constructed from macrocycle-based host-guest molecular recognition motifs.

    Science.gov (United States)

    Dong, Shengyi; Zheng, Bo; Wang, Feng; Huang, Feihe

    2014-07-15

    CONSPECTUS: Supramolecular polymers, fabricated via the combination of supramolecular chemistry and polymer science, are polymeric arrays of repeating units held together by reversible, relatively weak noncovalent interactions. The introduction of noncovalent interactions, such as hydrogen bonding, aromatic stacking interactions, metal coordination, and host-guest interactions, endows supramolecular polymers with unique stimuli responsiveness and self-adjusting abilities. As a result, diverse monomer structures have been designed and synthesized to construct various types of supramolecular polymers. By changing the noncovalent interaction types, numbers, or chemical structures of functional groups in these monomers, supramolecular polymeric materials can be prepared with tailored chemical and physical properties. In recent years, the interest in supramolecular polymers has been extended from the preparation of intriguing topological structures to the discoveries of potential applications as functional materials. Compared with traditional polymers, supramolecular polymers show some advantages in the fabrication of reversible or responsive materials. The development of supramolecular polymers also offers a platform to construct complex and sophisticated materials with a bottom-up approach. Macrocylic hosts, including crown ethers, cyclodextrins, calixarenes, cucurbiturils, and pillararenes, are the most commonly used building blocks in the fabrication of host-guest interaction-based supramolecular polymers. With the introduction of complementary guest molecules, macrocylic hosts demonstrate selective and stimuli-responsive host-guest complexation behaviors. By elaborate molecular design, the resultant supramolecular polymers can exhibit diverse structures based on the self-selectivity of host-guest interactions. The introduction of reversible host-guest interactions can further endow these supramolecular polymers with interesting and fascinating chemical

  8. Design of a multi-coordinating polymer as a platform for functionalizing metal, metal oxide and semiconductor nanocrystals

    Science.gov (United States)

    Wang, Wentao; Ji, Xin; Kapur, Anshika; Mattoussi, Hedi

    2016-03-01

    We introduce a new set of amphiphilic polymers as multifunctional, metal-coordinating ligands adapted to surfacefunctionalize quantum dots (QDs), iron oxide nanoparticles (IONPs) and gold nanoparticles/nanorods (AuNPs/AuNRs). The ligand design relies on the introduction of several anchoring groups, hydrophilic moieties and reactive functionalities into a polymer chain, via one-step nucleophilic addition reaction. Such synthetic scheme also allows the insertion of target biomolecules during the ligand synthesis. This functionalization strategy yields nanocrystals that exhibit long-term colloidal stability over a broad range of biological conditions, such as pH changes and when mixed with growth media. When zwitterion groups are used as hydrophilic motifs, this provides compact nanocrystals that are compatible with conjugation to proteins via metal-polyhistidine self-assembly. In addition, we show that QDs ligated with these polymers can engage in energy or charge transfer interactions. Furthermore, nanocrystals coated with folic acid-modified polymers could promote the delivery of nanoparticle-conjugates into cancer cells via folate receptormediated endocytosis.

  9. ACID-BASE INTERACTIONS BETWEEN POLYMERS AND FILLERS

    Institute of Scientific and Technical Information of China (English)

    WANG Qingguo; CHEN Fute; HUANG Yuanfu; ZHOU Qingli

    1987-01-01

    Inverse gas chromatography(IGC) and Fourier-transform infrared (FT-IR) techniques were applied to determining the relative acid-base strength of polymers and coupling agents. The acid-base characteristics of fillers such as CaCO3 could be altered by treatment with different coupling agents. It was shown that some mechanical properties of filled polymers were obviously associated with acid-base interactions between polymers and fillers.

  10. Polymer and small molecule based hybrid light source

    Science.gov (United States)

    Choong, Vi-En; Choulis, Stelios; Krummacher, Benjamin Claus; Mathai, Mathew; So, Franky

    2010-03-16

    An organic electroluminescent device, includes: a substrate; a hole-injecting electrode (anode) coated over the substrate; a hole injection layer coated over the anode; a hole transporting layer coated over the hole injection layer; a polymer based light emitting layer, coated over the hole transporting layer; a small molecule based light emitting layer, thermally evaporated over the polymer based light emitting layer; and an electron-injecting electrode (cathode) deposited over the electroluminescent polymer layer.

  11. White polymer light-emitting diodes based on star-shaped polymers with an orange dendritic phosphorescent core.

    Science.gov (United States)

    Zhu, Minrong; Li, Yanhu; Cao, Xiaosong; Jiang, Bei; Wu, Hongbin; Qin, Jingui; Cao, Yong; Yang, Chuluo

    2014-12-01

    A series of new star-shaped polymers with a triphenylamine-based iridium(III) dendritic complex as the orange-emitting core and poly(9,9-dihexylfluorene) (PFH) chains as the blue-emitting arms is developed towards white polymer light-emitting diodes (WPLEDs). By fine-tuning the content of the orange phosphor, partial energy transfer and charge trapping from the blue backbone to the orange core is realized to achieve white light emission. Single-layer WPLEDs with the configuration of ITO (indium-tin oxide)/poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS)/polymer/CsF/Al exhibit a maximum current efficiency of 1.69 cd A(-1) and CIE coordinates of (0.35, 0.33), which is very close to the pure white-light point of (0.33, 0.33). To the best of our knowledge, this is the first report on star-shaped white-emitting single polymers that simultaneously consist of fluorescent and phosphorescent species. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  12. Solid polymer MEMS-based fuel cells

    Science.gov (United States)

    Jankowski, Alan F.; Morse, Jeffrey D.

    2008-04-22

    A micro-electro-mechanical systems (MEMS) based thin-film fuel cells for electrical power applications. The MEMS-based fuel cell may be of a solid oxide type (SOFC), a solid polymer type (SPFC), or a proton exchange membrane type (PEMFC), and each fuel cell basically consists of an anode and a cathode separated by an electrolyte layer. The electrolyte layer can consist of either a solid oxide or solid polymer material, or proton exchange membrane electrolyte materials may be used. Additionally catalyst layers can also separate the electrodes (cathode and anode) from the electrolyte. Gas manifolds are utilized to transport the fuel and oxidant to each cell and provide a path for exhaust gases. The electrical current generated from each cell is drawn away with an interconnect and support structure integrated with the gas manifold. The fuel cells utilize integrated resistive heaters for efficient heating of the materials. By combining MEMS technology with thin-film deposition technology, thin-film fuel cells having microflow channels and full-integrated circuitry can be produced that will lower the operating temperature an will yield an order of magnitude greater power density than the currently known fuel cells.

  13. Interpenetrating 2D Manganese(Ⅱ) Coordination Polymer Supported by 4,4'-Bis(dimethoxyphosphorylmethyl)-biphenyl Ligands

    Institute of Scientific and Technical Information of China (English)

    ZHANG Xiangdong; GE Chunhua; YIN Jing; ZHAO Yang; HE Cui

    2009-01-01

    A novel coordination polymer [Mn(bdpbp)2(NO3)2] n (1), where bdpbp=4,4'-bis(dimethoxyphosphoryl-methyl)biphenyl, was prepared under mild condition. The structure has been determined by single-crystal X-ray diffraction analyses and further characterized by elemental analyses, IR spectra, luminescent property and thermo-gravimetric analyses. Structure of 1 exhibits infinite grid frameworks and forms two fold interpenetrating nets.Weak C--H…O hydrogen bonds ensure the formation and stability of a three dimensional supramolecular network.

  14. Design and synthesis of chiral Ti-1,1'-bi-2-naphthol coordination polymers for heterogeneous catalytic asymmetric oxidation of sulfides

    Institute of Scientific and Technical Information of China (English)

    YUAN Xiao-ya; WANG Xiao-tian

    2008-01-01

    Polymer-immobilized catalysis has many advantages such as easy recovery and reuse of catalyst. We prepared three novel chiral 1,1'-bi-2-naphthol-Ti coordination polymers with properly designed ligands and Ti(OiPr)4 under mild conditions. The prepared polymers exhibited good activity and excellent enantioselectivity (over 99%ee) in catalyzing the asymmetric oxidation of sulfides. The bridge linker in the polymer and the reaction solvent noticeably affected the enantioselectivity. The chiral coordination polymer was very stable and easy to separate from catalyzed reaction systems, with no significant loss of activity or enantioselectivity after reuse for at least ten times. These findings suggest a promising type of catalysts for synthesizing the widely used sulfoxides by asymmetrically oxidizing sulfides.

  15. Syntheses,crystal structures and properties of three novel coordination polymers with tripodal imidazole-containing ligands and benzenetetracarboxylate

    Institute of Scientific and Technical Information of China (English)

    2010-01-01

    Three novel coordination polymers, [Ni2(tib)2(btec)]·2H2O (1), [Co2(tib)2(btec)]·2H2O (2) and [Zn4(tib)2(btec)Cl4]·2H2O (3), have been synthesized by using mixed ligands of 1,3,5-tris(1-imidazolyl)benzene (tib) and 1,2,4,5-benzenetetracarboxylic acid (H4btec) under hydrothermal conditions. Complexes 1 and 2 have the same structure and are rare three-dimensional (3D) self-penetrating (3,4,5)-connected nets, while complex 3 is an unprecedented (3,4)-connected 3D net. The different structures of 1 (2) and 3 are ascribed to the distinct coordination geometry of the metal centers. The thermal stability and photoluminescence property of the complexes were investigated.

  16. Structural and thermodiffractometric analysis of coordination polymers. Part II: zinc and cadmium derivatives of the Bim ligand [Bim = bis(1-imidazolyl)methane].

    Science.gov (United States)

    Masciocchi, Norberto; Pettinari, Claudio; Alberti, Enrica; Pettinari, Riccardo; Nicola, Corrado Di; Albisetti, Alessandro Figini; Sironi, Angelo

    2007-12-10

    New polynuclear coordination species containing the ditopic bis(1-imidazolyl)methane (Bim) ligand have been prepared as microcrystalline powders and structurally characterized by ab initio X-ray powder diffraction methods. [Zn(CH3COO)2(Bim)]n contains 1D chains with tetrahedral metal atoms bridged by Bim ligands; [CdBr2(Bim)]n shows a dense packing with hexacoordinated Cd(II) ions and mu-Br and mu-Bim bridges; at variance, the isomorphous [ZnCl2(Bim)]n and [ZnBr2(Bim)]n species contain cyclic dimers based on tetrahedral Zn(II) ions. Thermodiffractometric analysis allowed estimation of the linear thermal expansion coefficients and strain tensors derived there from. Bim-rich phases, with 2:1 ligand-to-metal ratio, were also isolated: ZnBr2(Bim)2(H2O)3 and [Cd(CH3COO)2(Bim)2]n containing cis and trans MN4O2 chromophores, respectively, show 1D polymers built upon M2Bim2 cycles, hinged on the metal ions. In all species the conformation of the Bim ligands is Cs (or nearly so), while in the few sparse reports of similar coordination polymers the alternative C2 one was preferentially observed.

  17. Effect of Coordinate Bond in Molecular Recognition of Enrofloxacin with Imprinted Polymers

    Institute of Scientific and Technical Information of China (English)

    Recilas-mota; J; Jesús; Gracia-mora; Jesús; Bernad-bernad; Josefa

    2007-01-01

    1 Results Molecular imprinting is a technique for the preparation of functional materials with molecular recognition properties.Molecular imprinted polymers (MIPs) have become an increasingly active field of study for the construction of new material capable of molecular recognition.In general,MIPs are synthesized by polymerization of cross-linking complexes of template molecules and functional monomers.After removing the template molecules from de polymers,binding sites are formed by functional monomer...

  18. Coordination Polymers Derived from Non-Steroidal Anti-Inflammatory Drugs for Cell Imaging and Drug Delivery.

    Science.gov (United States)

    Paul, Mithun; Dastidar, Parthasarathi

    2016-01-18

    A new series of Mn(II) coordination polymers, namely, [{Mn(L)(H2 O)2 }⋅2 Nap]∞ (CP1), [{Mn(L)(Ibu)2 (H2 O)2 }]∞ (CP2), [{Mn(L)(Flr)2 (H2 O)2 }]∞ (CP3), [{Mn(L)(Ind)2 (H2 O)2 }⋅H2 O]∞ (CP4), [{Mn2 (L)2 (μ-Flu)4 (H2 O)}⋅L]∞ (CP5), [{Mn2 (L)2 (μ-Tol)4 (H2 O)2 }]∞ (CP6) and [{Mn2 (L)2 (μ-Mef)4 (H2 O)2 }]∞ (CP7) (Nap=naproxen, Ibu=ibuprofen, Flr=flurbiprofen, Ind=indometacin, Flu=flufenamic acid, Tol=tolfenamic acid and Mef=mefenamic acid) derived from various non-steroidal anti-inflammatory drugs (NSAIDs) and the organic linker 1,2-bis(4-pyridyl)ethylene (L) have been synthesized with the aim of being used for cell imaging and drug delivery. Single-crystal X-ray diffraction (SXRD) studies revealed that the NSAID molecules were part of the coordination polymeric network either through coordination to the metal center (in the majority of the cases) or through hydrogen bonding. Remarkably, all the Mn(II) coordination polymers were found to be soluble in DMSO, thereby making them particularly suitable for the desired biological applications. Two of the coordination polymers (namely, CP1 and CP3) reported herein, were found to be photoluminescent both in the solid as well as in the solution state. Subsequent experiments (namely, MTT (3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyltetrazolium bromide), and PGE2 (prostaglandin E2 ) assays) established their biocompatibility and anti-inflammatory response. In vitro studies by using a macrophage cell line (i.e., RAW 264.7) revealed that both CP1 and CP3 were excellent cell imaging agents. Finally, biodegradability studies under simulated physiological conditions in phosphate-buffered saline (PBS) at pH 7.6 showed that slow and sustained release of the corresponding NSAID was indeed possible from both CP1 and CP3.

  19. Construction of Four Zn(II Coordination Polymers Used as Catalysts for the Photodegradation of Organic Dyes in Water

    Directory of Open Access Journals (Sweden)

    Lei-Lei Liu

    2016-01-01

    Full Text Available Hydrothermal reactions of Zn(OAc2·2H2O with flexible bipyridyl benzene ligand and three dicarboxylic derivatives gave rise to four new coordination polymers, [Zn7(μ4-O2(OAc10(bpmb]n (1, [Zn(5-OH-1,3-BDC(bpmb]n (2, [Zn(1,2-BDC(bpmb]n (3 and [Zn2(ADB2(bpmb]n (4 (bpmb = 1,4-bis(pyridine-3-ylmethoxybenzene, 5-OH-1,3-H2BDC = 5-hydroxy-1,3-benzenedicarboxylic acid, 1,2-H2BDC = 1,2-benzenedicarboxylic acid, H2ADB = 2,2’-azodibenzoic acid. Their structures were characterized by single-crystal X-ray diffraction, elemental analyses, IR spectra, powder X-ray diffraction (PXRD and thermogravimetric analyses (TGA. Compound 1 features a one-dimensional (1D chain structure based on the rare heptanuclear [Zn7(μ4-O(μ3-OAc2(μ2-OAc8] units. Compound 2 exhibits a novel 2D bilayer structure built from the two parallel 2D (4,4 layers. Compound 3 holds a 2D structure in which the 1,2-BDC ligands work as lockers interlocking 1D [Zn(bpmb]n chain. Compound 4 comprises a 3D framework constructed by 2D wrinkled [Zn2(ADB4]n networks and bpmb linkers with a six-connected pcu net. These results suggest that the motifs of the dicarboxylic ligands have significant effect on the final structures. These compounds exhibited relatively good photocatalytic activity towards the degradation of methylene blue (MB in aqueous solution under a Xe lamp irradiation.

  20. Metal coordination polymers of 2,3-bis(benzimidazol-1-ylmethyl)quinoxaline: Syntheses, crystal structures and luminescent properties

    Science.gov (United States)

    Du, Jian-Long; Wei, Zi-Zhang; Hu, Tong-Liang

    2011-06-01

    Two new metal-organic frameworks, {[Cu LI]·CHCl 3} ∞( 1) and {[Hg L(Br) 2] 4·2CH 2Cl 2} ∞ ( 2) have been prepared by reacting CuI and HgBr 2 with the new flexible ligand L [ L = 2,3-Bis(benzimidazol-1-ylmethyl)quinoxaline]. Both complexes have been characterized by elemental analysis, IR, TGA, XRPD, and single crystal X-ray diffraction determination. In 1, the Cu(I) ion takes tetrahedral coordination geometry, and the flexible ligands bridge dinuclear units (Cu 2I 2) to form a one dimensional (1D) double chain structure. While in 2, the Hg(II) coordinates to two bromine ions and two nitrogen donors of L to form a 1D coordination polymer. The structure differences of the two complexes mainly depend on the geometry of the metal ions and the influence of anions. The coordination features of the ligand have also been primarily investigated by density functional theory (DFT) calculations. In addition, the fluorescent properties of the complexes and free ligand L have been investigated in the solid state at room temperature.

  1. Synthesis of Lanthanide Coordination Polymers with Benzophenone-4,4'-dicarboxylate:Effect of Lanthanide Contraction on Structures

    Institute of Scientific and Technical Information of China (English)

    WANG, Yi-Bo(王轶博); JIN, Lin-Pei(金林培)

    2004-01-01

    Four lanthanide coordination polymers with benzophenone-4,4'-dicarboxylic acid (H2bpndc) and 1,10-phenanthroline(phen),[Ln2(bpndc)3(phen)](Ln=La(1),Pr(2) and Tb(3)),[Yb(bpndc)1.5(phen)]·0.5H2O(4) were obtained through solvothermal synthesis. The crystallographic data show that 1, 2, and 3 are isostructural, the Ln(Ⅲ)ions in 1, 2 and 3 are all eight- and ten-coordinated, respectively, and thus the Ln(Ⅲ) ions are connected by bpndc ligands, resulting in an interpenetrating 3D structure. While in 4, the Yb(Ⅲ) ions are eight-coordinated and connected by bpndc ligands into a 3D structure with 1D rhombic channels, which result from the effect of lanthanide contraction from La(Ⅲ) to Yb(Ⅲ) ions, and the bpndc ligands in 1, 2, 3, and 4 display three types of coordination modes.

  2. A two-dimensional yttrium phthalate coordination polymer, [Y4(H2O)2(C8H4O4)6]∞, exhibiting different coordination geometries

    Indian Academy of Sciences (India)

    A Thirumurugan; Srinivasan Natarajan

    2003-10-01

    A hydrothermal reaction of a mixture of Y(NO3)3, 1,2-benzenedicarboxylic 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, CN7 = pentagonal bipyramid, CN8 = dodecahedron and CN9 =capped square antiprism). The oxygen atoms of the 1,2-BDC are fully deprotonated, and show variations in their connectivity with Y atoms. The Y atoms themselves are connected through their vertices forming infinite Y-O-Y one-dimensional chains. The Y-O-Y chains are cross-linked by the 1,2-BDC anions forming a corrugated layer structure. The layers are supported by favourable $\\ldots$ interactions between the benzene rings of the 1,2-BDC anions. The variations in the coordination environment of the Y atoms and the presence of Y-O-Y interactions along with the favourable $\\ldots$ interactions between the benzene rings from different layers are noteworthy structural features. Crystal data: triclinic, space group = -1 (no. 2), = 12.6669 (2), = 13.8538 (2), = 16.0289 Å, = 75.20 (1), = 69.012 (1), = 65.529 (1)°, = 2371.28 (7) Å3, calc = 1.922 g cm-1, (MoK) = 4.943 mm-1. A total of 9745 reflections collected and merged to give 6566 unique reflections (int = 0.0292) of which 5252 with > 2() were considered to be observed. Final 2 = 0.0339, 2 = 0.0724 and =1.036 were obtained for 704 parameters.

  3. Renewable Energy for Electric Vehicles: Price Based Charging Coordination

    NARCIS (Netherlands)

    Richstein, J.C.; Schuller, A.; Dinther, C.; Ketter, W.; Weinhardt, C.

    2012-01-01

    In this paper we investigate the charging coordination of battery electric vehicles (BEV) with respect to the availability of intermittent renewable energy generation considering individual real world driving profiles in a deterministic simulation based analysis, mapping a part of the German power

  4. Renewable Energy for Electric Vehicles: Price Based Charging Coordination

    NARCIS (Netherlands)

    Richstein, J.C.; Schuller, A.; Dinther, C.; Ketter, W.; Weinhardt, C.

    2012-01-01

    In this paper we investigate the charging coordination of battery electric vehicles (BEV) with respect to the availability of intermittent renewable energy generation considering individual real world driving profiles in a deterministic simulation based analysis, mapping a part of the German power s

  5. Ionic-Liquid-Based Polymer Electrolytes for Battery Applications.

    Science.gov (United States)

    Osada, Irene; de Vries, Henrik; Scrosati, Bruno; Passerini, Stefano

    2016-01-11

    The advent of solid-state polymer electrolytes for application in lithium batteries took place more than four decades ago when the ability of polyethylene oxide (PEO) to dissolve suitable lithium salts was demonstrated. Since then, many modifications of this basic system have been proposed and tested, involving the addition of conventional, carbonate-based electrolytes, low molecular weight polymers, ceramic fillers, and others. This Review focuses on ternary polymer electrolytes, that is, ion-conducting systems consisting of a polymer incorporating two salts, one bearing the lithium cation and the other introducing additional anions capable of plasticizing the polymer chains. Assessing the state of the research field of solid-state, ternary polymer electrolytes, while giving background on the whole field of polymer electrolytes, this Review is expected to stimulate new thoughts and ideas on the challenges and opportunities of lithium-metal batteries.

  6. Optimization of salt concentration in polymer based ionic conductor

    Science.gov (United States)

    Thakur, Deep Kumar; Sharma, A. L.

    2017-07-01

    Free standing polymeric films (electrolytes) have been prepared by PAN as a polymer host and Li salt (LiPF6) using the standard solution cast process. Interaction of polymer-salt complex of the host matrix has also been observed in the Fourier transform infrared (FTIR) spectrum results. The cation (Li+) coordination at nitrile (-C≡N) site of the polymer backbone along with the appearance of a shoulder suggesting strong evidence of polymer-ion interaction. Field Emission Scanning Electron Microscopy (FESEM), was used to study morphological information of grain boundaries and cracks while Complex impedance spectroscopy suggests bulk electrical conduction. Solid electrolytes provide advantages in terms of simplicity of design and operational safety, but typically SPE's have the conductivities that are lower than those of organic liquid electrolytes.

  7. Load management through agent based coordination of flexible electricity consumers

    DEFF Research Database (Denmark)

    Clausen, Anders; Jørgensen, Bo Nørregaard

    2015-01-01

    Demand Response (DR) offers a cost-effective and carbonfriendly way of performing load balancing. DR describes a change in the electricity consumption of flexible consumers in response to the supply situation. In DR, flexible consumers may perform their own load balancing through load management....... In this paper, we propose an approach to perform such coordination through a Virtual Power Plant (VPP)[1]. We represent flexible electricity consumers as software agents and we solve the coordination problem through multi-objective multi-issue optimization using a mediator-based negotiation mechanism. We...... illustrate how we can coordinate flexible consumers through a VPP in response to external events simulating the need for load balancing services....

  8. Quantum coordinated multi-point communication based on entanglement swapping

    Science.gov (United States)

    Du, Gang; Shang, Tao; Liu, Jian-wei

    2017-05-01

    In a quantum network, adjacent nodes can communicate with each other point to point by using pre-shared Einsten-Podolsky-Rosen (EPR) pairs, and furthermore remote nodes can establish entanglement channels by using quantum routing among intermediate nodes. However, with the rapid development of quantum networks, the demand of various message transmission among nodes inevitably emerges. In order to realize this goal and extend quantum networks, we propose a quantum coordinated multi-point communication scheme based on entanglement swapping. The scheme takes full advantage of EPR pairs between adjacent nodes and performs multi-party entanglement swapping to transmit messages. Considering various demands of communication, all nodes work cooperatively to realize different message transmission modes, including one to many, many to one and one to some. Scheme analysis shows that the proposed scheme can flexibly organize a coordinated group and efficiently use EPR resources, while it meets basic security requirement under the condition of coordinated communication.

  9. 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.

  10. Two new hexacoordinated coordination polymers of cadmium(II) containing bridging units only: Syntheses, structures and molecular properties

    Indian Academy of Sciences (India)

    DIPU SUTRADHAR; HABIBAR CHOWDHURY; SUSHOVAN KONER; SUBHASIS ROY; BARINDRA KUMAR GHOSH

    2016-09-01

    The syntheses, characterizations and structures of a neutral 2D coordination polymer [Cd(bnzd)(NCS)₂]n (1) and a polycationic 3D coordination polymer isolated as perchlorate salt [Cd(bnzd)₃]n(ClO₄)₂n (2) (bnzd = benzidine) are described. X-ray structural analyses reveal that each hexacoordinated cadmium(II) center in 1 adopts a distorted octahedral geometry with a CdN₄S₂ chromophore bound by two N atoms of two different bnzd units and two N and two S atoms of symmetric doubly bridged end-toend NCS− units extended in a 2D sheet. Six N atoms of six different bridged bnzd units are bonded to each cadmium(II) in 2 in a non-ended fashion affording a 3D network structure. In the crystalline state, each 2D sheet structure in 1 is further stabilized by π· · ·π interaction which in turn affords a 3D network structure through multiple intermolecular N-H· · · S hydrogen bonds. On the other hand, the 3D network structure in 2 is stabilized by weak intermolecular N-H· · ·O hydrogen bonds and C-H· · ·π interactions. Bnzd, 1 and 2 display intraligand 1(π-π*) fluorescence in DMF solution at room temperature.

  11. 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.

  12. Asphaltenes-based polymer nano-composites

    Science.gov (United States)

    Bowen, III, Daniel E

    2013-12-17

    Inventive composite materials are provided. The composite is preferably a nano-composite, and comprises an asphaltene, or a mixture of asphaltenes, blended with a polymer. The polymer can be any polymer in need of altered properties, including those selected from the group consisting of epoxies, acrylics, urethanes, silicones, cyanoacrylates, vulcanized rubber, phenol-formaldehyde, melamine-formaldehyde, urea-formaldehyde, imides, esters, cyanate esters, allyl resins.

  13. Development of controlled drug release systems based on thiolated polymers.

    Science.gov (United States)

    Bernkop-Schnürch, A; Scholler, S; Biebel, R G

    2000-05-03

    The purpose of the present study was to generate mucoadhesive matrix-tablets based on thiolated polymers. Mediated by a carbodiimide, L-cysteine was thereby covalently linked to polycarbophil (PCP) and sodium carboxymethylcellulose (CMC). The resulting thiolated polymers displayed 100+/-8 and 1280+/-84 micromol thiol groups per gram, respectively (means+/-S.D.; n=6-8). In aqueous solutions these modified polymers were capable of forming inter- and/or intramolecular disulfide bonds. The velocity of this process augmented with increase of the polymer- and decrease of the proton-concentration. The oxidation proceeded more rapidly within thiolated PCP than within thiolated CMC. Due to the formation of disulfide bonds within thiol-containing polymers, the stability of matrix-tablets based on such polymers could be strongly improved. Whereas tablets based on the corresponding unmodified polymer disintegrated within 2 h, the swollen carrier matrix of thiolated CMC and PCP remained stable for 6.2 h (mean, n=4) and more than 48 h, respectively. Release studies of the model drug rifampicin demonstrated that a controlled release can be provided by thiolated polymer tablets. The combination of high stability, controlled drug release and mucoadhesive properties renders matrix-tablets based on thiolated polymers useful as novel drug delivery systems.

  14. Isoindigo-based polymer photovoltaics: modifying polymer molecular structures to control the nanostructural packing motif.

    Science.gov (United States)

    Kim, Yu Jin; Lee, Yun-Ji; Kim, Yun-Hi; Park, Chan Eon

    2016-07-21

    Donor molecular structures, and their packing aspects in donor:acceptor active blends, play a crucial role in the photovoltaic performance of polymer solar cells. We systematically investigated a series of isoindigo-based donor polymers within the framework of a three-dimensional (3D) crystalline motif by modifying their chemical structures, thereby affecting device performances. Although our isoindigo-based polymer series contained polymers that differed only by their alkyl side chains and/or donating units, they showed quite different nanoscale morphological properties, which resulted in significantly different device efficiencies. Notably, blends of our isoindigo-based donor polymer systems with an acceptor compound, whereby the blends had more intermixed network morphologies and stronger face-on orientations of the polymer crystallites, provided better-performing photovoltaic devices. This behavior was analyzed using atomic force microscopy (AFM) and two-dimensional grazing incidence wide angle X-ray diffraction (2D-GIWAXD). To the best of our knowledge, no correlation has been reported previously between 3D nano-structural donor crystallites and device performances, particularly for isoindigo-based polymer systems.

  15. Coordinated SLNR based Precoding in Large-Scale Heterogeneous Networks

    KAUST Repository

    Boukhedimi, Ikram

    2017-03-06

    This work focuses on the downlink of large-scale two-tier heterogeneous networks composed of a macro-cell overlaid by micro-cell networks. Our interest is on the design of coordinated beamforming techniques that allow to mitigate the inter-cell interference. Particularly, we consider the case in which the coordinating base stations (BSs) have imperfect knowledge of the channel state information. Under this setting, we propose a regularized SLNR based precoding design in which the regularization factor is used to allow better resilience with respect to the channel estimation errors. Based on tools from random matrix theory, we provide an analytical analysis of the SINR and SLNR performances. These results are then exploited to propose a proper setting of the regularization factor. Simulation results are finally provided in order to validate our findings and to confirm the performance of the proposed precoding scheme.

  16. Coordination-directed one-dimensional coordination polymers generated from a new oxadiazole bridging ligand and HgX2 (X=Cl, Br and I).

    Science.gov (United States)

    Yang, Rui; Ma, Jian Ping; Huang, Ru Qi; Dong, Yu Bin

    2011-06-01

    A new 1,3,4-oxadiazole bridging bent organic ligand, 2,5-bis{5-methyl-2-[(4-pyridyl)methoxy]phenyl}-1,3,4-oxadiazole, C(28)H(24)N(4)O(3), L, has been used to create three novel one-dimensional isomorphic coordination polymers, viz. catena-poly[[[dichloridomercury(II)]-μ-2,5-bis{5-methyl-2-[(4-pyridyl)methoxy]phenyl}-1,3,4-oxadiazole] methanol monosolvate], {[HgCl(2)(C(28)H(24)N(4)O(3))]·CH(3)OH}(n), catena-poly[[[dibromidomercury(II)]-μ-2,5-bis{5-methyl-2-[(4-pyridyl)methoxy]phenyl}-1,3,4-oxadiazole] methanol monosolvate], {[HgBr(2)(C(28)H(24)N(4)O(3))]·CH(3)OH}(n), and catena-poly[[[diiodidomercury(II)]-μ-2,5-bis{5-methyl-2-[(4-pyridyl)methoxy]phenyl}-1,3,4-oxadiazole] methanol monosolvate], {[HgI(2)(C(28)H(24)N(4)O(3))]·CH(3)OH}(n). The free L ligand itself adopts a cis conformation, with the two terminal pyridine rings and the central oxadiazole ring almost coplanar [dihedral angles = 5.994 (7) and 9.560 (6)°]. In the Hg(II) complexes, however, one of the flexible pyridylmethyl arms of ligand L is markedly bent and helical chains are obtained. The Hg(II) atom lies in a distorted tetrahedral geometry defined by two pyridine N-atom donors from two L ligands and two halide ligands. The helical chains stack together via interchain π-π interactions that expand the dimensionality of the structure from one to two. The methanol solvent molecules link to the complex polymers through O-H···N and O-H···O hydrogen bonds. © 2011 International Union of Crystallography

  17. Fabrication of Ag/CPs composite material, an effective strategy to improve the photocatalytic performance of coordination polymers under visible irradiation.

    Science.gov (United States)

    Xu, Xinxin; Cui, Zhongping; Qi, Ji; Liu, Xiaoxia

    2013-10-01

    To enhance the photocatalytic property of coordination polymers (CPs) in the visible light region, Ag loaded coordination polymer composite materials (Ag/CPs) were synthesized successfully through a photoreduction reaction of Ag(+) on the surface of CPs. Photoluminescence (PL) was used to investigate the separation of photogenerated electron-hole pairs and the results illustrated Ag/CPs display higher quantum yields than CPs. This can be attributed to the strong interactions between Ag nanorods and coordination polymers, which lead to electron-hole pair separation between Ag nanorods and CPs. The degradation of Rhodamine B (RhB) was investigated to study the photocatalytic activities. Ag/CPs exhibited excellent photocatalytic activity in the UV and visible light region, while CPs can only decompose RhB under the irradiation of UV light. Furthermore, Ag/CPs showed outstanding stability during degradation of RhB.

  18. Robust Photocatalytic H2O2 Production by Octahedral Cd3(C3N3S3)2 Coordination Polymer under Visible Light

    Science.gov (United States)

    Zhuang, Huaqiang; Yang, Lifang; Xu, Jie; Li, Fuying; Zhang, Zizhong; Lin, Huaxiang; Long, Jinlin; Wang, Xuxu

    2015-11-01

    Herein, we reported a octahedral Cd3(C3N3S3)2 coordination polymer as a new noble metal-free photocatalyst for robust photocatalytic H2O2 production from methanol/water solution. The coordination polymer can give an unprecedented H2O2 yield of ca. 110.0 mmol • L-1 • g-1 at pH = 2.8 under visible light illumination. The characterization results clearly revealed that the photocatalytic H2O2 production proceeds by a pathway of two-electron reduction of O2 on the catalyst surface. This work showed the potential perspective of Mx(C3N3S3)y (M = transitional metals) coordination polymers as a series of new materials for solar energy storage and conversion.

  19. Mixed ligand coordination polymers with flexible bis-imidazole linker and angular sulfonyldibenzoate: Crystal structure, photoluminescence and photocatalytic activity

    Science.gov (United States)

    Bisht, Kamal Kumar; Rachuri, Yadagiri; Parmar, Bhavesh; Suresh, Eringathodi

    2014-05-01

    Four ternary coordination polymers (CPs) namely, {[Ni(SDB)(BITMB)(H2O)]·H2O}n (CP1), {[Cd(SDB)(BITMB) (H2O)]·(THF)(H2O)}n (CP2), {[Zn2(SDB)2(BITMB)]·(THF)2}n (CP3) and {[Co2(SDB)2(BITMB)]·(Dioxane)3}n (CP4) composed of angular dicarboxylate SDB (4,4'-sulfonyldibenzoate) and N-donor BITMB (1,3-bis(imidazol-1-ylmethyl)-2,4,6-trimethyl benzene) have been synthesized by solvothermal reactions and characterized by single crystal X-ray diffraction and other physico-chemical techniques. CP1 possesses one-dimensional ribbon type metal-organic motifs glued together by H-bonds and π⋯π interactions, whereas CP2-CP4, exhibit non-interpenetrated sql networks supported by weak supramolecular interactions. Structural diversity of these CPs can be attributed to the coordination geometry adopted by the metal nodes, versatile coordination modes of SDB and conformational flexibility of BITMB. Solid state luminescence properties of CP1-CP4 were explored. Photocatalytic performance of all CPs for the decomposition of metanil yellow by dilute hydrogen peroxide in the presence of visible light was also investigated. 25-83% dye removal from aqueous solutions in the presence of CP1-CP4 was observed.

  20. 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.

  1. Crystal Structure and Fluorescent Property of a 2D Coordination Polymer: [Eu(PCPA)3(H2O)]n

    Institute of Scientific and Technical Information of China (English)

    SUN Rui-Qing; ZHANG Han-Hui; CAO Yan-Ning; CHEN Yi-Ping; WANG Zhen; YANG Qi-Yu

    2006-01-01

    The title coordination polymer [Eu(PCPA)3(H2O)]n (PCPA = p-chlorophenoxyacetate) has been synthesized under hydrothermal condition, determined by single-crystal X-ray diffraction and characterized by FT-IR, UV-VIS and fluorescent spectra. The crystal belongs to triclinic system, space group P1 with a = 7.8036(1), b = 12.7458(4), c = 14.0208(3) (A), α =81.610(8), β = 79.406(8), γ = 77.567(7)°, V = 1330.40(5) (A)3, C24H20Cl3EuO10, Mr = 726.71, Z = 2,F(000) = 716, Dc= 1.814 g/cm3, λ(MoKα) = 0.71073 (A), μ(MoKα) = 2.713 mm-1, the final R =0.0284 and wR = 0.0678 for 5529 observed reflections with 1 > 2σ(Ⅰ). The europium ions are located in a nine-coordinate environment. PCPA ions with two different coordination modes connect the metal ions to form 1D zigzag chains which are arranged to generate 2D supramolecular layers by intermolecular hydrogen bonds. The luminescence properties of the rare-earth ions are studied in this paper.

  2. Two new pyridine-2,3-dicarboxylate coordination polymers prepared from zerovalent metal precursor: Syntheses, luminescent and magnetic properties

    Science.gov (United States)

    Semerci, Fatih; Yeşilel, Okan Zafer; Soylu, Mustafa Serkan; Yerli, Yusuf; Dal, Hakan

    2014-02-01

    Two new K+/Cu(II) and Zn(II) coordination polymers with pyridine-2,3-dicarboxylate (pydc), {K2[Cu(μ-pydc)2]·3H2O}n (1) and {[Zn(μ-pydc)(H2O)(4-mim)]·H2O}n (2) (4-mim=4-methylimidazole) have been synthesized from zerovalent metal and characterized by IR, EPR spectroscopy, thermal analysis and single crystal X-ray diffraction techniques. In the sandwiched 3D anionic framework of 1, pydc ligands exhibit hexadentate coordination; tridentate coordination bond with Cu(II) and tridentate ionic interaction with K+ ions. {K2[Cu(μ-pydc)2]·3H2O}n shows a rare topology consists of three dimensional (3,4,5)-connected network with the point symbol of {42.6}2{42.84}{43.6.86}2. The distorted square pyramidal geometry of 2 is completed with an nitrogen atom from 4-mim and aqua ligand to form a 1D polynuclear structure. The hydrogen bonds link the 1D chains into 3D architecture. The temperature dependent magnetic property of complex 1 has been studied. Complex 2 exhibits unusual yellow luminescence in the solid state at room temperature.

  3. GUIDELESS SPATIAL COORDINATE MEASUREMENT TECHNOLOGY BASED ON CODING POLE

    Institute of Scientific and Technical Information of China (English)

    ZHAO Min; QIU Zongming; QU Jiamin; LIU Hongzhao

    2008-01-01

    A new method of guideless spatial coordinate measurement technology based on coding pole and vision measurement is proposed. Unequal spacing of bar code is adopted to pole, so that the code combination of pole image in measuring field is unique. Holographic characteristics of numeric coding pole are adopted to obtain pole pose and pole probe position by any section of bar code on the pole. Spatial coordinates of measuring points can be obtained by coordinate transform. The contradiction between high resolution and large visual field of image sensor is resolved, thereby providing a new concept for surface shape measurement of large objects with high precision. The measurement principles of the system are expounded and mathematic model is established. The measurement equation is evaluated by simulation experiments and the measurement precision is analyzed. Theoretical analysis and simulation experiments prove that this system is characterized by simple structure and wide measurement range. Therefore it can be used in the 3-dimentional coordinate measurement of large objects.

  4. Study of a thiophene-based polymer for optoelectronic applications

    Energy Technology Data Exchange (ETDEWEB)

    Cheylan, S. [ICFO, Institut de Ciencies Fotoniques, Edificio NEXUS II, c. Jordi Girona 29, 08034 Barcelona (Spain)]. E-mail: Stephanie.cheylan@icfo.es; Fraleoni-Morgera, A. [Department of Industrial and Materials Chemistry, University of Bologna, V. Risorgimento 4, 40136 Bologna (Italy); Puigdollers, J. [Departamento de Ingenieria Electronica, Universidad Politecnica de Cataluna, UPC, Campus Nord Edifici C4, c/ Jordi Girona 1-3, 08034 Barcelona (Spain); Voz, C. [Departamento de Ingenieria Electronica, Universidad Politecnica de Cataluna, UPC, Campus Nord Edifici C4, c/ Jordi Girona 1-3, 08034 Barcelona (Spain); Setti, L. [Department of Industrial and Materials Chemistry, University of Bologna, V. Risorgimento 4, 40136 Bologna (Italy); Alcubilla, R. [Departamento de Ingenieria Electronica, Universidad Politecnica de Cataluna, UPC, Campus Nord Edifici C4, c/ Jordi Girona 1-3, 08034 Barcelona (Spain); Badenes, G. [ICFO, Institut de Ciencies Fotoniques, Edificio NEXUS II, c. Jordi Girona 29, 08034 Barcelona (Spain); Costa-Bizzarri, P. [Department of Industrial and Materials Chemistry, University of Bologna, V. Risorgimento 4, 40136 Bologna (Italy); Lanzi, M. [Department of Industrial and Materials Chemistry, University of Bologna, V. Risorgimento 4, 40136 Bologna (Italy)

    2006-02-21

    A thiophene-based conjugated polymer bearing a cyano group (-CN) as a side chain substituent was successfully synthesized. The polymer evidences an excellent film ability from various organic solvents as well as an enhanced photoluminescence. The polymer has been characterized optically (Fourier Transformed Infrared spectroscopy, absorption and photoluminescence) in solution and in film, while X-ray diffraction measurements (XRD) of thin films were performed to investigate its bulk morphological features. From the absorption edge of the spectrum of a thin polymer film, the optical band gap of the polymer is estimated to be 2.0 eV, which corresponds to orange emission. Furthermore, a single layer light emitting diode (LED) was fabricated. The device produced bright stable electroluminescence at room temperature. All of the results indicate that this polymer is a promising emissive material for application in polymeric LEDs.

  5. Gas Sensors Based on Polymer Field-Effect Transistors

    Science.gov (United States)

    Lv, Aifeng; Pan, Yong; Chi, Lifeng

    2017-01-01

    This review focuses on polymer field-effect transistor (PFET) based gas sensor with polymer as the sensing layer, which interacts with gas analyte and thus induces the change of source-drain current (ΔISD). Dependent on the sensing layer which can be semiconducting polymer, dielectric layer or conducting polymer gate, the PFET sensors can be subdivided into three types. For each type of sensor, we present the molecular structure of sensing polymer, the gas analyte and the sensing performance. Most importantly, we summarize various analyte–polymer interactions, which help to understand the sensing mechanism in the PFET sensors and can provide possible approaches for the sensor fabrication in the future. PMID:28117760

  6. Gas Sensors Based on Polymer Field-Effect Transistors.

    Science.gov (United States)

    Lv, Aifeng; Pan, Yong; Chi, Lifeng

    2017-01-22

    This review focuses on polymer field-effect transistor (PFET) based gas sensor with polymer as the sensing layer, which interacts with gas analyte and thus induces the change of source-drain current (ΔISD). Dependent on the sensing layer which can be semiconducting polymer, dielectric layer or conducting polymer gate, the PFET sensors can be subdivided into three types. For each type of sensor, we present the molecular structure of sensing polymer, the gas analyte and the sensing performance. Most importantly, we summarize various analyte-polymer interactions, which help to understand the sensing mechanism in the PFET sensors and can provide possible approaches for the sensor fabrication in the future.

  7. 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.

  8. Self-Assembly of 1D/2D Hybrid Nanostructures Consisting of a Cd(II Coordination Polymer and NiAl-Layered Double Hydroxides

    Directory of Open Access Journals (Sweden)

    Gonzalo Abellán

    2015-12-01

    Full Text Available The preparation and characterization of a novel hybrid material based on the combination of a 2D-layered double hydroxide (LDH nanosheets and a 1D-coordination polymer (1D-CP has been achieved through a simple mixture of suspensions of both building blocks via an exfoliation/restacking approach. The hybrid material has been thoroughly characterized demonstrating that the 1D-CP moieties are intercalated as well as adsorbed on the surface of the LDH, giving rise to a layered assembly with the coexistence of the functionalities of their initial constituents. This hybrid represents the first example of the assembly of 1D/2D nanomaterials combining LDH with CP and opens the door for a plethora of different functional hybrid systems.

  9. Self-Construction from 2D to 3D: One-Pot Layer-by-Layer Assembly of Graphene Oxide Sheets Held Together by Coordination Polymers.

    Science.gov (United States)

    Zakaria, Mohamed B; Li, Cuiling; Ji, Qingmin; Jiang, Bo; Tominaka, Satoshi; Ide, Yusuke; Hill, Jonathan P; Ariga, Katsuhiko; Yamauchi, Yusuke

    2016-07-11

    Deposition of Ni-based cyanide bridged coordination polymer (NiCNNi) flakes onto the surfaces of graphene oxide (GO) sheets, which allows precise control of the resulting lamellar nanoarchitecture by in situ crystallization, is reported. GO sheets are utilized as nucleation sites that promote the optimized crystal growth of NiCNNi flakes. The NiCNNi-coated GO sheets then self-assemble and are stabilized as ordered lamellar nanomaterials. Regulated thermal treatment under nitrogen results in a Ni3 C-GO composite with a similar morphology to the starting material, and the Ni3 C-GO composite exhibits outstanding electrocatalytic activity and excellent durability for the oxygen reduction reaction.

  10. Lithium ion conducting solid polymer blend electrolyte based on bio-degradable polymers

    Indian Academy of Sciences (India)

    Natarajan Rajeswari; Subramanian Selvasekarapandian; Moni Prabu; Shunmugavel Karthikeyan; C Sanjeeviraja

    2013-04-01

    Lithium ion conducting polymer blend electrolyte films based on poly(vinyl alcohol) (PVA) and poly(vinyl pyrrolidone) (PVP) with different Mwt% of lithium nitrate (LiNO3) salt, using a solution cast technique, have been prepared. The polymer blend electrolyte has been characterized by XRD, FTIR, DSC and impedance analyses. The XRD study reveals the amorphous nature of the polymer electrolyte. The FTIR study confirms the complex formation between the polymer and salt. The shifts in g values of 70 PVA–30 PVP blend and 70 PVA–30 PVP with different Mwt% of LiNO3 electrolytes shown by DSC thermograms indicate an interaction between the polymer and the salt. The dependence of g and conductivity upon salt concentration has been discussed. The ion conductivity of the prepared polymer electrolyte has been found by a.c. impedance spectroscopic analysis. The PVA–PVP blend system with a composition of 70 wt% PVA: 30 wt% PVP exhibits the highest conductivity of 1.58 × 10-6 Scm-1 at room temperature. Polymer samples of 70 wt% PVA–30 wt% PVP blend with different molecular weight percentage of lithium nitrate with DMSO as solvent have been prepared and studied. High conductivity of 6.828 × 10-4 Scm-1 has been observed for the composition of 70 PVA:30 PVP:25 Mwt% of LiNO3 with low activation energy 0.2673 eV. The conductivity is found to increase with increase in temperature. The temperature dependent conductivity of the polymer electrolyte follows the Arrhenius relationship which shows hopping of ions in the polymer matrix. The relaxation parameters () and () of the complexes have been calculated by using loss tangent spectra. The mechanical properties of polymer blend electrolyte such as tensile strength, elongation and degree of swelling have been measured and the results are presented.

  11. A Novel Borophosphate Coordination Polymer with Sandwich-type Supramolecular Architecture

    Institute of Scientific and Technical Information of China (English)

    Mao Feng LI; Heng Zhen SHI; Yong Kui SHAN; Ming Yuan HE

    2004-01-01

    A novel borophosphate (Hmel)3{Co2[(mel)2(HPO4)2(PO4)](H3BO3·H2O} (mel = melamine) has been synthesized under mild solvothermal conditions. The structure of the compound exists a high ordered organic-inorganic sandwich-type supramolecular architecture via metal-coordination, hydrogen bonds and π-π stacking interactions.

  12. 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.

  13. Rapid and enhanced activation of microporous coordination polymers by flowing supercritical CO.sub.2

    Science.gov (United States)

    Matzger, Adam J.; Liu, Baojian; Wong-Foy, Antek G.

    2016-07-19

    Flowing supercritical CO.sub.2 is used to activate metal organic framework materials (MOF). MOFs are activated directly from N,N-dimethylformamide (DMF) thus avoiding exchange with a volatile solvent. Most MCPs display increased surface areas directly after treatment although those with coordinatively unsaturated metal centers benefit from additional heating.

  14. Polymer based interfaces as bioinspired 'smart skins'.

    Science.gov (United States)

    De Rossi, Danilo; Carpi, Federico; Scilingo, Enzo Pasquale

    2005-11-30

    This work reports on already achieved results and ongoing research on the development of complex interfaces between humans and external environment, based on organic synthetic materials and used as smart 'artificial skins'. They are conceived as wearable and flexible systems with multifunctional characteristics. Their features are designed to mimic or augment a broad-spectrum of properties shown by biological skins of humans and/or animals. The discussion is here limited to those properties whose mimicry/augmentation is achievable with currently available technologies based on polymers and oligomers. Such properties include tactile sensing, thermal sensing/regulation, environmental energy harvesting, chromatic mimetism, ultra-violet protection, adhesion and surface mediation of mobility. Accordingly, bioinspired devices and structures, proposed as suitable functional analogous of natural architectures, are analysed. They consist of organic piezoelectric sensors, thermoelectric and pyroelectric sensors and generators, photoelectric generators, thermal and ultra-violet protection systems, electro-, photo- and thermo-chromic devices, as well as structures for improved adhesion and reduced fluid-dynamic friction.

  15. Synthesis and Crystal Structure of a Novel 1D Mercury(II) Iodide Coordination Polymer Containing 40-Membered Macrocycle%Synthesis and Crystal Structure of a Novel 1D Mercury(II) Iodide Coordination Polymer Containing 40-Membered Macrocycle

    Institute of Scientific and Technical Information of China (English)

    GAN Xiao-Ping; KONG Ling; WU Peng; LV Chen; TU Yu-Long; CHEN Yi-Xin; ZHOU Hong-Ping; WU Jie-Ying; TIAN Yu-Peng

    2011-01-01

    A mercury coordination polymer [Hg3(TizT)216]n (Mr = 1921.72, TizT = 2,4,6- tri(imidazole- 1-yl)- 1,3,5-triazine) containing a 40-membered macrocycle which was constructed by four TizT ligands and four mercury(II) iodide molecules had been synthesized by the reaction of HgI2 with TizT. The complex was characterized by elemental analysis, FT-IR, ^1H NMR spectra and X-ray crystallography. The crystal of the complex belongs to the monoclinic system and C2/c space group with a = 35.840(5), b = 8.169(5), c = 14.980(5) A, β = 104.466(5)°, Z= 4, V= 4247(3) A^3, De = 3.006 g·cm^-3, μ= 15.223 mm^-1, F(000) = 3384, Rint = 0.0504, wR = 0.0833 and constructs a chair-like conformation of cyclohexane one by one, which forms a 1-D polymer through the fashion of fused ring aromatic hydrocarbon. The hydrogen bonds and π-π interactions shape the 2-D network structure. The two compounds excited weak fluorescence.

  16. Superacid-Based Lithium Salts For Polymer Electrolytes

    Science.gov (United States)

    Nagasubramanian, Ganesan; Prakash, Surya; Shen, David H.; Surampudi, Subbarao; Olah, George

    1995-01-01

    Solid polymer electrolytes exhibiting high lithium-ion conductivities made by incorporating salts of superacids into thin films of polyethylene oxide (PEO). These and other solid-polymer electrolytes candidates for use in rechargeable lithium-based electrochemical cells. Increases in room-temperature lithium-ion conductivities of solid electrolytes desirable because they increase achievable power and energy densities.

  17. Aromatic N-oxides in construction of different carboxylate coordination polymers of zinc(II), cadmium(II) and mercury(II)

    Science.gov (United States)

    Sarma, Rupam; Baruah, Jubaraj B.

    2011-09-01

    The coordination polymers [Zn(C 6H 5COO) 2(PNO)] n ( 1), [Zn 2(C 6H 5COO) 4(4,4'-BPNO)] n ( 2), [Zn 4(C 6H 4C 2O 4) 4(4,4'-BPNO) 2(H 2O) 5] n· nH 2O ( 3), [Cd(C 6H 5COO) 2(PNO)] n ( 4), [Cd 3(C 6H 5COO) 6(4,4'-BPNO) 2] n·2 nH 2O ( 5), [Cd(C 6H 4C 2O 4)(4,4'-BPNO)(H 2O)] n ( 6) and [Hg(C 6H 5COO) 2(4,4'-BPNO) 2] n ( 7), (where PNO = pyridine N-oxide, 4,4'-BPNO = 4,4'-bipyridyl- N,N'-dioxide) are synthesized and structurally characterized. The structures of these coordination polymers exhibit mononuclear to trinuclear nodes built by ligation of carboxylate to metal ions connected by N-oxide ligands. Pyridine N-oxide interconnects metal nodes by acting as μ 2-bridging ligand in complexes 1, and 4. In the linear coordination polymer 2, the paddle wheel structure of zinc(II) benzoate units are interconnected by 4,4'-bipyridyl- N,N'-dioxide which acts as a bidentate spacer ligand adopting a trans μ 2-η 1 : η 1 coordination mode. The polymeric structure of 3 formed by terephthalate and 4,4'-bipyridyl- N,N'-dioxide with zinc(II) contains self-assembled dinuclear Zn 2O 2 type of carboxylate cores, with 4,4'-bipyridyl- N,N'-dioxide coordinating through cis μ 2-η 1 : η 1 coordination mode. The cadmium coordination polymer 5, comprising of 4,4'-bipyridyl- N,N'-dioxide and benzoate, has trinuclear cadmium benzoate cores wherein the terminal cadmium ions are interconnected by monodentate 4,4'-bipyridyl- N,N'-dioxide bridges. The coordination polymer 6 comprises of mononuclear cadmium nodes independently bridged by terephthalate and 4,4'-bipyridyl- N,N'-dioxide thereby leading to a 3-fold interpenetrated three dimensional network. Double helical polymeric structure is observed in the coordination polymer 7 derived from mononuclear mercury(II) benzoate nodes bridged by 4,4'-bipyridyl- N,N'-dioxide with cis μ 2-η 1 : η 1 coordination mode.

  18. The cytotoxic effect of denture base polymers.

    Science.gov (United States)

    Hensten-Pettersen, A; Wictorin, L

    1981-01-01

    The cytotoxic potential of autopolymerized pour and dough type resins and heat cured resins was studied by in vitro cell culture techniques. Human epithelial cells (NCTC 2544) were grown in Eagle's minimal essential medium on the surface of the polymer disks. The cell multiplication on the surface of the specimens was measured. One heat cured resin and one pour type resin demonstrated a slight cytotoxic effect. The other polymers gave a moderate cytotoxic effect. The study did not indicate any difference in the cytotoxicity of the polymers when manufactured by alternate processing methods.

  19. Mixed ligand coordination polymers with flexible bis-imidazole linker and angular sulfonyldibenzoate: Crystal structure, photoluminescence and photocatalytic activity

    Energy Technology Data Exchange (ETDEWEB)

    Bisht, Kamal Kumar; Rachuri, Yadagiri [Analytical Discipline and Centralized Instrument Facility, CSIR—Central Salt and Marine Chemicals Research Institute, Council of Scientific and Industrial Research, G. B. Marg, Bhavnagar-364 002, Gujarat (India); Academy of Scientific and Innovative Research (AcSIR), CSIR—Central Salt and Marine Chemicals Research Institute, Council of Scientific and Industrial Research, G. B. Marg, Bhavnagar-364 002, Gujarat (India); Parmar, Bhavesh [Analytical Discipline and Centralized Instrument Facility, CSIR—Central Salt and Marine Chemicals Research Institute, Council of Scientific and Industrial Research, G. B. Marg, Bhavnagar-364 002, Gujarat (India); Suresh, Eringathodi, E-mail: esuresh@csmcri.org [Analytical Discipline and Centralized Instrument Facility, CSIR—Central Salt and Marine Chemicals Research Institute, Council of Scientific and Industrial Research, G. B. Marg, Bhavnagar-364 002, Gujarat (India); Academy of Scientific and Innovative Research (AcSIR), CSIR—Central Salt and Marine Chemicals Research Institute, Council of Scientific and Industrial Research, G. B. Marg, Bhavnagar-364 002, Gujarat (India)

    2014-05-01

    Four ternary coordination polymers (CPs) namely, ([Ni(SDB)(BITMB)(H{sub 2}O)]·H{sub 2}O){sub n} (CP1), ([Cd(SDB)(BITMB) (H{sub 2}O)]·(THF)(H{sub 2}O)){sub n} (CP2), ([Zn{sub 2}(SDB){sub 2}(BITMB)]·(THF){sub 2}){sub n} (CP3) and ([Co{sub 2}(SDB){sub 2}(BITMB)]·(Dioxane){sub 3}){sub n} (CP4) composed of angular dicarboxylate SDB (4,4'-sulfonyldibenzoate) and N-donor BITMB (1,3-bis(imidazol-1-ylmethyl)-2,4,6-trimethyl benzene) have been synthesized by solvothermal reactions and characterized by single crystal X-ray diffraction and other physico-chemical techniques. CP1 possesses one-dimensional ribbon type metal–organic motifs glued together by H-bonds and π⋯π interactions, whereas CP2–CP4, exhibit non-interpenetrated sql networks supported by weak supramolecular interactions. Structural diversity of these CPs can be attributed to the coordination geometry adopted by the metal nodes, versatile coordination modes of SDB and conformational flexibility of BITMB. Solid state luminescence properties of CP1–CP4 were explored. Photocatalytic performance of all CPs for the decomposition of metanil yellow by dilute hydrogen peroxide in the presence of visible light was also investigated. 25–83% dye removal from aqueous solutions in the presence of CP1–CP4 was observed. - Graphical abstract: Four new ternary transition metal CPs have been hydrothermally prepared and their structural aspects as well as photocatalytic activity for decolourization of metanil yellow (MY) dye have been investigated. - Highlights: • Four ternary coordination polymers containing Ni, Cd, Zn and Co center are prepared. • Crystal structure and thermal stability of all four CPs has been described. • PL and diffuse reflectance spectra of synthesized CPs have also been examined. • Band gap values suggest semiconducting behavior of prepared CPs. • Photocatalytic activity of CPs for oxidative degradation of metanil yellow is studied.

  20. The Diphosphorus Complex [Cp2Mo2(CO)4(η(2)-P2)] as a Building Block for the Synthesis of Mixed-Hybrid Coordination Polymers.

    Science.gov (United States)

    Moussa, Mehdi Elsayed; Attenberger, Bianca; Fleischmann, Martin; Schreiner, Andrea; Scheer, Manfred

    2016-10-01

    The three-component reaction of the tetrahedral diphosphorus complex [Cp2Mo2(CO)4(η(2)-P2)] (1), with Ag[BF4] (2) in the presence of 2,2'-bipyrimidine (3) leads to the formation of the two novel two-dimensional networks 4 and 5. Compound 4 is a new two-dimensional organometallic-organic hybrid polymer, while derivative 5 represents a unique two-dimensional organometallic-inorganic-organic hybrid polymer. These results show the possibility of synthesizing a new class of coordination polymers, which could not be obtained from two-component reactions with organic molecules in addition of metal ions.

  1. Synthesis, Structure and Properties of Three-dimensional Gd(Ⅲ), Eu(Ⅲ) Coordination Polymers via in situ Decarboxylation

    Institute of Scientific and Technical Information of China (English)

    WANG Chuan-sheng; GU Xiao-fu; SUN Ya-guang; GAO En-jun; ZHANG Wan-zhong

    2009-01-01

    Two three-dimensional lanthanide(Ⅲ) coordination polymers with the formula [Ln(PYDC)(NA)(H_2O)]n [Ln=Gd(l), Eu(2), H2PYDC=pyridine-2,5-bicarboxylic acid, HNA=nicotinic acid] have been hydrothermally synthesized and characterized by elemental analysis, IR, and single crystal X-ray diffraction. The NA came from in situ decarboxylation of the part of PYDC. X-ray single crystal structural analyses reveal that complexes 1 and 2 are iso-morphous, they possess the 4~3·6~3 topology assembled by Gd~(3+)/Eu~(3+) and two different multidentate carboxylate ligands. Magnetic measurements show that antiferromagnetic coupling exists between adjacent Gd~(3+) ions in complex 1. The complex 2 exhibits the corresponding characteristic luminescence in the visible region under an excitation at 305 nm.

  2. Hydrothermal Synthesis, Crystal Structure, and Characterization of a Novel Terbium(Ⅲ) Coordination Polymer Bridged by 5-Sulfoisophthalate Trivalent Anions

    Institute of Scientific and Technical Information of China (English)

    2007-01-01

    Hydrothermal reaction of terbium( Ⅲ ) chloride with 5-sulfoisophthalic acid monosodium salt and 1, 10-phenanthroline(phen) at 415 K resulted in the formation of a novel coordination polymer, [Tb(sip) (phen) (H2O)]n( sip = 5-sulfoisophthalate trivalent anion) with a three-dimensional network structure. Each centrosymmetrically related pair of terbium ions are linked by two sip anions, forming a binuclear unit, and each binuclear unit links to four adjacent tetranuclear units, extending a two-dimensional hybrid layer at crystallographic bc plane. On the other hand,every three-terbium ion is connected by three sip anions, generating a trinuclear ring, and the trinuclear ring connects six neighboring trinuclear rings to produce another two-dimensional layer at crystallographic ab plane. Moreover, each sip anion acts as a pentadentate bridge, interconnecting two different types of layers to yield a novel three-dimensional framework.

  3. Synthesis, structure and properties of a 3D acentric coordination polymer with noninterpenetrated (10,3)-d topology

    Science.gov (United States)

    Lun, Huijie; Li, Xuefei; Wang, Xiao; Li, Haiyan; Li, Yamin; Bai, Yan

    2017-01-01

    A new coordination polymer, {[Mn(HPIDC)(H2O)]·2H2O}n (1) (H3PIDC = 2-(pyridin-4-yl)-1H-imidazole-4,5-dicarboxylic acid), has been obtained by hydrothermal method and structurally characterized by X-ray single crystal diffraction, elemental analysis and thermogravimetric analysis (TGA). X-ray single crystal diffraction reveals that compound 1 crystallizing in acentric Pna21 space group, exhibits an ultimate racemic three-dimension framework with rare noninterpenetrated (10,3)-d (or utp) topology due to the alternate array of left- and right-handed helixes. Moreover, compound 1 also features ferroelectric, nonlinear optical (NLO) and antiferromagnetic behaviors.

  4. Monomers, dimers, and trimers of [Au(CN2]− in a Ba(diaza-18-crown-62+ coordination polymer

    Directory of Open Access Journals (Sweden)

    2009-03-01

    Full Text Available The structure of the title compound, poly[triaquatetra-μ-cyanido-tetracyanidobis(1,4,10,13-tetraoxa-7,16-diazacyclooctadecanedibarium(IItetragold(I], [Au4Ba2(CN8(C12H26N2O42(H2O3]n, displays O—H...N hydrogen bonding between water molecules and cyano ligands and an unusual pattern of aurophilic interactions that yields a monomer, dimer, and trimer of [Au(CN2]− within the same crystal structure. In two of the five Au positions, the atom resides on a center of inversion. The overall arrangement is that of a coordination polymer assisted by aurophilic and hydrogen-bonded interactions.

  5. 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).

  6. Sonochemical synthesis of two new nano lead(II) coordination polymers: Evaluation of structural transformation via mechanochemical approach.

    Science.gov (United States)

    Aboutorabi, Leila; Morsali, Ali

    2016-09-01

    Two new lead(II) mixed-ligand coordination polymers, [Pb(PNO)(SCN)]n (1) and [Pb(PNO)(N3)]n (2), (HPNO=picolinic acid N-oxide) were synthesized by a sonochemical method and characterized by scanning electron microscopy, X-ray powder diffraction, IR spectroscopy and elemental analysis. Compounds 1 and 2 were structurally characterized by single crystal X-ray diffraction. The thermal behavior of 1 and 2 were studied by thermal gravimetric analysis. Structural transformations of compounds 1 and 2 were evaluated through anion-replacement processes by mechanochemical method. Moreover, the effect of sonication conditions including time, concentrations of initial reagents and power of irradiation were evaluated on size and morphology of compounds 1 and 2.

  7. Porous polymers based on aryleneethynylene building blocks.

    Science.gov (United States)

    Bunz, Uwe H F; Seehafer, Kai; Geyer, Florian L; Bender, Markus; Braun, Ingo; Smarsly, Emanuel; Freudenberg, Jan

    2014-09-01

    Porous conjugated polymers are synthesized by metal-catalyzed coupling reactions. The progress for porous polymers when planar or tetrahedral building blocks are connected by alkyne units into novel materials is highlighted. The most prominent reaction for the buildup of the microporous alkyne-bridged polymers is the Sonogashira reaction, connecting alkynes to aromatic iodides or bromides. The availability of the building blocks and the potency of the Sonogashira reaction allow preparing a large variety of intrinsically porous polymeric materials, in which rigid struts connect multipronged centers. The microporous polymers are used as catalysts and as storage materials for gases and sensors. Postfunctionalization schemes, understanding of structure-property relationships, and the quest for high porosity are pertinent.

  8. Graphene-based polymer nanocomposites in electronics

    CERN Document Server

    Sadasivuni, Kishor Kumar; Kim, Jaehwan

    2015-01-01

    This book covers graphene reinforced polymers, which are useful in electronic applications, including electrically conductive thermoplastics composites, thermosets and elastomers. It systematically introduces the reader to fundamental aspects and leads over to actual applications, such as sensor fabrication, electromagnetic interference shielding, optoelectronics, superconductivity, or memory chips. The book also describes dielectric and thermal behaviour of graphene polymer composites - properties which are essential to consider for the fabrication and production of these new electronic materials. The contributions in this book critically discuss the actual questions in the development and applications of graphene polymer composites. It will thus appeal to chemists, physicists, materials scientists as well as nano technologists, who are interested in the properties of graphene polymer composites.

  9. Conducting polymer based biomolecular electronic devices

    Indian Academy of Sciences (India)

    B D Malhotra; Rahul Singhal

    2003-08-01

    Biomolecular electronics is rapidly evolving from physics, chemistry, biology, electronics and information technology. Organic materials such as proteins, pigments and conducting polymers have been considered as alternatives for carrying out the functions that are presently being performed by semiconductor silicon. Conducting polymers such as polypyrroles, polythiophenes and polyanilines have been projected for applications for a wide range of biomolecular electronic devices such as optical, electronic, drug-delivery, memory and biosensing devices. Our group has been actively working towards the application of conducting polymers to Schottky diodes, metal–insulator–semiconductor (MIS) devices and biosensors for the past 10 years. This paper is a review of some of the results obtained at our laboratory in the area of conducting polymer biomolecular electronics.

  10. Effect of Solvent Molecule in Pore for Flexible Porous Coordination Polymer upon Gas Adsorption and Iodine Encapsulation.

    Science.gov (United States)

    Arıcı, Mürsel; Yeşilel, Okan Zafer; Taş, Murat; Demiral, Hakan

    2015-12-07

    Four new Zn(II)-coordination polymers, namely, [Zn2(μ6-ao2btc)(μ-obix)2]n (1), [Zn2(μ4-ao2btc)(μ-obix)2]n (2), [Zn2(μ4-ao2btc)(μ-mbix)2]n (3), and {[Zn2(μ4-ao2btc)(μ-pbix)2] · 2DMF · 8H2O}n (4), where ao2btc = dioxygenated form of 3,3',5,5'-azobenzenetetracarboxylate and obix, mbix, and pbix = 1,2-, 1,3-, and 1,4-bis(imidazol-1-ylmethyl)benzene, have been synthesized with azobenzenetetracarboxylic acid and isomeric bis(imidazole) ligands and characterized by elemental analyses, IR spectra, single-crystal X-ray diffraction, powder X-ray diffraction, and thermal analyses. X-ray results showed that 1, 2, and 4 had two-dimensional structures with 3,4L13 topology, while 3 was a three-dimensional coordination polymer with bbf topology. For 4, two types of activation strategies, solvent exchange + heating (which produced 4a) and direct heating (which produced 4b), were used to investigate the effect of a guest molecule in a flexible framework. Gas adsorption and iodine encapsulation properties of activated complexes were studied. The CO2 uptake capacities for 4a and 4b were 3.62% and 9.50%, respectively, and Langmuir surface areas calculated from CO2 isotherms were 167.4 and 350.7 m(2)/g, respectively. Moreover, 4b exhibited 19.65% and 15.27% iodine uptake in vapor phase and cyclohexane solution, respectively, which corresponded to 1.47 and 0.97 molecules of iodine/formula unit, respectively. Moreover, photoluminescence properties of the complexes were studied.

  11. Coordinates and intervals in graph-based reference genomes.

    Science.gov (United States)

    Rand, Knut D; Grytten, Ivar; Nederbragt, Alexander J; Storvik, Geir O; Glad, Ingrid K; Sandve, Geir K

    2017-05-18

    It has been proposed that future reference genomes should be graph structures in order to better represent the sequence diversity present in a species. However, there is currently no standard method to represent genomic intervals, such as the positions of genes or transcription factor binding sites, on graph-based reference genomes. We formalize offset-based coordinate systems on graph-based reference genomes and introduce methods for representing intervals on these reference structures. We show the advantage of our methods by representing genes on a graph-based representation of the newest assembly of the human genome (GRCh38) and its alternative loci for regions that are highly variable. More complex reference genomes, containing alternative loci, require methods to represent genomic data on these structures. Our proposed notation for genomic intervals makes it possible to fully utilize the alternative loci of the GRCh38 assembly and potential future graph-based reference genomes. We have made a Python package for representing such intervals on offset-based coordinate systems, available at https://github.com/uio-cels/offsetbasedgraph . An interactive web-tool using this Python package to visualize genes on a graph created from GRCh38 is available at https://github.com/uio-cels/genomicgraphcoords .

  12. Clean and Efficient Synthesis Using Mechanochemistry: Coordination Polymers, Metal-Organic Frameworks and Metallodrugs

    OpenAIRE

    Friščić, Tomislav; Halasz, Ivan; Štrukil, Vjekoslav; Maksić, Mirjana; Dinnebier, Robert E

    2012-01-01

    This review briefly discusses recent advances and future prospects in the mechanochemical synthesis of coordination compounds by ball milling and grinding, and highlights our contributions to the mechanosynthesis of porous metal-organic frameworks (MOFs) and zeolitic imidazolate frameworks (ZIFs), metal-organic pharmaceutical derivatives and metallodrugs using the recently developed mechanochemical methods of liquid-assisted grinding (LAG) and ion- and liquid-assisted grinding (ILAG). The...

  13. 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

  14. Revealing and tuning the core, structure, properties and function of polymer micelles with lanthanide-coordination complexes.

    Science.gov (United States)

    Wang, Junyou; Groeneveld, Andrea; Oikonomou, Maria; Prusova, Alena; Van As, Henk; van Lent, Jan W M; Velders, Aldrik H

    2016-01-07

    Controlling self-assembly processes is of great interest in various fields where multifunctional and tunable materials are designed. We here present the versatility of lanthanide-complex-based micelles (Ln-C3Ms) with tunable coordination structures and corresponding functions (e.g. luminescence and magnetic relaxation enhancement). Micelles are prepared by charge-driven self-assembly of a polycationic-neutral diblock copolymer and anionic coordination complexes formed by Ln(III) ions and the bis-ligand L2EO4, which contains two dipicolinic acid (DPA) ligand groups (L) connected by a tetra-ethylene oxide spacer (EO4). By varying the DPA/Ln ratio, micelles are obtained with similar size but with different stability, different aggregation numbers and different oligomeric and polymeric lanthanide(III) coordination structures in the core. Electron microscopy, light scattering, luminescence spectroscopy and magnetic resonance relaxation experiments provide an unprecedented detailed insight into the core structures of such micelles. Concomitantly, the self-assembly is controlled such that tunable luminescence or magnetic relaxation with Eu-C3Ms, respectively, Gd-C3Ms is achieved, showing potential for applications, e.g. as contrast agents in (pre)clinical imaging. Considering the various lanthanide(III) ions have unique electron configurations with specific physical chemical properties, yet very similar coordination chemistry, the generality of the current coordination-structure based micellar design shows great promise for development of new materials such as, e.g., hypermodal agents.

  15. 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.

  16. Bio-Based Polymers with Potential for Biodegradability

    OpenAIRE

    Thomas F. Garrison; Amanda Murawski; Rafael L. Quirino

    2016-01-01

    A variety of renewable starting materials, such as sugars and polysaccharides, vegetable oils, lignin, pine resin derivatives, and proteins, have so far been investigated for the preparation of bio-based polymers. Among the various sources of bio-based feedstock, vegetable oils are one of the most widely used starting materials in the polymer industry due to their easy availability, low toxicity, and relative low cost. Another bio-based plastic of great interest is poly(lactic acid) (PLA), wi...

  17. Norbornene-Based Polymer Electrolytes for Lithium Cells

    Science.gov (United States)

    Cheung, Iris; Smart, Marshall; Prakash, Surya; Miyazawa, Akira; Hu, Jinbo

    2007-01-01

    Norbornene-based polymers have shown promise as solid electrolytes for lithium-based rechargeable electrochemical cells. These polymers are characterized as single-ion conductors. Single-ion-conducting polymers that can be used in lithium cells have long been sought. Single-ion conductors are preferred to multiple-ion conductors as solid electrolytes because concentration gradients associated with multiple-ion conduction lead to concentration polarization. By minimizing concentration polarization, one can enhance charge and discharge rates. Norbornene sulfonic acid esters have been synthesized by a ring-opening metathesis polymerization technique, using ruthenium-based catalysts. The resulting polymer structures (see figure) include sulfonate ionomers attached to the backbones of the polymer molecules. These molecules are single-ion conductors in that they conduct mobile Li+ ions only; the SO3 anions in these polymers, being tethered to the backbones, do not contribute to ionic conduction. This molecular system is especially attractive in that it is highly amenable to modification through functionalization of the backbone or copolymerization with various monomers. Polymers of this type have been blended with poly(ethylene oxide) to lend mechanical integrity to free-standing films, and the films have been fabricated into solid polymer electrolytes. These electrolytes have been demonstrated to exhibit conductivity of 2 10(exp -5)S/cm (which is high, relative to the conductivities of other solid electrolytes) at ambient temperature, plus acceptably high stability. This type of norbornene-based polymeric solid electrolyte is in the early stages of development. Inasmuch as the method of synthesis of these polymers is inherently flexible and techniques for the fabrication of the polymers into solid electrolytes are amenable to optimization, there is reason to anticipate further improvements.

  18. Hybrid Thin Films Based Upon Polyoxometalates-Polymer Assembly

    Science.gov (United States)

    Qi, Na; Jing, Benxin; Zhu, Yingxi

    2014-03-01

    Block copolymers (BCPs) and polyoxometalates (POMs) have been used individually as building blocks for design and synthesis of novel functional materials. POM nanoclusters, the assemblies of transition metal oxides with well-defined atomic coordination structure, have been recently explored as novel nanomaterials... for catalysis, semiconductors, and even anti-cancer treatment due to their unique chemical, optical and electrical characteristics. We have explored the blending of inorganic POM nanocluster with BCPs into hierarchaically structured inorganic-organic hybrid nanocomposites. Using polystyrene-b-poly(ethylene oxide) (PS-b-PEO) thin films as the template, we have observed that the spatial organization of BCP thin films is modified by molybdenum based POM nanocluster to form 2D in-plane hexagonal ordered or 3D ordered network of POM-BCP assemblies, depending on the concentration ratio of POM to PS-b-PEO. The dielectric properties of such hybrid thin films can be enhanced by embedded POMs but show a strong dependence on the supramolecular structures of POM-polymer complexes. The assembly of nanoclusters in BCP-templated thin films could pave a new path to design new hybrid nanocomposites with uniquely combined functionality and material properties.

  19. Toward flexible polymer and paper-based energy storage devices.

    Science.gov (United States)

    Nyholm, Leif; Nyström, Gustav; Mihranyan, Albert; Strømme, Maria

    2011-09-01

    All-polymer and paper-based energy storage devices have significant inherent advantages in comparison with many currently employed batteries and supercapacitors regarding environmental friendliness, flexibility, cost and versatility. The research within this field is currently undergoing an exciting development as new polymers, composites and paper-based devices are being developed. In this report, we review recent progress concerning the development of flexible energy storage devices based on electronically conducting polymers and cellulose containing composites with particular emphasis on paper-based batteries and supercapacitors. We discuss recent progress in the development of the most commonly used electronically conducting polymers used in flexible device prototypes, the advantages and disadvantages of this type of energy storage devices, as well as the two main approaches used in the manufacturing of paper-based charge storage devices.

  20. 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.

  1. Single Spring Joint Element Based on the Mixed Coordinate System

    Directory of Open Access Journals (Sweden)

    Lanhao Zhao

    2015-01-01

    Full Text Available As a FEM for reinforced concrete bond-slip problems, one important feature of the typical double spring joint element method is the selection of the normal stiffness, which may cause the mutual embedding problem and bring challenges to the calculation. In this paper, a novel single spring joint element method based on the mixed coordinate system is proposed to simulate the interaction of two materials. Instead of choosing the normal stiffness arbitrarily, the proposed method makes DOFs of two materials in the normal direction equal to ensure deformation compatibility. And its solid elements for the concrete are solved in global coordinate system, while the beam elements for the steel bar are solved in local coordinate system. In addition, the proposed method can also be applied to RC structures with irregular arrangements of steel bars. Numerical examples demonstrate the validity and accuracy of the proposed approach. Furthermore, the bond model is applied to RC beams with the description of the damage process.

  2. The nanocrystalline coordination polymer of AMT-Ag for an effective detection of ciprofloxacin hydrochloride in pharmaceutical formulation and biological fluid.

    Science.gov (United States)

    Tiwari, Madhu; Kumar, Ashish; Shankar, Uma; Prakash, Rajiv

    2016-11-15

    The present report highlights a cost effective and portable AMT-Ag nanocrystalline coordination polymer (NCCP) based electrochemical sensor for an efficient sensing of biologically active drug molecule ciprofloxacin hydrochloride (CFX). The AMT-Ag NCCP, is synthesized using an easily accessible organic ligand 2-amino-5-mercapto-1,3,4-thiadiazole (AMT) with silver nitrate. In the infinite polymer array of AMT-Ag, silver (I) centers are bridged by tecton AMT through the exocyclic thiol and amino linkage. A successful ultra‒trace detection of CFX has been achieved due to the prominent electron channeling through the pores of polymeric nano-crystallites. The efficient charge transfer arises at the interface of electrolyte and AMT-Ag nano-crystals anchored electrode through hydrophobic interaction and π-π electron coupling. The voltammogram reveals the critical redox features of CFX and provides a clear representation about the steps involved in the AMT-Ag assisted oxidation of CFX. This specific signature further applied in the voltammetric assay of CFX in pharmaceutical formulation (eye drops) and biological fluid (urine) by a significantly high sensitivity (0.002µA/µM and 0.007µA/µM) and detection limit (22nM and 60nM) respectively without any interference. Therefore, the developed AMT-Ag NCCP could serve as a highly valuable platform for the fabrication of high-performance electrochemical sensors for the detection of biologically important drug molecules.

  3. Deconvolution of the role of metal and pH in metal coordinating polymers

    Science.gov (United States)

    Cazzell, Seth; Holten-Andersen, Niels

    Nature uses metal binding amino acids to engineer both mechanical properties and structural functionality. Some examples of this metal binding behavior can be found in both mussel foot protein and DNA binding protein. The mussel byssal thread contains reversible intermolecular protein-metal bonds, allowing it to withstand harsh intertidal environments. Zinc fingers form intramolecular protein-metal bonds to stabilize the tertiary structure of DNA binding proteins, allowing specific structural functionality. Inspired by both these metal-binding materials, we present mechanical and spectroscopic characterization of a model polymer system, designed to mimic this bonding. Through these studies, we are able to answer fundamental polymer physics questions, such as the role of pH and metal to ligand ratio, illuminating both the macroscopic and microscopic material behavior. These understandings further bio-inspired engineering techniques that are used to design viscoelastic soft materials. I was supported by the Department of Defense (DoD) through the National Defense Science & Engineering Graduate Fellowship (NDSEG) Program.

  4. Two New Dicyanamide Coordination Polymers with Alternating Parallel Chains: {Mn(dmpz)[N(CN)2]2}2 and {Cu(dmpz)[N(CN)2]2}2

    Institute of Scientific and Technical Information of China (English)

    罗俊; 周锡庚; 侯秀峰; 吴惠霞; 翁林红; 李艳荣

    2005-01-01

    Two new dicyanamide coordination polymers, {Mn(dmpz)[N(CN)2]2}2 (1) and {Cu(dmpz)[N(CN)2]2}2 (2)(dmpz=3,5-dimethylpyrazole), were synthesized and characterized by single crystal X-ray diffraction analysis and IR spectroscopy. In 1 and 2 the metal ions have two different coordination modes, where one is coordinated to four dicyanamide anions and two monodentate dmpz molecules to form a slightly distorted octahedral geometry, while the other adopts octahedral geometry, surrounded by four nitrile N atoms and two amide N atoms of the dicyanamide anions. Both complexes contain two alternating chains that are parallel to each other.

  5. Responsive supramolecular polymer metallogel constructed by orthogonal coordination-driven self-assembly and host/guest interactions.

    Science.gov (United States)

    Yan, Xuzhou; Cook, Timothy R; Pollock, J Bryant; Wei, Peifa; Zhang, Yanyan; Yu, Yihua; Huang, Feihe; Stang, Peter J

    2014-03-26

    An emerging strategy for the fabrication of advanced supramolecular materials is the use of hierarchical self-assembly techniques wherein multiple orthogonal interactions between molecular precursors can produce new species with attractive properties. Herein, we unify the spontaneous formation of metal-ligand bonds with the host/guest chemistry of crown ethers to deliver a 3D supramolecular polymer network (SPN). Specifically, we have prepared a highly directional dipyridyl donor decorated with a benzo-21-crown-7 moiety that undergoes coordination-driven self-assembly with a complementary organoplatinum acceptor to furnish hexagonal metallacycles. These hexagons subsequently polymerize into a supramolecular network upon the addition of a bisammonium salt due to the formation of [2]pseudorotaxane linkages between the crown ether and ammonium moieties. At high concentrations, the resulting 3D SPN becomes a gel comprising many cross-linked metallohexagons. Notably, thermo- and cation-induced gel-sol transitions are found to be completely reversible, reflecting the dynamic and tunable nature of such supramolecular materials. As such, these results demonstrate the structural complexity that can be obtained when carefully controlling multiple interactions in a hierarchical fashion, in this case coordination and host/guest chemistry, and the interesting dynamic properties associated with the materials thus obtained.

  6. Structural and spectral properties of a zinc(II) coordination polymer: a combined experimental and theoretical study.

    Science.gov (United States)

    Hao, Jin-Ming; Li, Guang-Yue; Li, Yue-Hua; Cui, Guang Hua

    2014-10-15

    A novel 1D zinc(II) coordination polymer [Zn(bbbm)Cl2]n (where bbbm=1,4-bis(N-benzimidazolyl)butane) was synthetized by ZnCl2 and bbbm ligand under hydrothermal conditions, and its structural and spectral properties were studied by both experimental and theoretical techniques. The center zinc(II) ion displays four-coordinated in a tetrahedral geometry by two chloride anions and two N atoms of distinct bbbm ligands. Adjacent chains are further connected into a 2D layer structure through π-π stacking interactions. Vibrational frequencies of [Zn(bbbm)Cl2]n have been calculated using DFT/B3LYP/TZVP method, and well reproduced IR data. Furthermore, the vertical excitation energies from time-dependent DFT calculation confirmed that the fluorescent peaks at 385nm and 450nm could respectively be assigned to the π→π(*) transition within the bbbm ligands and π→n transition from chloride anion to bbbm ligand.

  7. 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.

  8. Revealing and tuning the core, structure, properties and function of polymer micelles with lanthanide-coordination complexes

    NARCIS (Netherlands)

    Wang, J.; Groeneveld, A.; Oikonomou, M.E.; Prusova, A.; As, van H.; Lent, van J.W.M.; Velders, A.H.

    2016-01-01

    Controlling self-assembly processes is of great interest in various fields where multifunctional and tunable materials are designed. We here present the versatility of lanthanide-complex-based micelles (Ln-C3Ms) with tunable coordination structures and corresponding functions (e.g. luminescence and

  9. Highly selective CO2 adsorption accompanied with low-energy regeneration in a two-dimensional Cu(II) porous coordination polymer with inorganic fluorinated PF6(-) anions.

    Science.gov (United States)

    Noro, Shin-ichiro; Hijikata, Yuh; Inukai, Munehiro; Fukushima, Tomohiro; Horike, Satoshi; Higuchi, Masakazu; Kitagawa, Susumu; Akutagawa, Tomoyuki; Nakamura, Takayoshi

    2013-01-01

    High selectivity and low-energy regeneration for adsorption of CO(2) gas were achieved concurrently in a two-dimensional Cu(II) porous coordination polymer, [Cu(PF(6))(2)(4,4'-bpy)(2)](n) (4,4'-bpy = 4,4'-bipyridine), containing inorganic fluorinated PF(6)(-) anions that can act as moderate interaction sites for CO(2) molecules.

  10. The coating of conducting copolymer on coordination polymer nanorod: A visible light active p-n heterojunction photocatalyst for H2 production

    Science.gov (United States)

    Jia, Yuan; Mei, Ming-liang; Xu, Xin-xin; Wang, Lin-shan

    2016-06-01

    A visible light active p-n heterojunction photocatalyst was synthesized successfully through in-situ chemical oxidation copolymerization of aniline (ANI) and diphenylamine-4-sulfonate (DPAS) with the existence of coordination polymer nanorod (CPNR) under initiation of ammonium persulfate (APS). Compared with neat coordination polymer nanorod, the resulted p-n heterojunction photocatalyst exhibits higher H2 generationrate under visible light irradiation. In this heterojunction photocatalyst, as a p-type semiconductor possessing suitable energy levels with coordination polymer nanorod, poly-(aniline-co-N-(4-sulfophenyl)-aniline) (PAPSA) forms p-n heterojunction with n-type coordination polymer nanorod, the inner electric field of p-n heterojunction accelerates the separation of electrons and holes, which enhances H2 production performance. Furthermore, the influence of concentration ratio between DPAS and ANI on photocatalytic property of the p-n heterojunction photocatalyst was discussed and a reasonable condition to fabricate photocatalyst with high H2 generationrate had been obtained. During photocatalytic water splitting H2 generation, the p-n heterojunction photocatalyst exhibited outstanding stability.

  11. First examples of two ferromagnetic end-to-end cyanate bridged 1D linear coordination polymers of nickel(II) containing an unsymmetrical diamine.

    Science.gov (United States)

    Choubey, Somnath; Bhar, Kishalay; Chattopadhyay, Soumi; Hazra, Arpan; Maji, Tapas Kumar; Ribas, Joan; Ghosh, Barindra Kumar

    2012-10-14

    Two new end-to-end (EE) cyanate bridged 1D coordination polymers of Ni(II) are isolated which contain linear (180°) Ni-N-C and Ni-O-C angles in Ni-NCO-Ni bridges and show ferromagnetic (F) coupling in agreement with the reported theoretical model for linear EE bridges.

  12. Conducting-polymer-based supercapacitor devices and electrodes

    Science.gov (United States)

    Snook, Graeme A.; Kao, Pon; Best, Adam S.

    Supercapacitor electrodes and devices that utilise conducting polymers are envisaged to bridge the gap between existing carbon-based supercapacitors and batteries to form units of intermediate specific energy. This review looks at the major conducting polymer materials, namely, polyaniline, polypyrrole, polythiophene and derivatives of polythiophene, as well as composites of these materials with carbon nanotubes and inorganic battery materials. Various treatments of the conducting polymer materials to improve their properties are considered and comparisons are made with other supercapacitor materials such as carbon and with inorganic battery materials. Conducting polymers are pseudo-capacitive materials, which means that the bulk of the material undergoes a fast redox reaction to provide the capacitive response and they exhibit superior specific energies to the carbon-based supercapacitors (double-layer capacitors). In general conducting polymers are more conductive than the inorganic battery materials and consequently have greater power capability. On the downside, conducting polymers swell and contract substantially on charge and discharge, respectively. Consequently, cycle-life is poor compared with carbon-based supercapacitors which generally only charge via adsorption and desorption of ions (giving typically a few thousand cycles for conducting polymers compared with >500 000 cycles for carbon-based devices).

  13. The coordination chemistry of two symmetric fluorene-based organic ligands with cuprous chloride.

    Science.gov (United States)

    Liu, Yan-Fei; Zhao, Chao-Wei; Ma, Jian-Ping; Liu, Qi-Kui; Dong, Yu-Bin

    2013-12-15

    Two novel symmetric fluorene-based ligands, namely, 2,7-bis(1H-imidazol-1-yl)-9,9-dimethyl-9H-fluorene [L1 or (I), C21H18N4] and 2,7-bis(1H-imidazol-1-yl)-9,9-dipropyl-9H-fluorene (L2), have been used to construct the coordination polymers catena-poly[[dichloridodicopper(I)(Cu-Cu)]-μ-2,7-bis(1H-imidazol-1-yl)-9,9-dimethyl-9H-fluorene], [Cu2Cl2(C21H18N4)]n, (II), and catena-poly[[tetra-μ2-chlorido-tetracopper(I)]-bis[μ-2,7-bis(1H-imidazol-1-yl)-9,9-dipropyl-9H-fluorene

  14. Derivation and Testing of Explicit Equations of Motion for Polymers Described by Internal Coordinates

    Science.gov (United States)

    Mazur, A. K.; Dorofeev, V. E.; Abagyan, R. A.

    1991-02-01

    General Lagrange's equations of motion for a system of polymeric molecules are obtained in an explicit form. They can be used for simulating molecular dynamics of large molecules. The molecular conformations are described by internal coordinates, i.e., bond lengths, valence angles, and torsion angles. The equations derived permit any internal degrees of freedom to be frozen. The method is applied to an oligopeptide in an α-helical conformation. Three models of the molecule with different degrees of fixation are compared. It is shown that the method permits one to increase significantly the time step in molecular dynamics calculations.

  15. Assembling one-dimensional coordination polymers into threedimensional architectures via hydrogen bonds

    Indian Academy of Sciences (India)

    Lalit Rajput; Madhushree Sarkar; Kumar Biradha

    2010-09-01

    The reactions of bis(pyridylcarboxamido)alkanes (amides) and bis(3-pyridyl)alkanediamides (reverse amides) with copper(II) and zinc(II) in the presence of various anions resulted in onedimensional polymeric crystalline complexes with or without guest inclusion. The crystal structure 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$\\cdots$O hydrogen bonds.

  16. Novel Coordination Polymers Constructed from 4,4'-Bipyridine and Phosphate

    Institute of Scientific and Technical Information of China (English)

    Kwang-Hwa; Lii

    2001-01-01

    The synthesis of open-fiamework metal phosphates has been a subject of intense research owing to their interesting structural chemistry and potential applications as ionexchangers, catalysts and adsorbents. A large number of these materials are synthesized in the presence of organic amines as structure-directing agents. Recently, many research activities have focused on the synthesis of inorganic-organic hybrid frameworks. As compared with inorganic ligands, the advantage of using organic multidentate ligands is the efficacy of rational design of crystalline solids through their coordinating propensities and geometries.  ……

  17. Novel Coordination Polymers Constructed from 4,4'-Bipyridine and Phosphate

    Institute of Scientific and Technical Information of China (English)

    Kwang-Hwa Lii

    2001-01-01

    @@ The synthesis of open-fiamework metal phosphates has been a subject of intense research owing to their interesting structural chemistry and potential applications as ionexchangers, catalysts and adsorbents. A large number of these materials are synthesized in the presence of organic amines as structure-directing agents. Recently, many research activities have focused on the synthesis of inorganic-organic hybrid frameworks. As compared with inorganic ligands, the advantage of using organic multidentate ligands is the efficacy of rational design of crystalline solids through their coordinating propensities and geometries.

  18. Design and solvothermal synthesis of luminescent copper(I)-pyrazolate coordination oligomer and polymer frameworks.

    Science.gov (United States)

    He, Jun; Yin, Ye-Gao; Wu, Tao; Li, Dan; Huang, Xiao-Chun

    2006-07-21

    Two luminescent coordination compounds, [Cu(Pz)]3 (1) and [Cu2(Bpz)]n (2), were isolated from solvothermal reactions of Cu(NO3)2 with 3,5-dimethylpyrazole (HPz) and 3,3',5,5'-tetra-methyl-4,4'-bipyrazole (H2Bpz) respectively in the presence of NH3, of which 1 was revealed to be a planar trimer and 2 a three-dimensional framework, presenting a rare 3-connected binodal (6(2).10)(6.10(2)) topology and eight-fold interpenetration.

  19. Alternating current organic light emitting diodes based on polymer heterojunction

    Institute of Scientific and Technical Information of China (English)

    Yewen Jiang(蒋业文); Haishu Tan(谭海曙); Jianquan Yao(姚建铨)

    2003-01-01

    Most alternating current (ac) polymer EL (electroluminescent) devices to date are based on symmetricalstructure. Here novel alternating current EL devices with asymmetric structure are successfully fabricatedby using a hole type polymer PDDOPV [poly (2,5-bis (dodecyloxy)-phenylenevinylene)] and an electrontype polymer PPQ [poly (phenyl quinoxaline)]. We report that performance of polymer devices withheterojunction in ac operation is not so sensitive to thickness of the two polymer layers as in direct current(dc) operation. This new advantage of ac operation mode over dc means easy production and cheapfacilities in large-scale production in the near future. Different emission spectra are obtained when ourac devices operate in ac mode, forward and reverse bias. Emission spectrum at reverse bias includes twoparts: one is from PDDOPV, the other is from PPQ.

  20. Poly(hydroxyethyl methacrylate) based networked solid polymer electrolyte.

    Science.gov (United States)

    Lee, A-Ran; Kim, Young-Deok; Lee, Sang-Keol; Jo, Nam-Ju

    2013-10-01

    Solid polymer electrolytes (SPEs) have good safety for lithium battery compared to liquid electrolytes, but they have low ionic conductivity. To solve the problem, the polymer-in-salt system was introduced which has higher ionic conductivity than salt-in-polymer system. However, polymer-in-salt system has disadvantages that are poor mechanical properties with increasing salt concentration. In this study, networked polymer electrolytes consisting of poly(hydroxyethyl methacrylate) (P(HEMA)), lithium triflate (LiCF3SO3, LiTf) and hydrochloric acid (HCl) were prepared. And the electrochemical and mechanical properties of P(HEMA) based SPEs were investigated by using ac impedance analyzer and universal testing machine, respectively.

  1. 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

  2. Classification of physical activities based on body-segments coordination.

    Science.gov (United States)

    Fradet, Laetitia; Marin, Frederic

    2016-09-01

    Numerous innovations based on connected objects and physical activity (PA) monitoring have been proposed. However, recognition of PAs requires robust algorithm and methodology. The current study presents an innovative approach for PA recognition. It is based on the heuristic definition of postures and the use of body-segments coordination obtained through external sensors. The first part of this study presents the methodology required to define the set of accelerations which is the most appropriate to represent the particular body-segments coordination involved in the chosen PAs (here walking, running, and cycling). For that purpose, subjects of different ages and heterogeneous physical conditions walked, ran, cycled, and performed daily activities at different paces. From the 3D motion capture, vertical and horizontal accelerations of 8 anatomical landmarks representative of the body were computed. Then, the 680 combinations from up to 3 accelerations were compared to identify the most appropriate set of acceleration to discriminate the PAs in terms of body segment coordinations. The discrimination was based on the maximal Hausdorff Distance obtained between the different set of accelerations. The vertical accelerations of both knees demonstrated the best PAs discrimination. The second step was the proof of concept, implementing the proposed algorithm to classify PAs of new group of subjects. The originality of the proposed algorithm is the possibility to use the subject's specific measures as reference data. With the proposed algorithm, 94% of the trials were correctly classified. In conclusion, our study proposed a flexible and extendable methodology. At the current stage, the algorithm has been shown to be valid for heterogeneous subjects, which suggests that it could be deployed in clinical or health-related applications regardless of the subjects' physical abilities or characteristics. Copyright © 2016 Elsevier Ltd. All rights reserved.

  3. Synthesis, Structure and Luminescent Property of a Zinc(Ⅱ) Coordination Polymer Incorporating Flexible Cyclohexane- 1,2,3,4,5,6-hexacarboxylate Ligand

    Institute of Scientific and Technical Information of China (English)

    WANG Jing; LIU Zhao-qing; SU Ting-ting

    2011-01-01

    The hydrothermal reaction of Zn(NO3)2.4H20, cyclohexane-l,2,3,4,5,6-hexacarboxylic acid hydrate (H6LLH20, cis-conformation L1: a,e,a,e,a,e) and 2,21-bpy yielded a new coordination polymer [Zn2(H2L11)(2,21-bpy)]·2H20(trans-conformation L11: e,e,e,e,e,e), which was characterized by single-crystal X-ray diffraction, elemental analysis, IR and XRPD(X-ray powder diffraction). This complex crystallized in the triclinic system, with P1 space group and parameters a=0.66922(5) nm, b=0.97291(8) nm, c=1.22184(9) nm, a=99.0020(10)°, β=99.1300(10)°,γ=99.1910(10)°, V= 0.76176(10) nm3 and Z=2. The structure is a three-dimensional supramolecular network based on linear coordination chains through π-π stacking and hydrogen bonding interactions. The confromation of the starting ligand H6L1 transfromed to the H2LII. The complex emits strong luminescence at room temperature.

  4. Operator-based homogeneous coordinates: application in camera document scanning

    Science.gov (United States)

    Juarez-Salazar, Rigoberto; Diaz-Ramirez, Victor H.

    2017-07-01

    An operator-based approach for the study of homogeneous coordinates and projective geometry is proposed. First, some basic geometrical concepts and properties of the operators are investigated in the one- and two-dimensional cases. Then, the pinhole camera model is derived, and a simple method for homography estimation and camera calibration is explained. The usefulness of the analyzed theoretical framework is exemplified by addressing the perspective correction problem for a camera document scanning application. Several experimental results are provided for illustrative purposes. The proposed approach is expected to provide practical insights for inexperienced students on camera calibration, computer vision, and optical metrology among others.

  5. Multi-telerobot collaboration based on coordinated controller

    Institute of Scientific and Technical Information of China (English)

    2006-01-01

    A coordinated controller used for multi-telerobots collaboration was presented based on the strategy of shared control. First, it can overcome the effect of time delay. And, it combines the intelligence of the master side and the slave side, which cannot only increase the efficiency and the safety of the system but also relieve the burden and requirements of the operator. The controller can also cope with the collision between two telerobots. A simulation experiment was carried out to verify the validity of the controller for two slave robots.

  6. Polymer-based symmetric electrochromic devices

    Energy Technology Data Exchange (ETDEWEB)

    Arbizzani, Catia; Cerroni, Maria Grazia [Department of Chemistry `G. Ciamician`, University of Bologna, via Selmi 2, 40126 Bologna (Italy); Mastragostino, Marina [Department of Physical Chemistry, University of Palermo, via Archirafi 26, 20123 Palermo (Italy)

    1998-12-30

    The fact that conjugated polymers repeatedly undergo electrochemical doping/undoping processes, which are accompanied by color changes, makes these materials very attractive, and much effort has been devoted to their use in advanced devices. There is renewed interest in electroactive polymers that reversibly undergo both p- and n-doping because of their potential application in symmetric electrochemical devices. We employed fused molecules, dithienothiophenes, as monomers to obtain polymers with a narrow band gap suitable for n- and p-doping. The performance results of two symmetric electrochromic devices having as electrodes both poly(dithieno[3,4-b:3`,4`-d]thiophene) (pDTT1) and poly(dithieno[3,4-b:2`,3`-d]thiophene) (pDTT3) are reported and discussed

  7. Two different one-dimensional Cd(II) halide coordination polymers constructed through bridging carboxylate ligands.

    Science.gov (United States)

    Hou, Xue-Li; Wang, Hui-Ting

    2015-11-01

    Two cadmium halide complexes, catena-poly[[chloridocadmium(II)]-di-μ-chlorido-[chloridocadmium(II)]-bis[μ2-4-(dimethylamino)pyridin-1-ium-1-acetate]-κ(3)O:O,O';κ(3)O,O':O], [CdCl2(C9H12N2O2)]n, (I), and catena-poly[1-cyanomethyl-1,4-diazoniabicyclo[2.2.2]octane [[dichloridocadmium(II)]-μ-oxalato-κ(4)O(1),O(2):O(1'),O(2')] monohydrate], {(C8H15N3)[CdCl2(C2O4)]·H2O}n, (II), were synthesized in aqueous solution. In (I), the Cd(II) cation is octahedrally coordinated by three O atoms from two carboxylate groups and by one terminal and two bridging chloride ligands. Neighbouring Cd(II) cations are linked together by chloride anions and bridging O atoms to form a one-dimensional zigzag chain. Hydrogen-bond interactions are involved in the formation of the two-dimensional network. In (II), each Cd(II) cation is octahedrally coordinated by four O atoms from two oxalic acid ligands and two terminal Cl(-) ligands. Neighbouring Cd(II) cations are linked together by oxalate groups to form a one-dimensional anionic chain, and the water molecules and organic cations are connected to this one-dimensional zigzag chain through hydrogen-bond interactions.

  8. Synthesis and Structural Characterization of Magnesium Based Coordination Networks in Different Solvents

    Energy Technology Data Exchange (ETDEWEB)

    D Banerjee; J Finkelstein; A Smirnov; P Forster; L Borkowski; S Teat; J Parise

    2011-12-31

    Three magnesium based metal-organic frameworks, Mg{sub 3}(3,5-PDC){sub 3}(DMF){sub 3} {center_dot} DMF [1], Mg(3,5-PDC)(H{sub 2}O) {center_dot} (H{sub 2}O) [3], and Mg{sub 4}(3,5-PDC){sub 4}(DMF){sub 2}(H{sub 2}O){sub 2} {center_dot} 2DMF {center_dot} 4.5H{sub 2}O [4], and a 2-D coordination polymer, [Mg(3,5-PDC)(H{sub 2}O){sub 2}] [2] [PDC = pyridinedicarboxylate], were synthesized using a combination of DMF, methanol, ethanol, and water. Compound 1 [space group P2{sub 1}/n, a = 12.3475(5) {angstrom}, b = 11.1929(5) {angstrom}, c = 28.6734(12) {angstrom}, {beta} = 98.8160(10){sup o}, V = 3916.0(3) {angstrom}{sup 3}] consists of a combination of isolated and corner-sharing magnesium octahedra connected by the organic linkers to form a 3-D network with a 12.2 {angstrom} x 4.6 {angstrom} 1-D channel. The channel contains coordinated and free DMF molecules. In compound 2 [space group C2/c, a = 9.964(5) {angstrom}, b = 12.0694(6) {angstrom}, c = 7.2763(4) {angstrom}, {beta} = 106.4970(6){sup o}, V = 836.70(6) {angstrom}{sup 3}], PDC connects isolated seven coordinated magnesium polyhedra into a layered structure. Compound 3 [space group P6{sub 1}22, a = 11.479(1) {angstrom}, c = 14.735(3) {angstrom}, V = 1681.7(4) {angstrom}{sup 3}] (previously reported) contains isolated magnesium octahedra connected by the organic linker with each other forming a 3D network. Compound 4 [space group P2{sub 1}/c, a = 13.7442(14) {angstrom}, b = 14.2887(15) {angstrom}, c = 14.1178(14) {angstrom}, {beta} = 104.912(2){sup o}, V = 2679.2(5) {angstrom}{sup 3}] also exhibits a 3D network based on isolated magnesium octahedra with square cavities containing both disordered DMF and water molecules. The structural topologies originate due to the variable coordination ability of solvent molecules with the metal center. Water molecules coordinate with the magnesium metal centers preferably over other polar solvents (DMF, methanol, ethanol) used to synthesize the coordination networks. Despite

  9. Synthesis and Structural Characterization of Magnesium Based Coordination Networks in Different Solvents

    Energy Technology Data Exchange (ETDEWEB)

    Banerjee, Debasis; Finkelstein, Jeffrey; Smirnov, A.; Forster, Paul M.; Borkowski, Lauren A.; Teat, Simon J.; Parise, John B. (LBNL); (UNLV); (Buffalo)

    2015-10-15

    Three magnesium based metal-organic frameworks, Mg{sub 3}(3,5-PDC){sub 3}(DMF){sub 3} {center_dot} DMF [1], Mg(3,5-PDC)(H{sub 2}O) {center_dot} (H{sub 2}O) [3], and Mg4(3,5-PDC)4(DMF){sub 2}(H{sub 2}O){sub 2} {center_dot} 2DMF {center_dot} 4.5H{sub 2}O [4], and a 2-D coordination polymer, [Mg(3,5-PDC)(H{sub 2}O){sub 2}] [2] [PDC = pyridinedicarboxylate], were synthesized using a combination of DMF, methanol, ethanol, and water. Compound 1 [space group P2{sub 1}/n, a = 12.3475(5) {angstrom}, b = 11.1929(5) {angstrom}, c = 28.6734(12) {angstrom}, {beta} = 98.8160(10){sup o}, V = 3916.0(3) {angstrom}{sup 3}] consists of a combination of isolated and corner-sharing magnesium octahedra connected by the organic linkers to form a 3-D network with a 12.2 {angstrom} x 4.6 {angstrom} 1-D channel. The channel contains coordinated and free DMF molecules. In compound 2 [space group C2/c, a = 9.964(5) {angstrom}, b = 12.0694(6) {angstrom}, c = 7.2763(4) {angstrom}, {beta} = 106.4970(6){sup o}, V = 836.70(6) {angstrom}{sup 3}], PDC connects isolated seven coordinated magnesium polyhedra into a layered structure. Compound 3 [space group P6{sub 1}22, a = 11.479(1) {angstrom}, c = 14.735(3) {angstrom}, V = 1681.7(4) {angstrom}{sup 3}] (previously reported) contains isolated magnesium octahedra connected by the organic linker with each other forming a 3D network. Compound 4 [space group P2{sub 1}/c, a = 13.7442(14) {angstrom}, b = 14.2887(15) {angstrom}, c = 14.1178(14) {angstrom}, {beta} = 104.912(2){sup o}, V = 2679.2(5) {angstrom}{sup 3}] also exhibits a 3D network based on isolated magnesium octahedra with square cavities containing both disordered DMF and water molecules. The structural topologies originate due to the variable coordination ability of solvent molecules with the metal center. Water molecules coordinate with the magnesium metal centers preferably over other polar solvents (DMF, methanol, ethanol) used to synthesize the coordination networks. Despite testing

  10. Core-double-shell Fe3O4@carbon@poly(In(III)-carboxylate) microspheres: cycloaddition of CO2 and epoxides on coordination polymer shells constituted by imidazolium-derived Al(III)-Salen bifunctional catalysts.

    Science.gov (United States)

    An, Qiao; Li, Zifeng; Graff, Robert; Guo, Jia; Gao, Haifeng; Wang, Changchun

    2015-03-01

    A hydrid microsphere Fe3O4@carbon@poly(In(III)-carboxylate) consisting of a cluster of Fe3O4 nanoparticles as the core, a carbon layer as the inner shell and a porous In(III)-carboxylate coordination polymer as the outer shell was prepared and applied as a recyclable catalyst for the cycloaddition reaction of CO2 and epoxides. Construction of this hybrid microsphere was achieved in the two steps, including (1) the one-pot solvothermal synthesis of Fe3O4@C particles with the abundant carboxylic groups on the carbon surface and (2) the subsequent growth of the outer shell polymers based on the precipitation coordination polymerization. Imidazolium-substituted Salen ligands were synthesized and chelated with the In(III) ions using the terminal carboxylic groups. The coordination polymer shell was formed on the Fe3O4@C particles, and the structures including shell thickness, surface area and porosity could be varied by tuning the feeding ratios of the In(III) ions and the ligands. The optimal structure of the coordination polymers showed a shell thickness of ca. 45 nm with ∼5 nm of mesopore, 174.7 m(2)/g of surface area and 0.2175 cm(3)/g of pore volume. In light of gas uptake capability, catalytic activity and magnetic susceptibility, cycloaddition of CO2 with a series of epoxides were studied by using Al-complexed Fe3O4@C@In(III)-[IL-Salen] microspheres. The results validated that the self-supporting catalytic layer with high surface area was of remarkable advantages, which were attributed from great increment of effective active sites and combination of nucleophilic/electrophilic synergistic property and CO2 uptake capability. Therefore, these hybrid microspheres provided excellent catalytic activity, prominent selectivity to cyclic carbonates and outstanding recyclability with the assistance of an applied magnetic field.

  11. Performance of Lithium Polymer Cells with Polyacrylonitrile based Electrolyte

    DEFF Research Database (Denmark)

    Perera, Kumudu; Skaarup, Steen; West, Keld

    2006-01-01

    The performance of lithium polymer cells fabricated with Polyacrylonitrile (PAN) based electrolytes was studied using cycling voltammetry and continuous charge discharge cycling. The electrolytes consisted of PAN, ethylene carbonate (EC), propylene carbonate (PC) and lithium trifluoromethanesulfo......The performance of lithium polymer cells fabricated with Polyacrylonitrile (PAN) based electrolytes was studied using cycling voltammetry and continuous charge discharge cycling. The electrolytes consisted of PAN, ethylene carbonate (EC), propylene carbonate (PC) and lithium...

  12. Polymer composites based on gypsum matrix

    Energy Technology Data Exchange (ETDEWEB)

    Mucha, Maria; Mróz, Patrycja; Kocemba, Aleksandra [Faculty of Process and Environmental Engineering, Lodz University of Technology, Wólczańska 215 street, 90–924 Łódź (Poland)

    2016-05-18

    The role of polymers as retarder additives is to prolong the workability connected with setting time of gypsum. Various cellulose derivatives, soluble in water in concentration up to 1,5% by weight were applied taking different water/binder ratio. The hydration process of calcium sulfate hemihydrate (gypsum binder) into dihydrate (gypsum plaster) was observed by setting and calorimetric techniques. Scanning electron microscopy confirmed that the gypsum microstructure was varied when polymers are used. The mechanical properties of gypsum plasters were studied by bending strength test and they are correlated with sample microstructure.

  13. Polymers based on renewable raw materials

    Directory of Open Access Journals (Sweden)

    Jovanović Slobodan M.

    2002-01-01

    Full Text Available The basic raw materials for the chemical industry, which also means for polymer production, are mineral oil and natural gas. Mineral oil and natural gas resources are limited so that sooner or later they will be consumed. For this reason alternative, renewable raw materials for the chemical industry have become the object of intensive investigation all over the world. Some of the results of these investigations concerning renewable raw materials for the production of polymer materials are presented in this paper.

  14. Bio-Based Polymers with Potential for Biodegradability

    Directory of Open Access Journals (Sweden)

    Thomas F. Garrison

    2016-07-01

    Full Text Available A variety of renewable starting materials, such as sugars and polysaccharides, vegetable oils, lignin, pine resin derivatives, and proteins, have so far been investigated for the preparation of bio-based polymers. Among the various sources of bio-based feedstock, vegetable oils are one of the most widely used starting materials in the polymer industry due to their easy availability, low toxicity, and relative low cost. Another bio-based plastic of great interest is poly(lactic acid (PLA, widely used in multiple commercial applications nowadays. There is an intrinsic expectation that bio-based polymers are also biodegradable, but in reality there is no guarantee that polymers prepared from biorenewable feedstock exhibit significant or relevant biodegradability. Biodegradability studies are therefore crucial in order to assess the long-term environmental impact of such materials. This review presents a brief overview of the different classes of bio-based polymers, with a strong focus on vegetable oil-derived resins and PLA. An entire section is dedicated to a discussion of the literature addressing the biodegradability of bio-based polymers.

  15. Coordinate System And Coordinate Transformations Based On Wave Nature Of Light

    CERN Document Server

    Yagan, M F

    2006-01-01

    The Classical Coordinate System is geometrical by nature with time being an external variable. Constructing a classical coordinate system employs a point-like signal with infinite speed. In Special Relativity Theory the speed is limited but the signal is a point-like particle (photon). If the oscillatory nature of light is considered, an event in absolute space is to be characterized by three coordinates namely, distance, time and phase. The Galilean transformation equations for space and time coordinates should be complemented by a third equation that accounts for the phase transformation. Wave equation remains invariant under such transformation and kinematical equivalence of inertial reference frames is conserved. Lorentz transforms apply to wave length and wave period of the exchanged light signal in a dynamic set-up.

  16. Assembling supramolecular networks by halogen bonding in coordination polymers driven by 5-bromonicotinic acid

    Energy Technology Data Exchange (ETDEWEB)

    Gu, Jin-Zhong, E-mail: gujzh@lzu.edu.cn [State Key Laboratory of Applied Organic Chemistry, Key Laboratory of Nonferrous Metal Chemistry and Resources Utilization of Gansu Province, College of Chemistry and Chemical Engineering, Lanzhou University, Lanzhou 730000 (China); Wu, Jiang [State Key Laboratory of Applied Organic Chemistry, Key Laboratory of Nonferrous Metal Chemistry and Resources Utilization of Gansu Province, College of Chemistry and Chemical Engineering, Lanzhou University, Lanzhou 730000 (China); Kirillov, Alexander M. [Centro de Química Estrutural, Complexo I, Instituto Superior Técnico, The University of Lisbon, Av. Rovisco Pais, 1049-001 Lisbon (Portugal); Lv, Dong-Yu; Tang, Yu; Wu, Jin-Cai [State Key Laboratory of Applied Organic Chemistry, Key Laboratory of Nonferrous Metal Chemistry and Resources Utilization of Gansu Province, College of Chemistry and Chemical Engineering, Lanzhou University, Lanzhou 730000 (China)

    2014-05-01

    A series of six coordination compounds ([Zn(5-Brnic){sub 2}]·1.5H{sub 2}O){sub n} (1), [Cd(5-Brnic){sub 2}]{sub n} (2), [Co(5-Brnic){sub 2}(H{sub 2}O){sub 2}]{sub n} (3), [Zn(5-Brnic){sub 2}(H{sub 2}biim)]{sub n} (4), ([Cd(5-Brnic){sub 2}(phen)]·H{sub 2}O){sub n} (5), and [Pb(5-Brnic){sub 2}(phen)] (6) have been generated by the hydrothermal method from the metal(II) nitrates, 5-bromonicotinic acid (5-BrnicH), and an optional ancillary 1,10-phenanthroline (phen) or 2,2′-biimidazole (H{sub 2}biim) ligand. All the products 1–6 have been characterized by IR spectroscopy, elemental, thermal, powder and single-crystal X-ray diffraction analyses. Their 5-bromonicotinate-driven structures vary from the 3D metal-organic framework with the seh-3,5-P21/c topology (in 2) and the 2D interdigitated layers with the sql topology (in 1 and 3), to the 1D chains (in 4 and 5) and the 0D discrete monomers (in 6). The 5-bromonicotinate moiety acts as a versatile building block and its tethered bromine atom plays a key role in reinforcing and extending the structures into diverse 3D supramolecular networks via the various halogen bonding Br⋯O, Br⋯Br, and Br⋯π interactions, as well as the N–H⋯O and C–H⋯O hydrogen bonds. The obtained results demonstrate a useful guideline toward engineering the supramolecular architectures in the coordination network assembly under the influence of various halogen bonding interactions. The luminescent (for 1, 2, 4, 5, and 6) and magnetic (for 3) properties have also been studied and discussed in detail. - Graphical abstract: Six coordination compounds driven by 5-bromonicotinic acid have been generated and structurally characterized, revealing diverse metal-organic networks that are further reinforced and extended via various halogen bonding interactions. - Highlights: • 5-Bromonicotinic acid is a versatile ligand for Zn, Cd, Co and Pb derivatives. • Careful selection of co-ligands and metals resulted in different network

  17. Three new zinc(Ⅱ) coordination polymers: Modulation of extended structures driven by assistant ligands

    Institute of Scientific and Technical Information of China (English)

    DONG Zhe; ZHANG WeiHong; WANG YaoYu; LIU RuiTing; REN Chen; SHI QiZhen

    2009-01-01

    Three new complexes, [Zn(dtb)(4,4'-bipy)]·5H_2O (1), [Zn(dtb)(bpp)]·H_2O (2) and [Zn(dtb)(phen)_2].CH_3-propane, phen = 1,10-phenanthroline), have been constructed by dtb ligand and zinc salt in the pres-ence of different assistant N-containing ligands under hydrothermal conditions. The structures of the complexes were established by single-crystal X-ray diffraction analysis. Although compounds 1 and 2 are both 2D networks, the cavities' forms and pitch of helix are different. The structure of compound 3 shows a 1D helical chain, and is extended by the supermolecule interactions into a 2D framework. These neutral polymeric complexes exhibit structural and dimensional diversity due to the different coordination modes of the flexible dtb ligand and the effect of assistant ligands.

  18. Tuned synthesis of two coordination polymers of Cd(II) using substituted bent 3-pyridyl linker and succinate: structures and their applications in anion exchange and sorption properties.

    Science.gov (United States)

    Maity, Dilip Kumar; Bhattacharya, Biswajit; Halder, Arijit; Ghoshal, Debajyoti

    2015-12-28

    Two new Cd(II) coordination polymers, namely [Cd(3-bpdh)2(ClO4)2]n (1) and {[Cd(3-bpdh)(suc)(H2O)]·3(H2O)}n (2), have been synthesized using a substituted bent N,N'-donor ligand 2,5-bis-(3-pyridyl)-3,4-diaza-2,4-hexadiene (3-bpdh) and aliphatic dicarboxylate disodium succinate (suc) with Cd(II) perchlorate salts at room temperature by a slow diffusion technique for the exploration of our previous reported work. Both the structures were determined by single-crystal X-ray diffraction analysis and also by other physicochemical methods. Structure analysis revealed that complex 1 is a 1D chain structure containing coordinated perchlorate with a metal centre, and complex 2 shows a porous 3D framework with encapsulation of lattice water molecules into the void along the crystallographic a-axis. The PXRD study shows the bulk purity of both the complexes and TGA analysis of 2 exhibits that the structure is thermally stable up to 250 °C. Complex 1 shows a nice anion exchange property with replacement of weakly coordinated perchlorate with the inclusion of new anions; and the anion exchanged solids were characterised by FT-IR, PXRD and photoluminescence properties. The desolvated framework of 2 exhibits sorption of CO2 and water vapor and surface adsorption of N2 corroborating with the nature of the pore environment present in 2. The photoluminescence study has been also done for both complexes in the solid state which exhibits ligand based emissions at room temperature.

  19. Hyperbranched red light-emitting phosphorescent polymers based on iridium complex as the core

    Energy Technology Data Exchange (ETDEWEB)

    Guo, Ting; Yu, Lei; Yang, Yong; Li, Yanhu; Tao, Yun [Institute of Polymer Optoelectronic Materials and Devices, State Key Laboratory of Luminescent Materials and Devices, South China University of Technology, Guangzhou 510640 (China); Hou, Qiong [School of Chemistry & Environment, South China Normal University, Guangzhou 510006 (China); Ying, Lei, E-mail: msleiying@scut.edu.cn [Institute of Polymer Optoelectronic Materials and Devices, State Key Laboratory of Luminescent Materials and Devices, South China University of Technology, Guangzhou 510640 (China); Yang, Wei; Wu, Hongbin; Cao, Yong [Institute of Polymer Optoelectronic Materials and Devices, State Key Laboratory of Luminescent Materials and Devices, South China University of Technology, Guangzhou 510640 (China)

    2015-11-15

    A series of hyperbranched π-conjugated light-emitting polymers containing an iridium complex as the branched core unit and polyfluorene or poly(fluorene-alt-carbazole) as the branched segments were synthesized via a palladium catalyzed Suzuki polymerization. Apparent Förster energy transfer in the photoluminescent spectra as thin films was observed, while no discernible characteristic absorbance and photoluminescence of the iridium complex can be realized in dilute solutions. Copolymers based on poly(fluorene-alt-carbazole) as the branched segments demonstrated enhanced highest occupied molecular orbital energy levels relative to those based on polyfluorene. The electroluminescent spectra of these copolymers exclusively showed the characteristic emission of the iridium complex, with corresponding CIE coordinates of (0.67±0.01, 0.31). All devices exhibited relatively slow roll-off of efficiency, and the best device performance with the maximum luminous efficiency of 5.33 cd A{sup −1} was attained by using PFCzTiqIr3 as the emissive layer. These results indicated that the hyperbranched conjugated architectures can be a promising molecular design strategy for efficient electrophosphorescent light-emitting polymers. - Highlights: • Hyperbranched red light-emitting polymers are synthesized. • Red light-emitting iridium complex is used as the branched core unit. • Hyperbranched polymers based on PFCz exhibit higher luminescence. • The highest luminous efficiency of 5.33 cd A{sup −1} is attained.

  20. A coordination-based framework for distributed constraint solving

    NARCIS (Netherlands)

    P. Zoeteweij (Peter)

    2002-01-01

    textabstractDICE (DIstributed Constraint Environment) is a framework for the construction of distributed constraint solvers from software components in a number of predefined categories. The framework is implemented using the Manifold coordination language, and coordinates the components of a