Sample records for dinuclear nickel-ruthenium complexes

  1. Dinuclear Manganese Complexes for Artificial Photosynthesis : Synthesis and Properties


    Anderlund, Magnus


    This thesis deals with the synthesis and characterisation of a series of dinuclear manganese complexes. Their ability to donate electrons to photo-generated ruthenium(III) has been investigated in flash photolysis experiments followed by EPR-spectroscopy. These experiment shows several consecutive one-electron transfer steps from the manganese moiety to ruthenium(III), that mimics the electron transfer from the oxygen evolving centre in photosystem II. The redox properties of these complexes ...

  2. Formation of a dinuclear complex in collisions between light nuclei and entrance channel limitations to fusion

    International Nuclear Information System (INIS)

    Shapira, D.; Shivakumar, B.; Ayik, S.; Harmon, B.A.


    A model is described which addresses both the binary decay and the fusion of a dinuclear complex formed in the collision, and the model predictions are compared with data. In the model, the colliding ions can be trapped into the pocket of the entrance channel potential and a rotating dinuclear complex (DNC) is formed. The DNC evolves through the exchange of nucleons to different dinuclear configurations. At each state of its evolution there is a finite probability for the DNC to decay into two fragments. That part of the flux which does not decay into dinuclear channels (two separate nuclei) ends up fusing. 15 refs., 9 figs

  3. Dinuclear transition metal complexes in carbon nanostructured materials synthesis (United States)

    Ayuso, J. I.; Hernández, E.; Delgado, E.


    Carbon nanomaterials (CNMs) were prepared with two similar techniques using organometallic complexes as catalysts precursors. Chemical vapour deposition (CVD) and pyrolysis with chlorine gas approaches were employed in order to explore the effect of dinuclear transition metal compounds [Fe2(CO)6(μ-S2C6H2X2), (X=OH, Cl)] in synthesis of CNMs. Our to-date results have shown these complexes generate different carbonaceous materials when they are used in bulk, it was also observed that their performances in synthesis differ even though these compounds are analogous. With X=OH complex used in CVD process, metal nanoparticles of ca. 20-50 nm in size and embedded in carbon matrix were obtained. X=C1 complex has been used in pyrolysis experiments and showed an entire volatilisation or no reaction, depending on selected temperature. Furthermore, obtaining of a new tetranuclear iron cluster is presented in this work.

  4. Self-Assembly of Mono- and Dinuclear Metal Complexes; Oxidation Catalysis and Metalloenzyme Models

    NARCIS (Netherlands)

    Gelling, Onko-Jan; Rispens, Minze T.; Lubben, Marcel; Feringa, Bernard


    In this chapter several approaches to achieve assembly of mono- and dinuclear metal complexes, which can be considered structural and functional models for metalloenzymes, are described. The emphasis lies on oxidation chemistry, summarizing O2 binding, hydroxylation, demethylation, dehalogenation

  5. Biological processing of dinuclear ruthenium complexes in eukaryotic cells. (United States)

    Li, Xin; Heimann, Kirsten; Dinh, Xuyen Thi; Keene, F Richard; Collins, J Grant


    The biological processing - mechanism of cellular uptake, effects on the cytoplasmic and mitochondrial membranes, intracellular sites of localisation and induction of reactive oxygen species - of two dinuclear polypyridylruthenium(ii) complexes has been examined in three eukaryotic cells lines. Flow cytometry was used to determine the uptake of [{Ru(phen)2}2{μ-bb12}](4+) (Rubb12) and [Ru(phen)2(μ-bb7)Ru(tpy)Cl](3+) {Rubb7-Cl, where phen = 1,10-phenanthroline, tpy = 2,2':6',2''-terpyridine and bbn = bis[4(4'-methyl-2,2'-bipyridyl)]-1,n-alkane} in baby hamster kidney (BHK), human embryonic kidney (HEK-293) and liver carcinoma (HepG2) cell lines. The results demonstrated that the major uptake mechanism for Rubb12 and Rubb7-Cl was active transport, although with a significant contribution from carrier-assisted diffusion for Rubb12 and passive diffusion for Rubb7-Cl. Flow cytometry coupled with Annexin V/TO-PRO-3 double-staining was used to compare cell death by membrane damage or apoptosis. Rubb12 induced significant direct membrane damage, particularly with HepG2 cells, while Rubb7-Cl caused considerably less membrane damage but induced greater levels of apoptosis. Confocal microscopy, coupled with JC-1 assays, demonstrated that Rubb12 depolarises the mitochondrial membrane, whereas Rubb7-Cl had a much smaller affect. Cellular localisation experiments indicated that Rubb12 did not accumulate in the mitochondria, whereas significant mitochondrial accumulation was observed for Rubb7-Cl. The effect of Rubb12 and Rubb7-Cl on intracellular superoxide dismutase activity showed that the ruthenium complexes could induce cell death via a reactive oxygen species-mediated pathway. The results of this study demonstrate that Rubb12 predominantly kills eukaryotic cells by damaging the cytoplasmic membrane. As this dinuclear ruthenium complex has been previously shown to exhibit greater toxicity towards bacteria than eukaryotic cells, the results of the present study suggest that

  6. Formation of a dinuclear complex in collisions between light nuclei and entrance channel limitations to fusion

    International Nuclear Information System (INIS)

    Shapira, D.; Shivakumar, B.; Ayik, S.; Harmon, B.A.


    A model for fusion of light nuclei has been proposed recently wherein fusion progresses through nucleus-nucleus capture via a dinuclear stage which acts as a doorway to fusion. While this model accounts for the fusion cross sections, it makes no attempt at predicting observables associated with the non-fusion part of the captured flux. A study of products from the decay of the dinuclear complex into non-fusion channels can provide a stringent test for such a model. In this contribution a model which addresses both the binary decay and the fusion of a dinuclear complex formed in the collision is described and model predictions are compared with data. Accompanying contributions discuss the formalism which is used to describe the evolution of the dinuclear complex and present new data which provide information that helps justify the approximations made in applying this model

  7. Dinuclear titanium complexes with methylphenylsilylene bridge between cyclopentadienyl rings. Synthesis, characterization and reactivity towards ethylene

    Czech Academy of Sciences Publication Activity Database

    Horáček, Michal; Gyepes, R.; Merna, J.; Kubišta, Jiří; Mach, Karel; Pinkas, Jiří


    Roč. 695, č. 9 (2010), s. 1425-1433 ISSN 0022-328X R&D Projects: GA AV ČR KJB400400602; GA MPO FT-TA3/078 Institutional research plan: CEZ:AV0Z40400503 Keywords : ansa-titanocene * cyclopentadienyl * dinuclear complexes Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 2.205, year: 2010

  8. Dinuclear ruthenium sawhorse-type complexes containing carboxylato bridges and ferrocenyl substituents: Synthesis and electrochemistry

    Czech Academy of Sciences Publication Activity Database

    Auzias, M.; Süss-Fink, G.; Štěpnička, P.; Ludvík, Jiří


    Roč. 360, č. 6 (2007), s. 2023-2028 ISSN 0020-1693 Institutional research plan: CEZ:AV0Z40400503 Keywords : carboxylato bridges * dinuclear complexes * ruthenium * electrochemistry Subject RIV: CG - Electrochemistry Impact factor: 1.713, year: 2007

  9. Tuning interaction in dinuclear ruthenium complexes : HOMO versus LUMO mediated superexchange through azole and azine bridges

    NARCIS (Netherlands)

    Browne, Wesley; Hage, R; Vos, Johannes G.

    In this review the interaction between metal centers in dinuclear complexes based on azole and azine containing bridging ligands is reviewed. The focus of the review is on the manner in which the interaction pathway can be manipulated by variations in the nature of both the direct bridging unit and

  10. Dinuclear ruthenium(II) and/or osmium(II) complexes of bipyridyl ...

    Indian Academy of Sciences (India)


    Dinuclear ruthenium(II) and/or osmium(II) complexes of bipyridyl ligands bridged by rigid spacers: Synthesis, electrochemical behaviour, absorption spectra and luminescence properties. ANVARHUSEN K BILAKHIYA, BEENA TYAGI and PARIMAL PAUL. Discipline of Silicates and Catalysis, Central Salt & Marine ...

  11. Study of half-sandwich mono and dinuclear complexes of platinum ...

    Indian Academy of Sciences (India)

    Home; Journals; Journal of Chemical Sciences; Volume 124; Issue 3. Study of half-sandwich mono and dinuclear complexes of platinum group metals containing pyrazolyl pyridine analogues: Synthesis and spectral characterization. Venkateswara Rao Anna Kota Thirumala Prasad Peng Wang Kollipara Mohan Rao.

  12. Synthesis, characterization and biological activity of symmetric dinuclear complexes derived from a novel macrocyclic compartmental ligand

    International Nuclear Information System (INIS)

    Mruthyunjayaswamy, B.H.M.; Ijare, Omkar B.; Jadegoud, Y.


    A phenol based novel macrocyclic binucleating compartmental ligand N,N-bis(2,6-diiminomethyl-4-methyl-1-hydroxyphenyl)malonoyldicarboxamide was prepared. The complexes were prepared by template method by reacting 2,6-diformyl-4-methylphenol, malonoyl dihydrazide and the metal chlorides of Cu(II), Ni(II), Co(II), Cd(II), Zn(II) and Hg(II) in methanol to get a series of dinuclear complexes. The complexes were characterized by elemental analyses, conductivity measurements, magnetic susceptibility data, IR, UV-Vis, ESR, NMR and FAB mass spectral data. The dinuclear nature of the complexes was confirmed on the basis of elemental analyses, magnetic susceptibility, ESR and FAB mass spectral data. The ligand as well as Cu(II), Ni(II), Co(II) and Zn(II) complexes were tested for their antibacterial and antifungal properties against Escherichia coli, Staphyloccocus aureus, Aspergillus niger and Fusarium oxysporum. Magnetic susceptibility measurements of Cu(II), Ni(II) and Co(II) complexes reveal that these complexes exhibit antiferromagnetic coupling behavior due to the presence of two metal ions in close proximity. FAB mass spectrum of the Cu(II) complex gave a clear evidence for the dinuclear nature. The ligand and the complexes were found to be less active against the tested bacteria, but the ligand alone was found active against the fungus Fusarium oxysporum. (author)

  13. Syntheses and a Solid State Structure of a Dinuclear Molybdenum(V Complex with Pyridine

    Directory of Open Access Journals (Sweden)

    Jon Zubieta


    Full Text Available A mononuclear complex [MoOCl4(H2O]− readily forms a metal−metal bonded {Mo2O4}2+ core. A high content of pyridine in the reaction mixture prevents further aggregation of dinuclear cores into larger clusters and a neutral, dinuclear complex with the [Mo2O4Cl2(Py4] composition is isolated as a product. Solid state structures of two compounds containing this complex, [Mo2O4Cl2(Py4]·2.25Py (1 and [Mo2O4Cl2(Py4]·1.5PyHCl (2, were investigated by X-ray crystallography.

  14. Energy and Charge Transfer in Dinuclear Ru-based Complexes (United States)

    Kleiman, Valeria


    In this work, the excited state dynamics of a series of dinuclear compounds combining Ru based cromophores with M =Ru(II), Fe(II), Fe(III), Cr(III) are explored. Ru- μ-NC-M dimers are good candidates to investigate the competition between electron and energy transfer in arrays of chromophores. The presence of a μ-NC bridge affords a strong coupling between the moieties without providing acceptor states that might act as electron traps. Polypyridyl Ru based compounds play an important role on light-harvesting antennas for energy conversion. With proper knowledge of the excited state dynamics, multinuclear arrays of chromophores can be developed. Our studies focus on (i) energy/electron transfer from the Ru(II) to a 2nd M center through the cyanide bridge, and (ii) geometry changes due to the exchange of one of the Ru(II) polypiridyl ligands . Broadband ultrafast spectroscopy shows excited state dynamics in the psec time regime. These dynamics depend strongly on the nature of the acceptor and the orientation of the ligand involved in the photoinduced transition. Hence, the competition between energy and electron transfer across the bridge is modulated by the selective choice of the secondary M center. We conclude that transition metals from the 3rd row are good candidates for longer arrays since their lack of low-lying MC states precludes thermal deactivation. This work is based upon work supported by NSF (CHE-1058638) and CONICET.

  15. Experimental evidence for the involvement of dinuclear alkynylcopper(I) complexes in alkyne-azide chemistry. (United States)

    Buckley, Benjamin R; Dann, Sandra E; Heaney, Harry


    Dinuclear alkynylcopper(I) ladderane complexes are prepared by a robust and simple protocol involving the reduction of Cu(2)(OH)(3)OAc or Cu(OAc)(2) by easily oxidised alcohols in the presence of terminal alkynes; they function as efficient catalysts in copper-catalysed alkyne-azide cycloaddition reactions as predicted by the Ahlquist-Fokin calculations. The same copper(I) catalysts are formed during reactions by using the Sharpless-Fokin protocol. The experimental results also provide evidence that sodium ascorbate functions as a base to deprotonate terminal alkynes and additionally give a convincing alternative explanation for the fact that the Cu(I)-catalysed reactions of certain 1,3-diazides with phenylacetylene give bis(triazoles) as the major products. The same dinuclear alkynylcopper(I) complexes also function as catalysts in cycloaddition reactions of azides with 1-iodoalkynes.

  16. mu(2)-Oxido bridged dinuclear vanadium(V) complex: synthesis and characterization

    Czech Academy of Sciences Publication Activity Database

    Ghorbani, M.; Khalaji, A.D.; Feizi, N.; Akbari, A.; Eigner, Václav; Dušek, Michal


    Roč. 1130, Feb (2017), s. 442-446 ISSN 0022-2860 R&D Projects: GA ČR(CZ) GA15-12653S; GA MŠk LO1603 EU Projects: European Commission(XE) CZ.2.16/3.1.00/24510 Institutional support: RVO:68378271 Keywords : vanadium(V) complex * Schiff base * dinuclear * octahedral Subject RIV: CB - Analytical Chemistry, Separation OBOR OECD: Analytical chemistry Impact factor: 1.753, year: 2016

  17. CO assisted N2 functionalization activated by a dinuclear hafnium complex: a DFT mechanistic exploration. (United States)

    Ma, Xuelu; Zhang, Xin; Zhang, Wenchao; Lei, Ming


    In this paper, the reaction mechanisms of CO assisted N(2) cleavage and functionalization activated by a dinuclear hafnium complex are studied using a density function theory (DFT) method. Several key intermediates (Ia, Ib, Ic and Id) with axial/equatorial N=C=O coordination structures are found to be of importance along reaction pathways of CO assisted N(2) functionalization, which could provide a profound theoretical insight into the C-N bond formation and N-N bond cleavage. There are two different attack directions to insert the first CO molecule into the Hf-N bonds of the dinuclear hafnium complex, which lead to C-N bond formation. The calculated results imply that CO insertion into the Hf(1)-N(3) bond (Path A1) reacts more easily than that into the Hf(2)-N(3) bond (Path A3). But for the insertion of the second CO insertion to give 2A, there are two possibilities (Path A1 and Path A2) according to this insertion being after/before N-N bond cleavage. Two pathways (Path A1 and Path A2) are proved to be possible to form final dinitrogen functionalized products (oxamidide 2A, 2B and 2C) in this study, which explain the formation of different oxamidide isomers in CO assisted N(2) functionalization activated by a dinuclear hafnium complex.

  18. Dinuclear metal complexes derived from a bis-chelating heterocyclic ...

    African Journals Online (AJOL)

    The analytical data indicate that the metal to ligand ratio is 2:1 in all the complexes. The coordination of triethylamine, water and chloride ion are observed in the Co(II), Zn(II) and Ni(II) complexes. The absence of ionizable or coordinated chloride in Cu(II) complex is a notable feature. Octahedral geometry for Co(II), Zn(II) and ...

  19. and hetero-dinuclear complexes with a new septadentate Schiff

    Indian Academy of Sciences (India)


    with inner copper centre and outer nontransition/transition metal ions. The complexes ... interacting metal complexes derived from acyclic chelators incorporating thioether function. 2. Experimental ..... the decreased tendency to transfer charge from the bridging oxygen to the uranium on co- ordination to the second metal ion ...

  20. Thermal expansion and magnetic properties of benzoquinone-bridged dinuclear rare-earth complexes. (United States)

    Moilanen, Jani O; Mansikkamäki, Akseli; Lahtinen, Manu; Guo, Fu-Sheng; Kalenius, Elina; Layfield, Richard A; Chibotaru, Liviu F


    The synthesis and structural characterization of two benzoquinone-bridged dinuclear rare-earth complexes [BQ(MCl 2 ·THF 3 ) 2 ] (BQ = 2,5-bisoxide-1,4-benzoquinone; M = Y (1), Dy (2)) are described. Of these reported metal complexes, the dysprosium analogue 2 is the first discrete bridged dinuclear lanthanide complex in which both metal centres reside in pentagonal bipyramidal environments. Interestingly, both complexes undergo significant thermal expansion upon heating from 120 K to 293 K as illustrated by single-crystal X-ray and powder diffraction experiments. AC magnetic susceptibility measurements reveal that 2 does not show the slow relation of magnetization in zero dc field. The absent of single-molecule behaviour in 2 arises from the rotation of the principal magnetic axis as compared to the pseudo-C 5 axis of the pentagonal bipyramidal environment as suggested by ab initio calculations. The cyclic voltammetry and chemical reduction experiments demonstrated that complexes 1 and 2 can be reduced to radical species containing [BQ 3 ˙ - ]. This study establishes efficient synthetic strategy to make bridged redox-active multinuclear lanthanide complexes with a pentagonal bipyramidal coordination environment that are potential precursors for single-molecule magnets.

  1. Synthesis, structural characterization, cytotoxic properties and DNA binding of a dinuclear copper(II) complex. (United States)

    Ferreira, B J M Leite; Brandão, P; Meireles, M; Martel, Fátima; Correia-Branco, Ana; Fernandes, Diana M; Santos, T M; Félix, V


    In this study a novel dinuclear copper(II) complex with adenine and phenanthroline has been synthesized and its structure determined by single crystal X-ray diffraction. In the dinuclear complex [Cu₂(μ-adenine)₂(phen)₂(H2O)2](NO3)4·0.5H2O (phen=1,10-phenanthroline) (1) the two Cu(II) centres exhibit a distorted square pyramidal coordination geometry linked by two nitrogen donors from adenine bridges leading to a Cu-Cu distance of 3.242(3)Å. Intramolecular and intermolecular π⋯π interactions as well as an H-bonding network were observed. The antitumor capacity of the complex has been tested in vitro against human cancer cell lines, cervical carcinoma (HeLa) and colorectal adenocarcinoma (Caco-2), by metabolic tests, using 3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyl-tetrazolium bromide as reagent. The complex 1 has remarkable low IC50 values of 0.87±0.06μM (HeLa) and 0.44±0.06μM (Caco-2), when compared with values for cisplatin against the same cell lines. The interaction of complex 1 with calf thymus DNA (CT DNA) was further investigated by absorption and fluorescence spectroscopic methods. A binding constant of 5.09×10(5)M(-1) was obtained from UV-vis absorption studies. Copyright © 2016 Elsevier Inc. All rights reserved.

  2. Mono- and Dinuclear Phosphorescent Rhenium(I) Complexes: Impact of Subcellular Localization on Anticancer Mechanisms. (United States)

    Ye, Rui-Rong; Tan, Cai-Ping; Chen, Mu-He; Hao, Liang; Ji, Liang-Nian; Mao, Zong-Wan


    Elucidation of relationship among chemical structure, cellular uptake, localization, and biological activity of anticancer metal complexes is important for the understanding of their mechanisms of action. Organometallic rhenium(I) tricarbonyl compounds have emerged as potential multifunctional anticancer drug candidates that can integrate therapeutic and imaging capabilities in a single molecule. Herein, two mononuclear phosphorescent rhenium(I) complexes (Re1 and Re2), along with their corresponding dinuclear complexes (Re3 and Re4), were designed and synthesized as potent anticancer agents. The subcellular accumulation of Re1-Re4 was conveniently analyzed by confocal microscopy in situ in live cells by utilizing their intrinsic phosphorescence. We found that increased lipophilicity of the bidentate ligands could enhance their cellular uptake, leading to improved anticancer efficacy. The dinuclear complexes were more potent than the mononuclear counterparts. The molecular anticancer mechanisms of action evoked by Re3 and Re4 were explored in detail. Re3 with a lower lipophilicity localizes to lysosomes and induces caspase-independent apoptosis, whereas Re4 with higher lipophilicity specially accumulates in mitochondria and induces caspase-independent paraptosis in cancer cells. Our study demonstrates that subcellular localization is crucial for the anticancer mechanisms of these phosphorescent rhenium(I) complexes. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  3. DNA interactions of dinuclear RuII arene antitumor complexes in cell-free media

    Czech Academy of Sciences Publication Activity Database

    Nováková, Olga; Nazarov, A.A.; Hartinger, Ch.G.; Keppler, B.K.; Brabec, Viktor


    Roč. 77, č. 3 (2009), s. 364-374 ISSN 0006-2952 R&D Projects: GA MŠk(CZ) LC06030; GA MŠk(CZ) ME08017; GA MŠk(CZ) OC08003; GA AV ČR(CZ) 1QS500040581; GA AV ČR(CZ) KAN200200651 Institutional research plan: CEZ:AV0Z50040507; CEZ:AV0Z50040702 Keywords : dinuclear ruthenium complex * DNA * cross-links Subject RIV: BO - Biophysics Impact factor: 4.254, year: 2009

  4. Supramolecular architecture of metal-organic frameworks involving dinuclear copper paddle-wheel complexes. (United States)

    Gomathi, Sundaramoorthy; Muthiah, Packianathan Thomas


    The two centrosymmetric dinuclear copper paddle-wheel complexes tetrakis(μ-4-hydroxybenzoato-κ(2)O:O')bis[aquacopper(II)] dimethylformamide disolvate dihydrate, [Cu2(C7H5O3)4(H2O)2]·2C3H7NO·2H2O, (I), and tetrakis(μ-4-methoxybenzoato-κ(2)O:O')bis[(dimethylformamide-κO)copper(II)], [Cu2(C8H7O3)4(C3H7NO)2], (II), crystallize with half of the dinuclear paddle-wheel cage unit in the asymmetric unit and, in addition, complex (I) has one dimethylformamide (DMF) and one water solvent molecule in the asymmetric unit. In both (I) and (II), two Cu(II) ions are bridged by four syn,syn-η(1):η(1):μ carboxylate groups, showing a paddle-wheel cage-type structure with a square-pyramidal coordination geometry. The equatorial positions of (I) and (II) are occupied by the carboxylate groups of 4-hydroxy- and 4-methoxybenzoate ligands, and the axial positions are occupied by aqua and DMF ligands, respectively. The three-dimensional supramolecular metal-organic framework of (I) consists of three different R2(2)(20) and an R4(4)(36) ring motif formed via O-H···O and OW-HW···O hydrogen bonds. Complex (II) simply packs as molecular species.

  5. EPR interpretation, magnetism and biological study of a Cu(II) dinuclear complex assisted by a schiff base precursor. (United States)

    Das, Kuheli; Patra, Chiranjit; Sen, Chandana; Datta, Amitabha; Massera, Chiara; Garribba, Eugenio; El Fallah, Mohamed Salah; Beyene, Belete B; Hung, Chen-Hsiung; Sinha, Chittaranjan; Askun, Tulin; Celikboyun, Pinar; Escudero, Daniel; Frontera, Antonio


    A new Cu(II) dinuclear complex, Cu 2 L 2 (1) was afforded employing the potentially pentatentate Schiff base precursor H 2 L, a refluxed product of o-vanillin and diethylenetriamine in methanol. Complex 1 was systematically characterized by FTIR, UV-Vis, emission and EPR spectrometry. The single crystal X-ray diffraction analysis of 1 reveals that the copper atom exhibits a distorted square planar geometry, comprising two pairs of phenolato-O and imine-N donors from two different H 2 L ligands. The temperature dependent magnetic interpretation agrees with the existence of weak antiferromagnetic interactions between the bridging dinuclear Cu(II) ions. A considerable body of experimental evidence has been accumulated to elucidate the magneto-structural relationship in this dinuclear Cu(II) complex by DFT computation. Both the ligand and complex 1 exhibit anti-mycobacterial activity and considerable efficacy on M. tuberculosis H 37 Ra (ATCC 25177) and M. tuberculosis H 37 Rv (ATCC 25618) strains. The practical applicability of the ligand and complex 1 has been examined in living cells (African Monkey Vero Cells). The MTT assay proves the non-toxicity of the probe up to 100 mg mL -1 . A new homometallic dinuclear Cu(II) complex is afforded with a tetradentate Schiff base precursor. EPR interpretation and temperature dependent magnetic studies show that complex 1 has weak antiferromagnetic coupling and DFT computation is governed to explain the magneto-structural correlation.

  6. Synthesis, crystal structure and DFT studies of a novel dinuclear copper(I) complex with triphenylphosphine and 2-mercaptonicotinic acid (United States)

    Ahmad, Tayyaba; Mahmood, Rashid; Georgieva, Ivelina; Zahariev, Tsvetan; Tahir, Muhammad Nawaz; Shaheen, Muhammad Ashraf; Gilani, Mazhar Amjad; Ahmad, Saeed


    A novel dinuclear copper(I) complex, {[Cu2(Mnt)2(PPh3)2Cl2].2H2O.CH3CN}2 (1) (Mnt = Mercaptonicotinic acid, PPh3 = triphenylphosphine) was prepared and its structure was determined by X-ray crystallography. The complex 1 consists of two dinuclear molecules and in each molecule, the two copper atoms are bridged by S atoms of N-protonated mercaptonicotinic acid forming a four-membered ring. The planar Cu2S2 core is characterized by significant cuprophilic interactions (Cusbnd Cu distance = 2.7671(8), 2.8471(8) Å). Each copper atom in 1 is coordinated by two sulfur atoms of Mnt, one phosphorus atom of PPh3 and a chloride ion adopting a tetrahedral geometry. The calculated Gibbs energies for reaction in CH3CN supported the experimental structure and predicted more favorable formation of dinuclear Cu(I) complex as compared to the mononuclear Cu(I) complex. The dinuclear complex is stabilized by 65.98 kJ mol-1 by coupling of two mononuclear Cu(I) complexes. The IR spectra of 1 and Mnt ligand were reliably interpreted and the Mnt vibrations, which are sensitive to the ligand coordination to Cu(I) ion in 1 were selected with the help of DFT/ωB97XD calculations.

  7. Mono and dinuclear iridium, rhodium and ruthenium complexes containing chelating carboxylato pyrazine ligands: Synthesis, molecular structure and electrochemistry

    Czech Academy of Sciences Publication Activity Database

    Govindaswamy, P.; Therrien, B.; Süss-Fink, G.; Štěpnička, P.; Ludvík, Jiří


    Roč. 692, č. 8 (2007), s. 1661-1671 ISSN 0022-328X R&D Projects: GA MŠk LC510; GA MŠk(CZ) LC06070 Institutional research plan: CEZ:AV0Z40400503 Keywords : dinuclear complexes * iridium * rhodium * ruthenium * electrochemistry Subject RIV: CG - Electrochemistry Impact factor: 2.168, year: 2007

  8. Interaction of dinuclear cadmium(II) 5-Cl-salicylaldehyde complexes with calf-thymus DNA

    Energy Technology Data Exchange (ETDEWEB)

    Ristovic, Maja Sumar [Department of General and Inorganic Chemistry, Faculty of Chemistry, Aristotle University of Thessaloniki, GR-54124 Thessaloniki (Greece); Faculty of Chemistry, University of Belgrade, Studenski Trg 12-16, Belgrade (Serbia); Zianna, Ariadni; Psomas, George; Hatzidimitriou, Antonios G. [Department of General and Inorganic Chemistry, Faculty of Chemistry, Aristotle University of Thessaloniki, GR-54124 Thessaloniki (Greece); Coutouli-Argyropoulou, Evdoxia [Department of Organic Chemistry and Biochemistry, Faculty of Chemistry, Aristotle University of Thessaloniki, GR-54124 Thessaloniki (Greece); Lalia-Kantouri, Maria, E-mail: [Department of General and Inorganic Chemistry, Faculty of Chemistry, Aristotle University of Thessaloniki, GR-54124 Thessaloniki (Greece)


    Five dinuclear Cd(II) complexes with the anion of 5-Cl-salicylaldehyde (5-Cl-saloH) were synthesized in the absence or presence of the α-diimines: 2,2′-bipyridine (bipy), 1,10-phenanthroline (phen), 2,9-dimethyl-1,10-phenanthroline (neoc) or 2,2′-dipyridylamine (dpamH) and characterized as [Cd(5-Cl-salo){sub 2}(CH{sub 3}OH)]{sub 2} (1), [Cd(5-Cl-salo){sub 2}(bipy)]{sub 2} (2), [Cd(5-Cl-salo){sub 2}(phen)]{sub 2} (3), [Cd(5-Cl-salo)(neoc)(ONO{sub 2})]{sub 2} (4) and [Cd(5-Cl-salo)(dpamΗ)(ONO{sub 2})]{sub 2} (5). The complexes were characterized by spectroscopic techniques (IR, UV‐vis, {sup 1}H-NMR and {sup 13}C–NMR), elemental analysis and molar conductivity measurements. The structures of four complexes (1–3 and 5) were determined by X-ray crystallography, providing all three possible coordination modes of the ligand 5-Cl-salicylaldehyde, i.e. bidentate or tridentate chelating and/or bridging mode. The complexes bind to calf-thymus (CT) DNA mainly by intercalation, as concluded by the viscosity measurements and present relatively high DNA-binding constants. The complexes exhibit significant ability to displace ethidium bromide (EB) from the EB-DNA complex, thus indirectly proving the intercalation as the most possible binding mode to CT DNA. - Graphical abstract: Cadmium complexes of the formulae [Cd(5-Cl-salo){sub 2}(CH{sub 3}OH)]{sub 2} and [Cd(5-Cl-salo){sub 2}(α-diimine)]{sub 2} or [Cd(5-Cl-salo)(α-diimine)(ONO{sub 2})]{sub 2} have been synthesized and characterized. The complexes bind tightly to CT DNA probably by intercalation competing with ethidium bromide for the intercalation site of DNA. - Highlights: • Synthesis of a series of dinuclear Cd complexes • The complexes characterized by diverse techniques. • The crystal structures of four complexes have been determined. • Intercalation is the most possible binding mode of the complexes to DNA. • The complexes compete with ethidium bromide for the DNA-intercalating sites.

  9. A dinuclear zinc complex with (E-4-dimethylamino-N′-(2-hydroxybenzylidenebenzohydrazide

    Directory of Open Access Journals (Sweden)

    Jie Ma


    Full Text Available The title compound, bis[μ-(E-2-({2-[4-(dimethylaminobenzoyl]hydrazinylidene}methylphenolato]bis[formatozinc], [Zn2(C16H16N3O22(CHO22], is a dinuclear ZnII complex containing two ZnII cations, two monovalent anions of a Schiff base ligand, 4-dimethylamino-N′-(2-hydroxybenzylidenebenzohydrazide (L, and two formate ions. Each ZnII atom chelates with the hydroxy O atom of salicylaldehyde, the imine N atom, the carbonyl O atom, the formate carboxylate O atom and the hydroxy O atom of the salicylaldehyde moiety in a symmetry-related unit. The five-coordinate ZnII atoms form a dimeric centrosymmetric unit with a central parallelepiped Zn2O2 core and parallel faces derived from the Schiff base ligands. The crystal packing is stabilized by intermolecular N—H...O hydrogen bonds between the amide N atom and the formate carboxylate O atom.

  10. Dinuclear Tetrapyrazolyl Palladium Complexes Exhibiting Facile Tandem Transfer Hydrogenation/Suzuki Coupling Reaction of Fluoroarylketone

    KAUST Repository

    Dehury, Niranjan


    Herein, we report an unprecedented example of dinuclear pyrazolyl-based Pd complexes exhibiting facile tandem catalysis for fluoroarylketone: Tetrapyrazolyl di-palladium complexes with varying Pd-Pd distances efficiently catalyze the tandem reaction involving transfer hydrogenation of fluoroarylketone to the corresponding alcohol and Suzuki-Miyaura cross coupling reaction of the resulting fluoroarylalcohol under moderate reaction conditions, to biaryl alcohol. The complex with the shortest Pd-Pd distance exhibits the highest tandem activity among its di-metallic analogues, and exceeds in terms of activity and selectivity the analogous mononuclear compound. The kinetics of the reaction indicates clearly that reductive transformation of haloarylketone into haloaryalcohol is the rate determining step in the tandem reaction. Interestingly while fluoroarylketone undergoes the multistep tandem catalysis, the chloro- and bromo-arylketones undergo only a single step C-C coupling reaction resulting in biarylketone as the final product. Unlike the pyrazole based Pd compounds, the precursor PdCl2 and the phosphine based relevant complexes (PPh3)2PdCl2 and (PPh3)4Pd are found to be unable to exhibit the tandem catalysis.

  11. Bent and planar structures of μ-η²:η²-N₂ dinuclear early transition metal complexes. (United States)

    Ma, Xuelu; Tang, Yanhui; Lei, Ming


    This work studied the bent and planar structures of M2N2 cores of a series of dinuclear early transition-metal complexes (M = Zr, Hf, Nb, Ta, Mo and W) containing a side-on bridging dinitrogen ligand using DFT method. The calculated results propose three key factors favoring a bent structure: (1) the availability of a single electron in the metal centers which leads to the bonding interaction between two metal atoms, (2) no remarkable steric effect around the metal centers, and (3) the cis conformation of the ligands in the dinitrogen dinuclear complexes. In addition, the bent and planar structures of M2N2 could be transformed into each other if the steric hindrance was slight.

  12. Dinuclear nickel complexes with bidentate N,O ligands: synthesis, structure, and catalytic oligomerization of ethylene. (United States)

    Speiser, Fredy; Braunstein, Pierre; Saussine, Lucien


    The new dicationic dinuclear complexes [Ni(micro-Cl)(2)(N,OH)(2)]Cl(2) (11, N,OH = 2-(4,4-dimethyl-4,5-dihydrooxazol-2-yl)-propan-2-ol; 12, N,OH = 2-pyridin-2-yl-propan-2-ol) were prepared in good yields and evaluated as precatalyts in the oligomerization of ethylene, using MAO or AlEtCl(2) as cocatalyst. These paramagnetic complexes were characterized by single-crystal X-ray diffraction in the solid state and in solution with the help of the Evans method, which revealed agreement between the octahedral coordination spheres found in solution and in the solid state. The N donor atoms of each chelating ligand are in mutual cis position, and the OH donors are mutually trans situated. Selectivities for 1-butene within the C(4) fraction of 61% (11) and 58% (12) were observed in the presence of 200 equiv of MAO, but better turnover frequencies (28 300 (11) and 20 400 (12) mol of C(2)H(4)/(mol of Ni.h)) were obtained when 800 equiv of MAO was used. In the presence of 6 equiv of AlEtCl(2), the activities were considerably increased, up to 174 300 (11) and 97 100 (12) mol of C(2)H(4)/(mol of Ni.h), and the selectivity for C(4) olefins was 70% and 64%, respectively.

  13. Versatile deprotonated NHC: C,N-bridged dinuclear iridium and rhodium complexes

    Directory of Open Access Journals (Sweden)

    Albert Poater


    Full Text Available Bearing the versatility of N-heterocyclic carbene (NHC ligands, here density functional theory (DFT calculations unravel the capacity of coordination of a deprotonated NHC ligand (pNHC to generate a doubly C2,N3-bridged dinuclear complex. Here, in particular the discussion is based on the combination of the deprotonated 1-arylimidazol (aryl = mesityl (Mes with [M(cod(μ-Cl] (M = Ir, Rh generated two geometrical isomers of complex [M(cod{µ-C3H2N2(Mes-κC2,κN3}]2. The latter two isomers display conformations head-to-head (H-H and head-to-tail (H-T of CS and C2 symmetry, respectively. The isomerization from the H-H to the H-T conformation is feasible, whereas next substitutions of the cod ligand by CO first, and PMe3 later confirm the H-T coordination as the thermodynamically preferred. It is envisaged the exchange of the metal, from iridium to rhodium, confirming here the innocence of the nature of the metal for such arrangements of the bridging ligands.

  14. Synthesis, Crystal Structure, and Cytotoxic Activity of a Novel Eight-Coordinated Dinuclear Ca(II-Schiff Base Complex

    Directory of Open Access Journals (Sweden)

    Xi-Shi Tai


    Full Text Available A novel eight-coordinated dinuclear Ca(II complex, [Ca2(L2(H2O10]·H2O (L = 4-formylbenzene-1,3-disulfonate-3-pyridinecarboxylic hydrazone (1, was synthesized by the reaction of 3-pyridinecarboxylic hydrazide, disodium 4-formylbenzene-1,3-disulfonate, and Ca(ClO42·4H2O in ethanol-water solution (v:v = 3:1 at 50 °C. Complex 1 was characterized by elemental analysis, IR, 1H-NMR, 13C-NMR, and X-ray single crystal diffraction analysis. Dinuclear Ca(II complex 1 belongs to triclinic, space group P-1 with a = 7.186(3 Å, b = 11.978(5 Å, c = 12.263(5 Å, α = 90.318(5°, β = 91.922(5°, γ = 96.797(5°, V = 1047.5(8 Å3, Z = 1, Dc = 1.685 mg·m−3, μ = 0.572 mm−1, F(000 = 552, and final R1 = 0.0308, ωR2 = 0.0770. Dinuclear Ca(II molecules form a 1D chained structure by π–π stacking interaction. The 1D chains form a 3D framework structure by the π–π stacking interaction and hydrogen bonds. The in vitro cytotoxic activity activity of 1 against HL-60 and MLTC-1 was also investigated.

  15. Insights into the Halogen Oxidative Addition Reaction to Dinuclear Gold(I) Di(NHC) Complexes

    KAUST Repository

    Baron, Marco


    Gold(I) dicarbene complexes [Au2(MeIm-Y-ImMe)2](PF6)2(Y=CH2(1), (CH2)2(2), (CH2)4(4), MeIm=1-methylimidazol-2-ylidene) react with iodine to give the mixed-valence complex [Au(MeIm-CH2-ImMe)2AuI2](PF6)2(1 aI) and the gold(III) complexes [Au2I4(MeIm-Y-ImMe)2](PF6)2(2 cIand 4 cI). Reaction of complexes 1 and 2 with an excess of ICl allows the isolation of the tetrachloro gold(III) complexes [Au2Cl4(MeIm-CH2-ImMe)2](PF6)2(1 cCl) and [Au2Cl4(MeIm-(CH2)2-ImMe)2](Cl)2(2 cCl-Cl) (as main product); remarkably in the case of complex 2, the X-ray molecular structure of the crystals also shows the presence of I-Au-Cl mixed-sphere coordination. The same type of coordination has been observed in the main product of the reaction of complexes 3 or 4 with ICl. The study of the reactivity towards the oxidative addition of halogens to a large series of dinuclear bis(dicarbene) gold(I) complexes has been extended and reviewed. The complexes react with Cl2, Br2and I2to give the successive formation of the mixed-valence gold(I)/gold(III) n aXand gold(III) n cX(excluding compound 1 cI) complexes. However, complex 3 affords with Cl2and Br2the gold(II) complex 3 bX[Au2X2(MeIm-(CH2)3-ImMe)2](PF6)2(X=Cl, Br), which is the predominant species over compound 3 cXeven in the presence of free halogen. The observed different relative stabilities of the oxidised complexes of compounds 1 and 3 have also been confirmed by DFT calculations. © 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  16. Mechanism of Water Oxidation Catalyzed by a Dinuclear Ruthenium Complex Bridged by Anthraquinone

    Directory of Open Access Journals (Sweden)

    Tohru Wada


    Full Text Available We synthesized 1,8-bis(2,2′:6′,2″-terpyrid-4′-ylanthraquinone (btpyaq as a new dimerizing ligand and determined its single crystal structure by X-ray analysis. The dinuclear Ruthenium complex [Ru2(µ-Cl(bpy2(btpyaq](BF43 ([3](BF43, bpy = 2,2′-bipyridine was used as a catalyst for water oxidation to oxygen with (NH42[Ce(NO36] as the oxidant (turnover numbers = 248. The initial reaction rate of oxygen evolution was directly proportional to the concentration of the catalyst and independent of the oxidant concentration. The cyclic voltammogram of [3](BF43 in water at pH 1.3 showed an irreversible catalytic current above +1.6 V (vs. SCE, with two quasi-reversible waves and one irreversible wave at E1/2 = +0.62, +0.82 V, and Epa = +1.13 V, respectively. UV-vis and Raman spectra of [3](BF43 with controlled-potential electrolysis at +1.40 V revealed that [Ru(IV=O O=Ru(IV]4+ is stable under electrolysis conditions. [Ru(III, Ru(II] species are recovered after dissociation of an oxygen molecule from the active species in the catalytic cycle. These results clearly indicate that an O–O bond is formed via [Ru(V=O O=Ru(IV]5+.

  17. Thiolate-bridged dinuclear ruthenium and iron complexes as robust and efficient catalysts toward oxidation of molecular dihydrogen in protic solvents. (United States)

    Yuki, Masahiro; Sakata, Ken; Hirao, Yoshifumi; Nonoyama, Nobuaki; Nakajima, Kazunari; Nishibayashi, Yoshiaki


    Thiolate-bridged dinuclear ruthenium and iron complexes are found to work as efficient catalysts toward oxidation of molecular dihydrogen in protic solvents such as water and methanol under ambient reaction conditions. Heterolytic cleavage of the coordinated molecular dihydrogen at the dinuclear complexes and the sequential oxidation of the produced hydride complexes are involved as key steps to promote the present catalytic reaction. The catalytic activity of the dinuclear complexes toward the chemical oxidation of molecular dihydrogen achieves up to 10000 TON (turnover number), and electrooxidation of molecular dihydrogen proceeds quite rapidly. The result of the density functional theory (DFT) calculation on the reaction pathway indicates that a synergistic effect between the two ruthenium atoms plays an important role to realize the catalytic oxidation of molecular dihydrogen efficiently. The present dinuclear ruthenium complex is found to work as an efficient organometallic anode catalyst for the fuel cell. It is noteworthy that the present dinuclear complex worked not only as an effective catalyst toward chemical and electrochemical oxidation of molecular dihydrogen but also as a good anode catalyst for the fuel cell. We consider that the result described in this paper provides useful and valuable information to develop highly efficient and low-cost transition metal complexes as anode catalysts in the fuel cell.

  18. Ferromagnetic dinuclear mixed-valence Mn(II)/Mn(III) complexes: building blocks for the higher nuclearity complexes. structure, magnetic properties, and density functional theory calculations. (United States)

    Hänninen, Mikko M; Välivaara, Juha; Mota, Antonio J; Colacio, Enrique; Lloret, Francesc; Sillanpää, Reijo


    A series of six mixed-valence Mn(II)/Mn(III) dinuclear complexes were synthesized and characterized by X-ray diffraction. The reactivity of the complexes was surveyed, and structures of three additional trinuclear mixed-valence Mn(III)/Mn(II)/Mn(III) species were resolved. The magnetic properties of the complexes were studied in detail both experimentally and theoretically. All dinuclear complexes show ferromagnetic intramolecular interactions, which were justified on the basis of the electronic structures of the Mn(II) and Mn(III) ions. The large Mn(II)-O-Mn(III) bond angle and small distortion of the Mn(II) cation from the ideal square pyramidal geometry were shown to enhance the ferromagnetic interactions since these geometrical conditions seem to favor the orthogonal arrangement of the magnetic orbitals.


    Directory of Open Access Journals (Sweden)

    Masahiro Mikuriya


    Full Text Available Mixed-metal chain complexes constructed from lantern-type dinuclear ruthenium(II,III carboxylate unit and tetracyanidonickelate(II, (PPh4n[Ru2(O2CCH34Ni(CN4]n•nH2O (1 and (PPh4n[Ru2{O2CC(CH33}4]3n[Ni(CN4]2n•2nH2O (2, where very weak antiferromagnetic interaction is operating, were synthesized and characterized by elemental analysis and IR and UV-vis spectroscopies and temperature dependence of magnetic susceptibilities (4.5—300K.

  20. Study of dinuclear Rh(II) complexes of phenylalanine derivatives as potential anticancer agents by using X-ray fluorescence and X-ray absorption

    NARCIS (Netherlands)

    Majer, Zsuzsa; Bosze, Szilvia; Szabo, Ildiko; Mihucz, Victor G.; Gaal, Aniko; Szilvagyi, Gabor; Pepponi, Giancarlo; Meirer, Florian; Wobrauschek, Peter; Szoboszlai, Norbert; Ingerle, Dieter; Streli, Christina

    In vitro antitumor efficacy of several dinuclear bridgings and one chelate structure dirhodium(II) complex of N-protected phenylalanine derivatives were tested on HT-29 cells. The following synthesized and previously characterized complexes were applied in the present work: Rh-2(OAc)(4)(O-Phe-Z)(n)

  1. A novel dinuclear Ru(II) complex having a bridging ligand of a rigid and extended structure. Incorporation of an anthraquinone unit and efficient emission quenching

    International Nuclear Information System (INIS)

    Mishra, L.; Choi, Chang-Shik; Araki, Koji


    Dinuclear Ru(II) complex having extended conjugation within the bridging ligand was prepared by coupling of the Ru(II) polypyridyl complex having a benzoyl-substituted phenazine unit with diaminoanthraquinone in one step, in which emission from the excited Ru(II) center was efficiently quenched through the anthraquinone unit. (author)

  2. Crystal structure of a mixed-ligand dinuclear Ba—Zn complex with 2-methoxyethanol having triphenylacetate and chloride bridges

    Directory of Open Access Journals (Sweden)

    Józef Utko


    Full Text Available The dinuclear barium–zinc complex, μ-chlorido-1:2κ2Cl:Cl-chlorido-2κCl-bis(2-methoxyethanol-1κObis(2-methoxyethanol-1κ2O,O′bis(μ-triphenylacetato-1:2κ2O:O′bariumzinc, [BaZn(C20H15O22Cl2(C3H8O24], has been synthesized by the reaction of barium triphenylacetate, anhydrous zinc chloride and 2-methoxyethanol in the presence of toluene. The barium and zinc metal cations in the dinuclear complex are linked via one chloride anion and carboxylate O atoms of the triphenylacetate ligands, giving a Ba...Zn separation of 3.9335 (11 Å. The irregular nine-coordinate BaO8Cl coordination centres comprise eight O-atom donors, six of them from 2-methoxyethanol ligands (four from two bidentate O,O′-chelate interactions and two from monodentate interactions, two from bridging triphenylacetate ligands and one from a bridging Cl donor. The distorted tetrahedral coordination sphere of zinc comprises two O-atom donors from the triphenylacetate ligands and two Cl donors (one bridging and one terminal. In the crystal, O—H...Cl, O—H...O and C—H...Cl intermolecular interactions form a layered structure, lying parallel to (001.

  3. Ferromagnetic interactions in new double end-on-azide-bridged dinuclear Ni(II) complex: Synthesis, crystal structures, magnetic and photoluminescence properties (United States)

    Donmez, Adem; Oylumluoglu, Gorkem; Coban, M. Burak; Kocak, Cagdas; Aygun, Muhittin; Kara, Hulya


    A new double end-on azide-bridged dinuclear nickel(II) Schiff base complex, [Ni2(μ1,1-N3)2(HL)2(MeOH)2], [HL = 2-[(2-hydroxypropylimino)methyl)-3,5-chlorophenol] has been synthesized and characterized by elemental analysis, UV and IR spectroscopy, single crystal X-ray diffraction, magnetic and photoluminescence study. The asymmetric unit contains half of the dinuclear unit. The Ni(HL) units in each dinuclear molecule are connected to each other by two bridging end-on azide ligands. In the crystalline architecture of the Ni(II) complex, intermolecular Osbnd H⋯N hydrogen bonds link the molecules which form one-dimensional structure. Additionally, low temperature magnetic measurements indicate a dominant intradimer ferromagnetic interactions in double end-on azide-bridged dinuclear Ni(II) complex. Room temperature solid state photoluminescence measurements of Ni(II) complex show strong green emission band at λmax = 508 nm while its free ligand H2L shows broad yellow emission band at λmax = 594 nm. The luminescent performances making Ni(II) complex may be good candidates for potential luminescence materials.

  4. Highly luminescent, triple- and quadruple-stranded, dinuclear Eu, Nd, and Sm(III) lanthanide complexes based on bis-diketonate ligands

    NARCIS (Netherlands)

    Bassett, A.P.; Magennis, S.W.; Glover, P.B.; Lewis, D.J.; Spencer, N.; Parsons, S.; Williams, R.M.; De Cola, L.; Pikramenou, Z.


    The bis(beta-diketone) ligands 1,3-bis(3-phenyl-3-oxopropanoyl)benzene, H(2)L(1) and 1,3-bis(3-phenyl-3-oxopropanoyl) 5-ethoxy-benzene, H(2)L(2), have been prepared for the examination of dinuclear lanthanide complex formation and investigation of their properties as sensitizers for lanthanide

  5. Highly luminescent, triple- and quadruple-stranded, dinuclear Eu, Nd, and Sm(III) lanthanide complexes based on bis-diketonate ligands

    NARCIS (Netherlands)

    Bassett, A.P.; Magennis, S.W.; Glover, P.B.; Lewis, D.J.; Spencer, N.; Parsons, S.; Williams, R.M.; De Cola, L.; Pikramenou, Z.


    The bis(beta-diketone) ligands 1,3-bis(3-phenyl-3-oxopropanoyl)benzene, H2L1 and 1,3-bis(3-phenyl-3-oxopropanoyl) 5-ethoxy-benzene, H2L2, have been prepared for the examination of dinuclear lanthanide complex formation and investigation of their properties as sensitizers for lanthanide luminescence.

  6. Mono and dinuclear rhodium, iridium and ruthenium complexes containing chelating 2,2´-bipyrimidine ligands: Synthesis, molecular structure, electrochemistry and catalytic properties

    Czech Academy of Sciences Publication Activity Database

    Govindaswamy, P.; Canivet, J.; Therrien, B.; Süss-Fink, G.; Štěpnička, P.; Ludvík, Jiří


    Roč. 692, č. 17 (2007), s. 3664-3675 ISSN 0022-328X R&D Projects: GA MŠk(CZ) LC06070 Institutional research plan: CEZ:AV0Z40400503 Keywords : arene ligands * electrochemistry * dinuclear complexes * transfer hydrogenation Subject RIV: CG - Electrochemistry Impact factor: 2.168, year: 2007

  7. 155Gd Moessbauer spectroscopic investigation of 3d-4f and 4f-4f' dinuclear complexes containing Gd (III)

    International Nuclear Information System (INIS)

    Ayabe, T.; Takahashi, M.; Takeda, M.; Costes, J.P.


    155 Gd Moessbauer spectra for dinuclear complexes of Gd 3+ and lanthanide (III) ion having a Schiff base ligand (L) derived from tren and 3-ethoxysalicylaldehyde were measured at 12 K. Moessbauer spectra of these complexes showed quadrupole split spectra. Two kinds of isomer shift values are observed; i.e, δ=0.57 - 0.60 mm s -1 for LGdLn' (Ln' = Ce, Nd, Eu, Gd) and δ=0.64-0.66 mm s -1 for LLnGd (Ln=Dy, Er, Yb). The former values are very close to those of nitrogen-containing Gd (III) complexes (δ=0.59-0.62 mm s -1 ) such as edta and cyano-bridged complexes. The latter values are on the other hand, in the range of oxygen-coordinating Gd (III) complexes (δ=0.64-0.65 mm s -1 ) such as polyethylene glycol Gd (III) complexes. 155 Gd Moessbauer spectra for LLnLn' complexes indicate that the smaller lanthanide ion Ln is in the N 4 O 3 site and the larger ion Ln' in the O 10 site. (author)

  8. Mono- and dinuclear manganese(III) complexes showing efficient catechol oxidase activity: syntheses, characterization and spectroscopic studies. (United States)

    Banu, Kazi Sabnam; Chattopadhyay, Tanmay; Banerjee, Arpita; Mukherjee, Madhuparna; Bhattacharya, Santanu; Patra, Goutam Kumar; Zangrando, Ennio; Das, Debasis


    Four side-off compartmental ligands L1-L4 [L1 = N,N'-ethylenebis(3-formyl-5-methyl-salicylaldimine), L2 = N,N'-1-methylethylenebis(3-formyl-5-methylsalicylaldimine), L3 = N,N'-1,1-dimethylethylenebis(3-formyl-5-methylsalicylaldimine) and L4= N,N'-cyclohexenebis(3-formyl-5-methylsalicylaldimine)] having two binding sites, N2O2 and O4, have been chosen to synthesize mononuclear and dinuclear manganese(III) complexes with the aim to study their catecholase activity using 3,5-di-tert-butylcatechol (3,5-DTBC) as substrate in the presence of molecular oxygen. In all cases only mononuclear manganese complexes (1-4) were obtained, with manganese coordination taking place at the N2O2 binding site only, irrespective of the amount of manganese salt used. All these complexes have been characterized by routine physico-chemical techniques. Complex MnL2Cl.4H2O (2) has further been structurally characterized by X-ray single crystal structure analysis. Four dinuclear manganese complexes, 5-8, were obtained after condensing the two pending formyl groups on each ligand (L1-L4) with aniline followed by reaction with MnCl2 to put the second Mn atom onto another N2O2 site. The catalytic activity of all complexes 1-8 has been investigated following the oxidation of 3,5-di-tert-butylcatechol (3,5-DTBC) to 3,5-di-tert-butylbenzoquinone (3,5-DTBQ) with molecular oxygen in two different solvents, methanol and acetonitrile. The study reveals that the catalytic activity is influenced by the solvent and to a significant extent by the backbone of the diamine and the behavior seems to be related mainly to steric rather than electronic factors. Experimental data suggest that a correlation, the lower the E(1/2) value the higher the catalytic activity, can be drawn between E(1/2) and Vmax of the complexes in a particular solvent. The EPR measurements suggest that the catalytic property of the complexes is related to the metal center(s) participation rather than to a radical mechanism.

  9. Blue-emitting dinuclear N-heterocyclic dicarbene gold(I) complex featuring a nearly unit quantum yield

    KAUST Repository

    Baron, Marco


    Dinuclear N-heterocyclic dicarbene gold(I) complexes of general formula [Au 2(RIm-Y-ImR) 2](PF 6) 2 (R = Me, Cy; Y = (CH 2) 1-4, o-xylylene, m-xylylene) have been synthesized and screened for their luminescence properties. All the complexes are weakly emissive in solution whereas in the solid state some of them show significant luminescence intensities. In particular, crystals or powders of the complex with R = Me, Y = (CH 2) 3 exhibit an intense blue emission (λ max = 450 nm) with a high quantum yield (Φ em = 0.96). The X-ray crystal structure of this complex is characterized by a rather short intramolecular Au•••Au distance (3.272 Ǻ). Time dependent density functional theory (TDDFT) calculations have been used to calculate the UV/vis properties of the ground state as well as of the first excited state of the complex, the latter featuring a significantly shorter Au•••Au distance. © 2012 American Chemical Society.

  10. Synthesis, structure, magnetic and catalytic properties of new dinuclear chromium(III) complexes with oxazoline alcoholate ligands. (United States)

    Jie, Suyun; Pattacini, Roberto; Rogez, Guillaume; Loose, Claudia; Kortus, Jens; Braunstein, Pierre


    The dinuclear chromium complexes [Cr(2)(N,O)(3)Cl(3)] (6) (N,O = 4,4-dimethyl-2-oxazolylmethanolate), [Cr(2)(N,O(Me2))(2)(EtOH)(2)Cl(4)] (7) and [Cr(2)(N,O(Me2))(2)(H(2)O)(2)Cl(4)] (8) (N,O(Me2) = 4,4-dimethyl-2-oxazolyldimethylmethanolate) have been prepared and characterized, including by single-crystal X-ray diffraction. Complex 6 is unsymmetrical, with two chloride ligands terminally bound to one Cr atom, whereas 7 and 8 (in 8 x C(4)H(8)O) which contain two molecules of coordinated ethanol or water, respectively, are centrosymmetric. These chromium complexes are paramagnetic, and the magnetic properties of 6 and 7 in the solid state correspond to antiferromagnetic behaviour, which was confirmed by DFT calculations of their electronic structures. Complexes 6-8 were evaluated in the catalytic oligomerization and/or polymerization of ethylene with different aluminium-based cocatalysts, and MMAO proved to be the most effective one. In the presence of MMAO, the influence of different reaction parameters, such as the Al/Cr molar ratio, reaction temperature and ethylene pressure, was investigated. Complex 7 showed the highest activity for ethylene polymerization at both 1 atm and 10 atm of ethylene pressure, up to 620 000 g mol(-1)(Cr) h(-1) in the latter case.

  11. Rational design of a cytotoxic dinuclear Cu2 complex that binds by molecular recognition at two neighboring phosphates of the DNA backbone. (United States)

    Jany, Thomas; Moreth, Alexander; Gruschka, Claudia; Sischka, Andy; Spiering, Andre; Dieding, Mareike; Wang, Ying; Samo, Susan Haji; Stammler, Anja; Bögge, Hartmut; Fischer von Mollard, Gabriele; Anselmetti, Dario; Glaser, Thorsten


    The mechanism of the cytotoxic function of cisplatin and related anticancer drugs is based on their binding to the nucleobases of DNA. The development of new classes of anticancer drugs requires establishing other binding modes. Therefore, we performed a rational design for complexes that target two neighboring phosphates of the DNA backbone by molecular recognition resulting in a family of dinuclear complexes based on 2,7-disubstituted 1,8-naphthalenediol. This rigid backbone preorganizes the two metal ions for molecular recognition at the distance of two neighboring phosphates in DNA of 6-7 Å. Additionally, bulky chelating pendant arms in the 2,7-position impede nucleobase complexation by steric hindrance. We successfully synthesized the Cu(II)2 complex of the designed family of dinuclear complexes and studied its binding to dsDNA by independent ensemble and single-molecule methods like gel electrophoresis, precipitation, and titration experiments followed by UV-vis spectroscopy, atomic force microscopy (AFM), as well as optical tweezers (OT) and magnetic tweezers (MT) DNA stretching. The observed irreversible binding of our dinuclear Cu(II)2 complex to dsDNA leads to a blocking of DNA synthesis as studied by polymerase chain reactions and cytotoxicity for human cancer cells.

  12. Crystal structures of a novel NNN pincer ligand and its dinuclear titanium(IV alkoxide pincer complex

    Directory of Open Access Journals (Sweden)

    Jakub Pedziwiatr


    Full Text Available This report describes a synthetic protocols and the crystal structures involving a novel pincer-type H3[NNN] ligand, namely di-μ-bromido-μ-{2-(2,2-dimethylpropanimidoyl-N-[2-(2,2-dimethylpropanimidoyl-4-methylphenyl]-4-methylaniline}-bis[(diethyl etherlithium], [Li2Br2(C24H33N3(C4H10O2] (1 and a dinuclear metal complex, namely di-μ-bromido-2:3κ4Br:Br-bis{2-(2,2-dimethylpropanimidoyl-N-[2-(2,2-dimethylpropanimidoyl-4-methylphenyl]-4-methylaniline}-1κ3N,N′,N′′;4κ3N,N′,N′′-tetra-μ-isopropanolato-1:2κ4O:O;3:4κ4O:O-diisopropanolato-1κO,4κO-2,3-dilithium-1,4-dititanium, [Li2Ti2Br2(C24H32N32(C3H7O6] or {[NHNNH]Ti(OiPr3(LiBr2}2 (2. Complex 1, which sits on a twofold rotation axis, is a rare example of a pincer-type ligand which bears ketimine side arms. A unique feature of complex 1 is that the ketimine N atoms have an LiBr(Et2O fragment bonded to them, with the Li atom adopting a distorted tetrahedral geometry. This particular fragment creates an LiBr bridge between the two ketimine sidearms, which leads to a cage-type appearance of the ligand. Complex 2 consists of the previously described ligand and a TiIV metal atom in an octahedral environment, and is located on an inversion center. Complex 2 crystallizes as a dinuclear species with the metal atoms being bridged by an LiBr entity [the Br atoms are disordered and refined in two positions with their site occupation factors refining to 0.674 (12/0.372 (12], and the Li cation being bonded to the isopropoxide O atoms (Li having a tetrahedral coordination as in 1. The organic ligand of compound 2 exhibits disorder in its periphery groups; isopropyl and tert-butyl groups (occupation factors fixed at 0.6/0.4. The novel [NNN]H3 pincer-type ligand was characterized by multinuclear and multidimensional NMR, HRMS and X-ray crystallography. The dinuclear metal complex 2 was characterized by X-ray crystallography. Although each structure exhibits donor N—H groups, no hydrogen bonding

  13. Synthesis and Crystal Structure of a 4,4'-bipyridine Linked Dinuclear Copper(II) Complex Derived from 2-{[2-(2-hydroxyethylamino)ethylimino]methyl}-6-methylphenol. (United States)

    Zhang, Xiu-Zhen; Gu, Yitong; Li, Yuntong; Liu, Andong; Liu, Fuyao; You, Zhonglu; Zhu, Hai-Liang


    A novel 4,4'-bipyridine linked dinuclear copper(II) complex, [Cu2L2(bipy)](NO3)2·bipy (L = 2-[2-(2-hydroxyethylamino) ethylimino]methyl-6-methylphenol; bipy = 4,4'-bipyridine), was prepared and characterized by elemental analyses, IR spectroscopy, and single-crystal X-ray diffraction. The Cu···Cu distance is 11.129(2) Å. The CuII atom is coordinated by one phenolate O, one imine N, and one amine N atoms of a Schiff base ligand, and one N atom of the bridging 4,4'-bipyridine ligand, forming a square planar geometry. In the crystal structure of the complex, the dinuclear copper complex cations are linked by 4,4'-bipyridine molecules through intermolecular O-H···N hydrogen bonds, to form 1D chains running in the [2 0 -1] direction.

  14. Dinuclear manganese complexes for water oxidation: evaluation of electronic effects and catalytic activity. (United States)

    Arafa, Wael A A; Kärkäs, Markus D; Lee, Bao-Lin; Åkermark, Torbjörn; Liao, Rong-Zhen; Berends, Hans-Martin; Messinger, Johannes; Siegbahn, Per E M; Åkermark, Björn


    During recent years significant progress has been made towards the realization of a sustainable and carbon-neutral energy economy. One promising approach is photochemical splitting of H2O into O2 and solar fuels, such as H2. However, the bottleneck in such artificial photosynthetic schemes is the H2O oxidation half reaction where more efficient catalysts are required that lower the kinetic barrier for this process. In particular catalysts based on earth-abundant metals are highly attractive compared to catalysts comprised of noble metals. We have now synthesized a library of dinuclear Mn2(II,III) catalysts for H2O oxidation and studied how the incorporation of different substituents affected the electronics and catalytic efficiency. It was found that the incorporation of a distal carboxyl group into the ligand scaffold resulted in a catalyst with increased catalytic activity, most likely because of the fact that the distal group is able to promote proton-coupled electron transfer (PCET) from the high-valent Mn species, thus facilitating O-O bond formation.

  15. 1D polymeric copper(I) and dinuclear silver(I) complexes of a bidentate Schiff base ligand: synthesis, spectroscopic characterization and thermal studies

    Czech Academy of Sciences Publication Activity Database

    Khalaji, A.D.; Peyghoun, S.J.; Akbari, A.; Feizi, N.; Dušek, Michal; Eigner, Václav


    Roč. 119, Sep (2016), s. 429-433 ISSN 0277-5387 R&D Projects: GA ČR GA15-12653S; GA MŠk LO1603 EU Projects: European Commission(XE) CZ.2.16/3.1.00/24510 Institutional support: RVO:68378271 Keywords : one-dimensional polymer * copper(I) * di-nuclear complex * silver(I) * crystal structure analysis Subject RIV: BM - Solid Matter Physics ; Magnetism Impact factor: 1.926, year: 2016

  16. Structural Studies on Dinuclear Ruthenium(II) Complexes That Bind Diastereoselectively to an Antiparallel Folded Human Telomere Sequence (United States)


    We report DNA binding studies of the dinuclear ruthenium ligand [{Ru(phen)2}2tpphz]4+ in enantiomerically pure forms. As expected from previous studies of related complexes, both isomers bind with similar affinity to B-DNA and have enhanced luminescence. However, when tested against the G-quadruplex from human telomeres (which we show to form an antiparallel basket structure with a diagonal loop across one end), the ΛΛ isomer binds approximately 40 times more tightly than the ΔΔ, with a stronger luminescence. NMR studies show that the complex binds at both ends of the quadruplex. Modeling studies, based on experimentally derived restraints obtained for the closely related [{Ru(bipy)2}2tpphz]4+, show that the ΛΛ isomer fits neatly under the diagonal loop, whereas the ΔΔ isomer is unable to bind here and binds at the lateral loop end. Molecular dynamics simulations show that the ΔΔ isomer is prevented from binding under the diagonal loop by the rigidity of the loop. We thus present a novel enantioselective binding substrate for antiparallel basket G-quadruplexes, with features that make it a useful tool for quadruplex studies. PMID:24088028

  17. The Synthesis of a Coumarin Carbohydrazide Dinuclear Copper Complex Based Fluorescence Probe and Its Detection of Thiols.

    Directory of Open Access Journals (Sweden)

    Guangjie He

    Full Text Available Small-molecule thiols, such as cysteine (CYS and glutathione (GSH, are essential for maintaining the cellular redox environment and play important roles in regulating various cellular physiological functions. A fluorescence probe (compound 1-Cu2+ for thiols based on coumarin carbohydrazide dinuclear copper complex was developed. Compound 1 was synthesized from the reaction of 7-(diethylamino-2-oxo-2H-chromene-3-carbohydrazide with 4-tert-butyl-2,6- diformylphenol. Accordingly, the copper complex (compound 1-Cu2+ was prepared by mixing compound 1 with 2 equivalents copper ions. Compound 1 had strong fluorescence while compound 1-Cu2+ hardly possessed fluorescence owing to the quenching nature of paramagnetism Cu2+ to the fluorescence molecule excited state. However, the fluorescence intensity of compound 1-Cu2+ was increased dramatically after the addition of thiol-containing amino acids, but not the other non-sulfhydryl amino acids. UV-vis absorption and fluorescence spectra indicated that compound 1-Cu2+ had good selectivity and sensitivity for thiols such as glutathione in CH3CN:H2O (3:2, v/v PBS solution. The fluorescence imaging experiments implied that compound 1-Cu2+ has potential application in thiol-containing amino acids detection in living cells.

  18. Mono- and dinuclear non-heme iron–nitrosyl complexes: Models for key intermediates in bacterial nitric oxide reductases

    Energy Technology Data Exchange (ETDEWEB)

    Berto, Timothy C.; Speelman, Amy L.; Zheng, Sheng; Lehnert, Nicolai


    High-spin non-heme iron–nitrosyls are of direct interest to both the chemical and biological communities as these species exhibit interesting chemical properties and act as direct models for enzymatic intermediates. The electronic ground state of the ferrous NO complexes, {Fe–NO}7, is best described as high-spin FeIII antiferromagnetically coupled to NO-, generating the spectroscopically observed S = 3/2 ground state. These species have been identified as catalytically relevant to a variety of NO-reducing enzymes such as bacterial nitric oxide reductase (NorBC) and flavo(rubredoxin) nitric oxide reductase (FNOR). Recently, the corresponding one-electron reduced {Fe–NO}8 (nitroxyl) complexes have also been implicated as biologically significant species. In this review the available spectroscopic data for {Fe–NO}7 and {Fe–NO}8 mono- and dinuclear non-heme iron–nitrosyls are summarized, and the implications of these results with respect to the electronic structures and reactivities of these species, in particular towards NO reduction, are discussed.

  19. Dinuclear Silver(I) and Copper(II) Complexes of Hexadentate Macrocyclic Ligands Containing p-Xylyl Spacers

    DEFF Research Database (Denmark)

    McKenzie, Christine J.; Nielsen, Lars Preuss; Søtofte, Inger


    The cyclocondensation of terephthalic aldehyde with N,N-bis(3-aminopropyl)-methylamine in the presence of silver(I) gives the dinuclear tetramine Schiff base macrocyclic complex, [Ag2L1](NO3)2 (L1=7,22-N,N'-dimethyl-3,7,11,18, 22,26-hexaazatricyclo[]-tetratricosa-2,11,13,15,1 7......,26,28,30,31,33-decaene). [Ag2L1](NO3)2 crystallizes in the monoclinic space group P21/c, with a=14.153(6), b=12.263(4), c=9.220(2) Å, beta=97.52(3) Å and Z=2. The silver ions are strongly coordinated at each end of the macrocycle by the two imine nitrogen atoms [2.177(3) and 2.182(3) Å] with close interatomic...... interactions to an oxygen atom of a nitrate ion and an amine nitrogen atom [2.580(2) and 2.690(2) Å]. The Ag...Ag distance is 6.892(3) Å. The free tetraimine macrocycle, L1, was obtained by treatment of [Ag2L1](NO3)2 with an excess of iodide, and the reduced derivative 7,22-N,N'-dimethyl-3...

  20. Acid-Induced Mechanism Change and Overpotential Decrease in Dioxygen Reduction Catalysis with a Dinuclear Copper Complex (United States)

    Das, Dipanwita; Lee, Yong-Min; Ohkubo, Kei; Nam, Wonwoo; Karlin, Kenneth D.; Fukuzumi, Shunichi


    Catalytic four-electron reduction of O2 by ferrocene (Fc) and 1,1′-dimethylferrocene (Me2Fc) occurs efficiently with a dinuclear copper(II) complex [CuII2(XYLO)(OH)]2+ (1), where XYLO is a m-xylene-linked bis[(2-(2-pyridyl)ethyl)amine dinucleating ligand with copper-bridging phenolate moiety], in the presence of perchloric acid (HClO4) in acetone at 298 K. The hydroxide and phenoxo group in [CuII2(XYLO)(OH)]2+ (1) undergo protonation with HClO4 to produce [CuII2(XYLOH)]4+ (2) where the two copper centers become independent and the reduction potential shifts from −0.68 V vs SCE in the absence of HClO4 to 0.47 Vj this makes possible the use of relatively weak one-electron reductants such as Fc and Me2Fc, significantly reducing the effective overpotential in the catalytic O2-reduction reaction. The mechanism of the reaction has been clarified based on kinetic studies on the overall catalytic reaction as well as each step in the catalytic cycle and also by low-temperature detection of intermediates. The O2-binding to the fully reduced complex [CuI2(XYLOH)]2+ (3) results in the reversible formation of the hydroperoxo complex ([CuII2(XYLO)(OOH)]2+) (4), followed by proton-coupled electron-transfer (PCET) reduction to complete the overall O2-to-2H2O catalytic conversion. PMID:23442145

  1. Dinuclear platinum(II) 4,6-diphenyl-2,2'-bipyridine complexes tethered by a rigid bridging ligand: synthesis and photophysics in solution and in LB film. (United States)

    Mathew, Iswarya; Li, Yunjing; Li, Zhongjing; Sun, Wenfang


    Two dinuclear platinum(II) 4,6-diphenyl-2,2'-bipyridine (C^N^N) complexes (1 and 2) with a rigid bridging ligand cis-1,2-bis(diphenylphosphino)ethylene were synthesized and their photophysical properties were systematically investigated in solution for 1 and 2 and in LB film for 2. Similar to their corresponding mononuclear complexes, both complexes exhibit intense (1)π,π* absorption in the UV region and a broad, moderate absorption band in the visible region, which likely stems from the mixed (1)MLCT (metal-to-ligand charge transfer), (1)ILCT (intraligand charge transfer) and (1)π,π* transitions. Both complexes are emissive in solutions at room temperature and in glassy matrix at 77 K. The emitting state is tentatively assigned as (3)MLCT for 1 and (3)MLCT/(3)ILCT/(3)π,π* for 2 at room temperature. At 77 K, the emission observed for 1 is mainly from the emissive ground-state aggregates, which is concentration dependent; while in 2 the emission from the monomer dominates. Unlike the dinuclear platinum complex with flexible bridging ligand diphenylphosphinoethane, the electronic absorption and emission energies of 1 and 2 at room temperature are independent of their concentration, indicating a fixed conformation for these two complexes. In addition, the presence of alkoxyl substituents on the diphenylbipyridine ligands causes a bathochromic shift of the lowest-energy absorption band and the emission band at room temperature for 2, presumably due to the involvement of the ILCT character into the lowest excited states. The presence of alkoxyl substituents in 2 also makes 2 amphiphilic, allowing for the fabrication of LB films of 2. The electronic absorption and emission characteristics in the LB films of 2 are quite similar to those in solutions, indicating no intermolecular Pt-Pt interactions occur in the LB films. The dinuclear complex without alkoxyl substituent (1) exhibits vapochromic behavior to heteroatom-containing volatile organic compounds (VOC's).

  2. Catalysis and molecular magnetism of dinuclear iron(III) complexes with N-(2-pyridylmethyl)-iminodiethanol/-ate. (United States)

    Shin, Jong Won; Bae, Jeong Mi; Kim, Cheal; Min, Kil Sik


    The reaction of N-(2-pyridylmethyl)iminodiethanol (H2pmide) and Fe(NO3)3·9H2O in MeOH led to the formation of a dimeric iron(III) complex, [(Hpmide)Fe(NO3)]2(NO3)2·2CH3OH (1). Its anion-exchanged form, [(pmide)Fe(N3)]2 (2), was prepared by the reaction of 1and NaN3 in MeOH, during which the Hpmide ligand of 1 was also deprotonated. These compounds were investigated by single crystal X-ray diffraction and magnetochemistry. In complex 1, one iron(III) ion was bonded with a mono-deprotonated Hpmide ligand and a nitrate ion. The two iron(III) ions within the dinuclear unit were connected by two ethoxy groups with an inversion center. In 2, one iron(III) ion was coordinated with a deprotonated pmide ligand and an azide ion. The Fe(pmide)(N3) unit was related by symmetry through an inversion center. Both 1 and 2 efficiently catalyzed the oxidation of a variety of alcohols under mild conditions. The oxidation mechanism was proposed to involve an Fe(IV)=O intermediate as the major reactive species and an Fe(V)=O intermediate as a minor oxidant. Evidence for this proposal was derived from reactivity and Hammett studies, KIE (kH/kD) values, and the use of MPPH (2-methyl-1-phenylprop-2-yl hydroperoxide) as a mechanistic probe. Both compounds had significant antiferromagnetic interactions between the iron(III) ions via the oxygen atoms. 1 showed a strong antiferromagnetic interaction within the Fe(III) dimer, while 2 had a weak antiferromagnetic coupling within the Fe(III) dimer.

  3. Study of half-sandwich mono and dinuclear complexes of platinum ...

    Indian Academy of Sciences (India)

    N-donor ligands; mono and binuclear complexes; ruthenium; rhodium; iridium. 1. Introduction. Mono and binuclear complexes of platinum group metals containing heterocyclic nitrogen based ligands have received considerable attention owing to their catalytic activities1–7 as well as in the development of new biologically ...

  4. Formation and structures of dialkyltartrate-bridged dinuclear group 4 metallocene complexes

    Energy Technology Data Exchange (ETDEWEB)

    Spaether, W.; Rump, M.; Erker, G.; Frohlich, R.; Hecht, J.; Kruger, C.; Kuhnigk, J.


    Dimenthyltitanocene and dimethylhafnocene react with dialkyltartrates to selectively form the ({mu}-tartrato) (Cp{sub 2}MCH{sub 3}){sub 2} complexes 3 (M=Ti) or 6 (M=Hf), respectively. With dimethylzirconocene both metal-carbon {sigma}-bponds are cleaved. The related ({mu}-tartrato)(Cp{sub 2}ZrCH{sub 3}){sub 2} complex 8 was obtained by the selective reaction of the enolate complex Cp{sub 2}Zr(CH{sub 3})(-OCMe=CH{sub {sup )}} with dimenthyltartrate. (Author) 48 refs.

  5. One novel 1D coordination polymer with parallel dinuclear copper(II) macrocyclic platforms bridged by trans dimeric half-water molecules and two dinuclear copper(II) macrocyclic complexes with different coordination geometry obtained from different solvents (United States)

    Chu, Zhaolian; You, Wei; Huang, Wei


    Three dinuclear copper(II) macrocyclic complexes, formulated as [Cu 2L(N 3) 2(0.5H 2O) 2] n ( 1), [Cu 2L(ClO 4) 2(CH 3CH 2OH)] ( 2) and [Cu 2L(CH 3OH) 2](ClO 4) 2 ( 3) (LH 2 = [2+2] Schiff base macrocyclic ligand condensed from 4-chloro-2,6-diformylphenol and 1,3-diaminopropane), have been prepared and determined by X-ray single-crystal diffraction. Complex 1 shows two six-coordinate Cu(II) centers in which two monodentate N3- anions and two half-water molecules are bonded at the apical positions in the trans configuration. Furthermore, the dimeric half-water molecules serve as a μ2-bridge linking adjacent macrocyclic units together with the multiple O sbnd H…N hydrogen bonds with azide anions, forming a novel 1D chain-like coordination polymer. Complexes 2 and 3 are obtained from different solvents (ethanol and methanol) and they can be converted into each other. The molecular structures and packing mode of 2 and 3 are different where six-coordinate and five-coordinate copper(II) centers are present, respectively.

  6. Electron spin-lattice relaxation of the S0 state of the oxygen-evolving complex in photosystem II and of dinuclear manganese model complexes. (United States)

    Kulik, L V; Lubitz, W; Messinger, J


    The temperature dependence of the electron spin-lattice relaxation time T1 was measured for the S0 state of the oxygen-evolving complex (OEC) in photosystem II and for two dinuclear manganese model complexes by pulse EPR using the inversion-recovery method. For [Mn(III)Mn(IV)(mu-O)2 bipy4]ClO4, the Raman relaxation process dominates at temperatures below 50 K. In contrast, Orbach type relaxation was found for [Mn(II)Mn(III)(mu-OH)(mu-piv)2(Me3 tacn)2](ClO4)2 between 4.3 and 9 K. For the latter complex, an energy separation of 24.7-28.0 cm(-1) between the ground and the first excited electronic state was determined. In the S0 state of photosystem II, the T1 relaxation times were measured in the range of 4.3-6.5 K. A comparison with the relaxation data (rate and pre-exponential factor) of the two model complexes and of the S2 state of photosystem II indicates that the Orbach relaxation process is dominant for the S0 state and that its first excited state lies 21.7 +/- 0.4 cm(-1) above its ground state. The results are discussed with respect to the structure of the OEC in photosystem II.

  7. Self assembly of dialkoxo bridged dinuclear Fe(III) complex of pyridoxal Schiff base with C-C bond formation - structure, spectral and magnetic properties

    Czech Academy of Sciences Publication Activity Database

    Murašková, V.; Szabó, N.; Pižl, M.; Hoskovcová, I.; Dušek, Michal; Huber, Š.; Sedmidubský, D.


    Roč. 461, May (2017), s. 111-119 ISSN 0020-1693 R&D Projects: GA ČR(CZ) GA15-12653S; GA MŠk LO1603 EU Projects: European Commission(XE) CZ.2.16/3.1.00/24510 Institutional support: RVO:68378271 Keywords : iron (III) dinuclear complex * dialkoxo bridged pyridoxal Schiff base * C-C bond * crystal structure * magnetic properties Subject RIV: BM - Solid Matter Physics ; Magnetism OBOR OECD: Condensed matter physics (including formerly solid state physics, supercond.) Impact factor: 2.002, year: 2016

  8. Synthesis and magnetic Properties of dinuclear oxovanadium(IV) complexes bridged by tetracarboxylato groups

    International Nuclear Information System (INIS)

    Li, Y.-T.; Guan, H.-S.; Yan, C.-W.


    Three novel μ-tetracarboxylato-bridged oxovanadium(IV) complexes described by the overall formula [(VO) 2 (PMTA)L 2 ] where PMTA stands for the tetraanion of pyromellitic acid, and L denotes 2,2'-bipyridine(bpy), 4,4'-dimethyl-2,2'-bipyridine (Me 2 bpy) or 1,10-phenanthroline (phen), respectively, have been synthesized and characterized by elemental analyses, molar conductivity and room-temperature magnetic moment measurements, IR, ESR, and electronic spectral studies. It is proposed that these complexes have PMTA-bridged structures and consist of two oxovanadium(IV) ions, each in the square-pyramidal environment. The [(VO) 2 (PMTA)(bpy) 2 ] (1) and [(VO) 2 (PMTA)(phen) 2 ] (2) complexes were further characterized by variable temperature (4.2 - 300 K) magnetic susceptibility measurements and the observed data were fitted to the modified Bleaney-Bowers equation by the least-squares, giving the exchange integral J = -2.75 cm -1 for (1) and J -3.91 cm -1 for (2). This results indicates that there is a weak antiferromagnetic spin-exchange interaction between the two VO 2+ ions within each molecule. (author)

  9. Dinuclear ru-aqua complexes for selective epoxidation catalysis based on supramolecular substrate orientation effects

    KAUST Repository

    Di Giovanni, Carlo


    Ru-aqua complex {[RuII(trpy)(H2O)] 2(μ-pyr-dc)}+ is a powerful epoxidation catalyst for a wide range of linear and cyclic alkenes. High turnover numbers (TNs), up to 17000, and turnover frequencies (TOF), up to 24120 h-1 (6.7 s -1), have been obtained using PhIO as oxidant. This species presents an outstanding stereospecificity for both cis and trans olefins towards the formation of their corresponding cis and trans epoxides. In addition, it shows different reactivity to cis and trans olefins due to a substrate orientation supramolecular effect transmitted by its ligand scaffold. This effect together with the impressive reaction rates are rationalized using electrochemical techniques and DFT calculations. A new Ru-aqua complex that behaves as a powerful epoxidation catalyst for a wide range of linear and cyclic alkenes is reported. High turnover numbers and frequencies are obtained by using PhIO as oxidant. The complex shows an outstanding stereospecificity for both cis and trans olefins towards the formation of their corresponding cis and trans epoxides (see figure). © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  10. Efficient Light-Driven Water Oxidation Catalysis by Dinuclear Ruthenium Complexes. (United States)

    Berardi, Serena; Francàs, Laia; Neudeck, Sven; Maji, Somnath; Benet-Buchholz, Jordi; Meyer, Franc; Llobet, Antoni


    Mastering the light-induced four-electron oxidation of water to molecular oxygen is a key step towards the achievement of overall water splitting to produce alternative solar fuels. In this work, we report two rugged molecular pyrazolate-based diruthenium complexes that efficiently catalyze visible-light-driven water oxidation. These complexes were fully characterized both in the solid state (by X-ray diffraction analysis) and in solution (spectroscopically and electrochemically). Benchmark performances for homogeneous oxygen production have been obtained for both catalysts in the presence of a photosensitizer and a sacrificial electron acceptor at pH 7, and a turnover frequency of up to 11.1 s(-1) and a turnover number of 5300 were obtained after three successive catalytic runs. Under the same experimental conditions with the same setup, the pyrazolate-based diruthenium complexes outperform other well-known water oxidation catalysts owing to both electrochemical and mechanistic aspects. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  11. Nuclear inelastic scattering study of a dinuclear iron(II) complex showing a direct spin transition

    Energy Technology Data Exchange (ETDEWEB)

    Wolny, J. A., E-mail: [University of Kaiserslautern, Department of Physics (Germany); Garcia, Y. [Université Catholique de Louvain, Institute of Condensed Matter and Nanosciences, Molecules, Solids and Reactivity (IMCN/MOST) (Belgium); Faus, I.; Rackwitz, S. [University of Kaiserslautern, Department of Physics (Germany); Schlage, K.; Wille, H.-C. [DESY (Germany); Schünemann, V. [University of Kaiserslautern, Department of Physics (Germany)


    The results of the nuclear inelastic scattering (NIS)/nuclear resonance vibrational spectroscopy (NRVS) for the powder spectra of dimeric [Fe {sub 2}L{sub 5}(NCS) {sub 4}] (L = N-salicylidene-4-amino-1,2,4-triazole) complex are presented. This system is spin crossover (SCO) material tagged with a fluorophore that can sense or “feel” the SCO signal ripping through the molecular network and thereby providing an opportunity to register the SCO transition. The spectra have been measured for the low-spin and high-spin phases of the complex. The high-spin isomer reveals one broad band above 200 cm {sup −1}, while the low-spin one displays two intense bands in the range from 390 to 430 cm {sup −1}, accompanied by a number of weaker bands below this area and one at ca. 490 cm {sup −1}. A normal coordinate analysis based on density functional calculations yields the assignment of the spin marker bands to particular molecular modes. In addition the vibrational contribution to the spin transition has been estimated.

  12. Dinuclear Zn(II) complex catalyzed phosphodiester cleavage proceeds via a concerted mechanism: a density functional theory study. (United States)

    Gao, Hui; Ke, Zhuofeng; DeYonker, Nathan J; Wang, Juping; Xu, Huiying; Mao, Zong-Wan; Phillips, David Lee; Zhao, Cunyuan


    Density functional theory (DFT) calculations were used to study the mechanism for the cleavage reaction of the RNA analogue HpPNP (HpPNP = 2-hydroxypropyl-4-nitrophenyl phosphate) catalyzed by the dinuclear Zn(II) complex of 1,3-bis(1,4,7-triazacyclonon-1-yl)-2-hydroxypropane (Zn(2)(L(2)O)). We present a binding mode in which each terminal phosphoryl oxygen atom binds to one zinc center, respectively, and the nucleophilic 2-hydroxypropyl group coordinates to one of the zinc ions, while the hydroxide from deprotonation of a water molecule coordinates to the other zinc ion. Our calculations found a concerted mechanism for the HpPNP cleavage with a 16.5 kcal/mol reaction barrier. An alternative proposed stepwise mechanism through a pentavalent oxyphosphorane dianion reaction intermediate for the HpPNP cleavage was found to be less feasible with a significantly higher energy barrier. In this stepwise mechanism, the deprotonation of the nucleophilic 2-hydroxypropyl group is accompanied with nucleophilic attack in the rate-determining step. Calculations of the nucleophile (18)O kinetic isotope effect (KIE) and leaving (18)O KIE for the concerted mechanism are in reasonably good agreement with the experimental values. Our results indicate a specific-base catalysis mechanism takes place in which the deprotonation of the nucleophilic 2-hydroxypropyl group occurs in a pre-equilibrium step followed by a nucleophilic attack on the phosphorus center. Detailed comparison of the geometric and electronic structure for the HpPNP cleavage reaction mechanisms in the presence/absence of catalyst revealed that the catalyst significantly altered the determining-step transition state to become far more associative or tight, that is, bond formation to the nucleophile was remarkably more advanced than leaving group bond fission in the catalyzed mechanism. Our results are consistent with and provide a reliable interpretation for the experimental observations that suggest the reaction occurs

  13. Novel dinuclear platinum(II) complexes targets NFκB signaling pathway to induce apoptosis and inhibit metabolism of MCF-7 breast cancer cells

    International Nuclear Information System (INIS)

    Poplawska, B.; Bielawska, A.; Surazynski, A.; Czarnomysy, R.; Bielawski, K.


    Four novel dinuclear platinum(II) complexes of formula [Pt 2 L 4 (berenil) 2 ]Cl 4 (Pt1-Pt4) where L is piperazine Pt1), 4-picoline (Pt2), 3-picoline (Pt3) or isopropylamine (Pt4) were compared to cisplatin in respect to collagen biosynthesis, β1- integrin receptor, IGF-I receptor, phosphorylated MAP-kinases (ERK1/ERK2 and p38), phosphorylated Akt kinase expression and appearance of apoptosis in MCF-7 breast cancer cells. It was found that Pt1-Pt4 were more active inhibitor of collagen biosynthesis than cisplatin. The expression of IGF-I and β1 integrin receptor, as well as phosphorylated MAPK, (ERK1 and ERK2 and p38) was significantly increased in cells incubated for 24 h with 20 μM Pt1-Pt4 compared to the control, not treated cells. The phenomenon was related to the increase expression of NFκB by Pt1-Pt4 as shown by Western immunoblot analysis. Experiments made with annex in V-FITC and detection of apoptosis by a fluorescent microscopy assay revealed that novel dinuclear platinum(II) complexes (Pt1-Pt4) inhibited the proliferation of MCF-7 breast cancer cells by increasing the number of apoptotic and necrotic cells. (authors)

  14. Antibacterial, DNA interaction and cytotoxic activities of pendant-armed polyamine macrocyclic dinuclear nickel(II) and copper(II) complexes (United States)

    Arthi, P.; Haleel, A.; Srinivasan, P.; Prabhu, D.; Arulvasu, C.; Kalilur Rahiman, A.


    A series of dinuclear nickel(II) and copper(II) complexes (1-6) of hexaaza macrocycles of 2,6-diformyl-4-methylphenol with three different benzoyl pendant-arms, 2,2‧-benzoyliminodi(ethylamine) trihydrochloride (L), 2,2‧-4-nitrobenzoyliminodi(ethylamine) trihydrochloride (L‧) and 2,2‧-3,5-dinitrobenzoyliminodi(ethylamine) trihydrochloride (L″) have been synthesized and characterized by spectral methods. The electrochemical studies of these complexes depict two irreversible one electron reduction processes around E1pc = -0.62 to -0.76 V and E2pc = -1.21 to -1.31, and nickel(II) complexes (1-3) exhibit two irreversible one electron oxidation processes around E1pa = 1.08 to 1.14 V and E2pa = 1.71 to 1.74 V. The room temperature magnetic moment values (μeff, 1.52-1.54 BM) indicate the presence of an antiferromagnetic interaction in the binuclear copper(II) complexes (4-6) which is also observed from the broad ESR spectra with a g value of 2.14-2.15. The synthesized complexes (1-6) were screened for their antibacterial activity. The results of DNA interaction studies indicate that the dinuclear complexes can bind to calf thymus DNA by intercalative mode and display efficient cleavage of plasmid DNA. Further, the cytotoxic activity of complexes 2, 5 and 6 on human liver adenocarcinoma (HepG2) cell line has been examined. Nuclear-chromatin cleavage has also been observed with PI staining and comet assays.

  15. Structures, magnetochemistry, spectroscopy, theoretical study, and catechol oxidase activity of dinuclear and dimer-of-dinuclear mixed-valence Mn(III)Mn(II) complexes derived from a macrocyclic ligand. (United States)

    Jana, Arpita; Aliaga-Alcalde, Núria; Ruiz, Eliseo; Mohanta, Sasankasekhar


    The work in this paper presents syntheses, characterization, magnetic properties (experimental and density functional theoretical), catecholase activity, and electrospray ionization mass spectroscopic (ESI-MS positive) studies of two mixed-valence dinuclear Mn(III)Mn(II) complexes, [Mn(III)Mn(II)L(μ-O2CMe)(H2O)2](ClO4)2·H2O·MeCN (1) and [Mn(III)Mn(II)L(μ-O2CPh)(MeOH)(ClO4)](ClO4) (2), and a Mn(III)Mn(II)Mn(II)Mn(III) complex, [{Mn(III)Mn(II)L(μ-O2CEt)(EtOH)}2(μ-O2CEt)](ClO4)3 (3), derived from the Robson-type macrocycle H2L, which is the [2 + 2] condensation product of 2,6-diformyl-4-methylphenol and 2,2-dimethyl-1,3-diaminopropane. In 1 and 2 and in two Mn(III)Mn(II) units in 3, the two metal centers are bridged by a bis(μ-phenoxo)-μ-carboxylate moiety. The two Mn(II) centers of the two Mn(III)Mn(II) units in 3 are bridged by a propionate moiety, and therefore this compound is a dimer of two dinuclear units. The coordination geometry of the Mn(III) and Mn(II) centers are Jahn-Teller distorted octahedral and distorted trigonal prism, respectively. Magnetic studies reveal weak ferro- or antiferromagnetic interactions between the Mn(III) and Mn(II) centers in 1 (J = +0.08 cm(-1)), 2 (J = -0.095 cm(-1)), and 3 (J1 = +0.015 cm(-1)). A weak antiferromagnetic interaction (J2 = -0.20 cm(-1)) also exists between the Mn(II) centers in 3. DFT methods properly reproduce the nature of the exchange interactions present in such systems. A magneto-structural correlation based on Mn-O bridging distances has been proposed to explain the different sign of the exchange coupling constants. Utilizing 3,5-di-tert-butyl catechol (3,5-DTBCH2) as the substrate, catecholase activity of all the three complexes has been checked in MeCN and MeOH, revealing that all three are active catalysts with Kcat values lying in the range 7.5-64.7 h(-1). Electrospray ionization mass (ESI-MS positive) spectra of the complexes 1-3 have been recorded in MeCN solutions, and the positive ions have been


    Directory of Open Access Journals (Sweden)



    Full Text Available A novel dinuclear Tb(III complex, [Tb(bpy2L2] (bpy = 2,2’-bipyridine, H2L = homophthalic acid, has been synthesized and characterized by elemental analysis and single-crystal X-ray diffraction. The Tb(III complex is monoclinic, space group P21/c with a = 9.368(2 Å, b = 15.948(4 Å, c = 12.216(3 Å, β = 103.023(4º, V= 1778.2(7 Å3, Z = 2, Dc = 1.910 mg·m-3, μ = 4.011 mm-1, F(000 = 996, and final R1 = 0.0602, ωR2 = 0.2192. The result shows that the Tb(III center is seven-coordination with a N2O5 distorted pengonal bipyramidal geometry. The luminescent property of Tb(III complex was investigated.

  17. Preparation of CuO nanoparticles by thermal decomposition of double-helical dinuclear copper(II Schiff-base complexes

    Directory of Open Access Journals (Sweden)

    Aliakbar Dehno Khalaji


    Full Text Available In this paper, two double helical dinuclear copper(II complexes of bis-N,O-bidentate Schiff base ligands bis(3-methoxy-N-salicylidene-4,4'-diaminodiphenylsulfone (L1 and bis(5-bromo-N-salicylidene-4,4'-diaminodiphenylsulfone (L2 were prepared and characterized by elemental analyses (CHN, as well as thermal analysis. Elemental analyses (CHN suggested that the reaction between ligands and copper salt has been occurred in 1:1 molar ratio. In these complexes the Schiff base ligands behaves as an anionic and bis-bidentate chelate and is coordinated to the copper(II ion via two phenolic oxygen and two iminic nitrogen atoms. In these double helical dinuclear complexes, each copper(II center has a pseudo-tetrahedral coordination sphere two-wrapped ligands. Thermal analysis of ligands and their complexes were studied in the range of room temperature to 750 °C with a heating rate of 10 °C min-1. TG plots show that the ligands and their complexes are thermally decomposed via 2 and 3 thermal steps, respectively. In addition, the complexes thermally decomposed in air at 520 °C for 3 h. The obtained solids characterized by Fourier transform infrared spectroscopy (FT-IR, X-ray powder diffraction (XRD and transmission electron microscopy (TEM. The X-ray pattern result shows that the CuO nanoparticles are pure and single phase. The TEM result shows the as prepared CuO nanoparticles were very small and similar shape with particle size about

  18. Dinuclear 1,4,7-triazacyclononane (tacn) complexes of cobalt(III) with amido and tacn bridges. Synthesis, characterization and reversible acid-accelerated bridge cleavage

    DEFF Research Database (Denmark)

    Andersen, Peter; Glerup, Jørgen; Gumm, Andreas


    Amido-bridged dinuclear cobalt(III) complexes with 1,4,7-triazacyclononane (tacn) were synthesized from [Co(tacn)(O3SCF3)3] by treatment with potassium amide in liquid ammonia at 100 degrees C. Two isomeric triply bridged complexes, [(tacn)Co(mu-NH2)3Co(tacn)]3+ and [(tacn)Co(mu-NH2)2[mu-tacn(-H)......Amido-bridged dinuclear cobalt(III) complexes with 1,4,7-triazacyclononane (tacn) were synthesized from [Co(tacn)(O3SCF3)3] by treatment with potassium amide in liquid ammonia at 100 degrees C. Two isomeric triply bridged complexes, [(tacn)Co(mu-NH2)3Co(tacn)]3+ and [(tacn)Co(mu-NH2)2[mu......-tacn(-H)]Co(NH3)]3+, were isolated as perchlorates, and the crystal structure of the perrhenate of the latter complex was determined by X-ray diffraction. In this compound a nitrogen atom (deprotonated) from one of the tacn ligands forms a third bridge together with two amido bridges. In 1.0 M (Na,H)ClO4 ([H+] 0.......1-1.0 M) the two isomers undergo acid-accelerated amido bridge cleavage, as earlier found for chromium(III) analogues, in spite of the fact that such bridges are co-ordinatively saturated. The triamido-bridged isomer is in this acid medium in equilibrium with [(H2O)(tacn)Co(mu-NH2)2Co(tacn)(NH3...

  19. Solution Speciation, DFT Calculations, Luminescence Properties and Promoted Nitrophenyl-phosphate Hydrolysis Rates of Dinuclear Lanthanide(III)-m-ODO2A-dimer Macrocyclic Complexes. (United States)

    Chang, C Allen; Lee, Hwa-Yu; Lin, Syue-Liang; Meng, Ching-Ning; Wu, Tsung-Ta


    Potentiometric speciation studies, mass spectrometry and density functional theory (DFT) calculations helped to predict the various structural possibilities of the dinuclear trivalent lanthanide ion (LnIII, Ln = La, Eu, Tb, Yb, Y) complexes of a novel macrocyclic ligand, m-ODO2A-dimer (H4L) to correlate with their luminescence properties and the promoted BNPP and HPNP phosphodiester bond hydrolysis reaction rates. The stability constants of the dinuclear Ln2(m-ODO2A-dimer) complexes and various hydrolytic species confirmed by mass spectrometry were determined. DFT calculations revealed that the Y2LH-1 and the Y2LH-2 species tended to form structures with the respective "closed-form" and "open-form" conformations. Luminescence lifetime data for the heterodimetallic TbEuL system confirmed the fluorescence resonance energy transfer from TbIII ion to EuIII ion. The internuclear distance RTbEu values were estimated to be in the range 9.4Å - 11.3Å (pH 6.7 - 10.6) which were comparable to those of the DFT calculated "open-form" conformations. Multiple linear regression analysis of the kobs data was performed using the equation: kobs,corr. = kobs - kobs,OH = kLn2LH-1[Ln2LH-1] + kLn2LH-2[Ln2LH-2] for the observed Ln2L-promoted BNPP/HPNP hydrolysis reactions in solution pH from 7 to 10.5 (Ln = Eu, Yb). The results showed that the second-order rate constants for the Eu2LH-2 and Yb2LH-2 species were about 50-400 times more reactive than the structural analogous Zn2(m-12N3O-dimer) system. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  20. Synthesis, one- and two-photon photophysical and excited-state properties, and sensing application of a new phosphorescent dinuclear cationic iridium(III) complex. (United States)

    Xu, Wen-Juan; Liu, Shu-Juan; Zhao, Xin; Zhao, Ning; Liu, Zhi-Qiang; Xu, Hang; Liang, Hua; Zhao, Qiang; Yu, Xiao-Qiang; Huang, Wei


    A new phosphorescent dinuclear cationic iridium(III) complex (Ir1) with a donor-acceptor-π-bridge-acceptor-donor (D-A-π-A-D)-conjugated oligomer (L1) as a N^N ligand and a triarylboron compound as a C^N ligand has been synthesized. The photophysical and excited-state properties of Ir1 and L1 were investigated by UV/Vis absorption spectroscopy, photoluminescence spectroscopy, and molecular-orbital calculations, and they were compared with those of the mononuclear iridium(III) complex [Ir(Bpq)(2)(bpy)](+)PF(6)(-) (Ir0). Compared with Ir0, complex Ir1 shows a more-intense optical-absorption capability, especially in the visible-light region. For example, complex Ir1 shows an intense absorption band that is centered at λ=448 nm with a molar extinction coefficient (ε) of about 10(4) , which is rarely observed for iridium(III) complexes. Complex Ir1 displays highly efficient orange-red phosphorescent emission with an emission wavelength of 606 nm and a quantum efficiency of 0.13 at room temperature. We also investigated the two-photon-absorption properties of complexes Ir0, Ir1, and L1. The free ligand (L1) has a relatively small two-photon absorption cross-section (δ(max) =195 GM), but, when complexed with iridium(III) to afford dinuclear complex Ir1, it exhibits a higher two-photon-absorption cross-section than ligand L1 in the near-infrared region and an intense two-photon-excited phosphorescent emission. The maximum two-photon-absorption cross-section of Ir1 is 481 GM, which is also significantly larger than that of Ir0. In addition, because the strong B-F interaction between the dimesitylboryl groups and F(-) ions interrupts the extended π-conjugation, complex Ir1 can be used as an excellent one- and two-photon-excited "ON-OFF" phosphorescent probe for F(-) ions. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  1. Luminescence of tartrate bridged dinuclear 2,2'-bipyridine platinum(ii) complexes: emission color controlled by intra- and inter-molecular interactions in the solid state. (United States)

    Ohno, Keiji; Tanuma, Honami; Kusano, Yukiko; Kaizaki, Sumio; Nagasawa, Akira; Fujihara, Takashi


    Novel dinuclear Pt II complexes with a chiral (l-) and an achiral (meso-) tartrate [{Pt II (bpy)} 2 (μ-x-tart)] (bpy: 2,2'-bipyridine; tartH 2 2- : tartrate; x = l (1), meso (2)) and with a racemic (dl-) tartrate [{Pt II (bpy)} 2 (μ-d-tart)][{Pt II (bpy)} 2 (μ-l-tart)] (3) were synthesized, and the influence of their stereochemistry on their molecular and crystal structures affecting their luminescence was discussed. Effects of the dinuclearity on the structures and luminescence were revealed by comparison with those of a novel racemic mononuclear complex [Pt II (bpy)(d-tartH 2 )][Pt II (bpy)(l-tartH 2 )] (4). The X-ray crystallography showed the crystallization of 1 in two polymorphs, namely monoclinic 3[1·6H 2 O] (1α) and triclinic 2[1·6H 2 O] (1β), and those of other complexes in monoclinic hydrate crystals 2·12.5H 2 O, 3·4H 2 O, and 4·H 2 O. The chiral complexes in 1α, 1β, and 3·4H 2 O showed clamshell-like structures with Pt-Pt and π-π interactions, while the achiral complex in 2·12.5H 2 O displayed a twisted form without intramolecular interactions. The complexes in 1α were assembled in a right-handed helical arrangement through significant Pt-Pt interactions, and those in 1β and 3·4H 2 O were stacked in one-dimensional columns through significant and slight π-π interactions, respectively. The complex in 2·12.5H 2 O constructed an intermolecular dimer through Pt-Pt interactions with its adjacent complex. The crystal structure of 4·H 2 O displayed a three-dimensional network architecture through π-π interactions and hydrogen bonding. These crystals exhibited luminescence depending on their molecular and crystal structures (λ max nm = 535 (4·H 2 O), 569 (3·4H 2 O), 621 (2·12.5H 2 O), 649 (1β), and 656 (1α)). The formations of intermolecular dimers and clamshell-like structures through Pt-Pt interactions in 2·12.5H 2 O and in 3·4H 2 O, respectively, lead to red-shifts in emissions compared to 4·H 2 O, and further low

  2. Di- and Triphosphate Recognition and Sensing with Mono- and Dinuclear Fluorescent Zinc(II) Complexes: Clues for the Design of Selective Chemosensors for Anions in Aqueous Media. (United States)

    Bartoli, Francesco; Bencini, Andrea; Garau, Alessandra; Giorgi, Claudia; Lippolis, Vito; Lunghi, Alessandro; Totti, Federico; Valtancoli, Barbara


    The synthesis of a new ligand (L1) containing two 1,4,7-triazacyclononane ([9]aneN 3 ) moieties linked by a 4,5-dimethylenacridine unit is reported. The binding and fluorescence sensing properties toward Cu 2+ , Zn 2+ , Cd 2+ , and Pb 2+ of L1 and receptor L2, composed of two [9]aneN 3 macrocycles bridged by a 6,6''-dimethylen-2,2':6',2''-terpyridine unit, have been studied by coupling potentiometric, UV/Vis absorption, and emission measurements in aqueous media. Both receptors can selectively detect Zn 2+ thanks to fluorescence emission enhancement upon metal binding. The analysis of the binding and sensing properties of the Zn 2+ complexes toward inorganic anions revealed that the dinuclear Zn 2+ complex of L1 selectively binds and senses the triphosphate anion (TP), whereas the mononuclear Zn 2+ complex of L2 displays selective recognition of diphosphate (DP). Binding of TP or DP induces emission quenching of the Zn 2+ complexes with L1 and L2, respectively. These results are exploited to discuss the role played by pH, number of coordinated metal cations, and binding ability of the bridging units in metal and/or anion coordination and sensing. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  3. Thermodynamic stability and energetics of DNA duplexes containing major intrastrand cross-links of second-generation antitumor dinuclear Pt(II) complexes. (United States)

    Florian, Jakub; Kasparkova, Jana; Farrell, Nicholas P; Brabec, Viktor


    The effects of major DNA intrastrand cross-links of antitumor dinuclear Pt(II) complexes [{trans-PtCl(NH(3))(2)}(2)-μ-{trans-(H(2)N(CH(2))(6)NH(2)(CH(2))(2)NH(2)(CH(2))(6)NH(2))}](4+) (1) and [{PtCl(DACH)}(2)-μ-{H(2)N(CH(2))(6)NH(2)(CH(2))(2)NH(2)(CH(2))(6)NH(2))}](4+) (2) (DACH is 1,2-diaminocyclohexane) on DNA stability were studied with emphasis on thermodynamic origins of that stability. Oligodeoxyribonucleotide duplexes containing the single 1,2, 1,3, or 1,5 intrastrand cross-links at guanine residues in the central TGGT, TGTGT, or TGTTTGT sequences, respectively, were prepared and analyzed by differential scanning calorimetry. The unfolding of the platinated duplexes was accompanied by unfavorable free energy terms. The efficiency of the cross-links to thermodynamically destabilize the duplex depended on the number of base pairs separating the platinated bases. The trend was 1,5→1,2→1,3 cross-link of 1 and 1,5→1,3→1,2 cross-link of 2. Interestingly, the results showed that the capability of the cross-links to reduce the thermodynamic stability of DNA (ΔG(298)(0)) correlated with the extent of conformational distortions induced in DNA by various types of intrastrand cross-links of 1 or 2 determined by chemical probes of DNA conformation. We also examined the efficiency of the mammalian nucleotide excision repair systems to remove from DNA the intrastrand cross-links of 1 or 2. The efficiency of the excinucleases to remove the cross-links from DNA depended on the length of the cross-link; the trend was identical to that observed for the efficiency of the intrastrand cross-links to thermodynamically destabilize the duplex. Thus, the results are consistent with the thesis that an important factor that determines the susceptibility of the intrastrand cross-links of dinuclear platinum complexes 1 and 2 to be removed from DNA by nucleotide excision repair is the efficiency of these lesions to thermodynamically destabilize DNA.

  4. Coordination studies of 1,2-bis(diphenylphosphinoethane with di-μ-hydroxo dinuclear complexes of tungsten(IV and molybdenum(IV

    Directory of Open Access Journals (Sweden)

    Minato Makoto


    Full Text Available The new trifluoroethoxo phosphine complexes [Cp2M(η1-dppe(CF3CH2O]+ and [Cp2(CF3CH2OM(μ-dppeMCp2(CF3CH2O]2+ (M = Mo or W, Cp = η-C5H5 and dppe = Ph2PCH2CH2PPh2 have been prepared by reaction of cationic di-μ-hydroxo dinuclear complex of molybdenocene or tungstenocene [Cp2M(μ-OH2MCp2]2+ with dppe. From the 1H and 31P NMR data, the configurations of the products could be assigned. Furtheremore, X-ray crystallography was used to definitively identify one of the product [Cp2(CF3CH2OMo(μ-dppeMoCp2(CF3CH2O]2+, which crystallizes in space group P21/c(#14 with a = 12.230(5 Å, b = 11.149(5 Å, c = 28.966(7 Å, β = 101.07(3°, V = 3876(2 Å3, and Z = 2. It was ascertained that the amount of dppe added to the reaction mixture could influence the product distribution. A mechanism involving initial replacement of the hydroxo ligand by the alkoxo group followed by nucleophilic attack of the phosphine is proposed on the basis of the reaction profile.

  5. Structural, MALDI-TOF-MS, magnetic and spectroscopic studies of new dinuclear copper(II), cobalt(II) and zinc(II) complexes containing a biomimicking μ-OH bridge. (United States)

    Núñez, Cristina; Bastida, Rufina; Macías, Alejandro; Valencia, Laura; Neuman, Nicolás I; Rizzi, Alberto C; Brondino, Carlos D; González, Pablo J; Capelo, José Luis; Lodeiro, Carlos


    The Py(2)N(4)S(2) octadentate coordinating ligand afforded dinuclear cobalt, copper and zinc complexes and the corresponding mixed metal compounds. The overall geometry and bonding modes have been deduced on the basis of elemental analysis data, MALDI-TOF-MS, IR, UV-vis and EPR spectroscopies, single-crystal X-Ray diffraction, conductivity and magnetic susceptibility measurements. In the copper and zinc complexes, a μ-hydroxo bridge links the two metal ions. In both cases, the coordination geometry is distorted octahedral. Magnetic and EPR data reveal weakly antiferromagnetic high spin Co(II) ions, compatible with a dinuclear structure. The magnetic characterization of the dinuclear Cu(II) compound indicates a ferromagnetically coupled dimer with weak antiferromagnetic intermolecular interactions. The intra-dimer ferromagnetic behaviour was unexpected for a Cu(II) dimer with such μ-hydroxo bridging topology. We discuss the influence on the magnetic properties of non-covalent interactions between the bridging moiety and the lattice free water molecules.

  6. Visible Light-Induced Electron Transfer from Di-mu-oxo Bridged Dinuclear Mn Complexes to Cr Centers in Silica Nanopores

    Energy Technology Data Exchange (ETDEWEB)

    Frei, Heinz; Weare, Walter W.; Pushkar, Yulia; Yachandra, Vittal K.; Frei, Heinz


    The compound (bpy)2MnIII(mu-O)2MnIV(bpy)2, a structural model relevant for the photosynthetic water oxidation complex, was coupled to single CrVI charge-transfer chromophores in the channels of the nanoporous oxide AlMCM-41. Mn K-edge EXAFS spectroscopy confirmed that the di-mu-oxo dinuclear Mn core of the complex is unaffected when loaded into the nanoscale pores. Observation of the 16-line EPR signal characteristic of MnIII(mu-O)2MnIV demonstrates that the majority of the loaded complexes retained their nascent oxidation state in the presence or absence of CrVI centers. The FT-Raman spectrum upon visible light excitation of the CrVI-OII --> CrV-OI ligand-to-metal charge-transfer reveals electron transfer from MnIII(mu-O)2MnIV (Mn-O stretch at 700 cm-1) to CrVI, resulting in the formation of CrV and MnIV(mu-O)2MnIV (Mn-O stretch at 645 cm-1). All initial and final states are directly observed by FT-Raman or EPR spectroscopy, and the assignments corroborated by X-ray absorption spectroscopy measurements. The endoergic charge separation products (DELTA Eo = -0.6 V) remain after several minutes, which points to spatial separation of CrV and MnIV(mu-O)2MnIV as a consequence of hole (OI) hopping as a major contributing mechanism. This is the first observation of visible light-induced oxidation of a potential water oxidation complex by a metal charge-transfer pump in a nanoporous environment. These findings will allow for the assembly and photochemical characterization of well defined transition metal molecular units, with the ultimate goal of performing endothermic, multi-electron transformations that are coupled to visible light electron pumps in nanostructured scaffolds.

  7. Dinuclear nickel and palladium complexes with bridging 2,5-diamino-1,4-benzoquinonediimines: synthesis, structures, and catalytic oligomerization of ethylene. (United States)

    Taquet, Jean-Philippe; Siri, Olivier; Braunstein, Pierre; Welter, Richard


    Dinuclear, divalent acetylacetonato (acac) complexes of the type [M(acac){mu-C6H2(--NR)4}M(acac)] (M = Ni, Pd) have been prepared by the reaction of the corresponding bis(acac) metal precursor with 2,5-diamino-1,4-benzoquinonediimines C6H2(NHR)2(=NR)2 (4a, R = CH2-t-Bu; 4b, R = CH2Ph; 4c, R = Ph), which are metalated and become bridging ligands, also like in the complex [(C8H11)Pt{mu-C6H2(--NCH2-t-Bu)4}Pt(C8H11)] (6) obtained by the reaction of 4a with [PtCl2(COD)]. The complexes were fully characterized, including by X-ray diffraction for [Ni(acac){mu-C6H2(--NCH2Ph)4}Ni(acac)] (9b) and [Pd(acac){mu-C6H2(--NCH2-t-Bu)4}Pd(acac)] (10a). The coordination geometry around the metal ions is square-planar, and a complete electronic delocalization of the quinonoid pi system occurs between the metal centers over the two N--C--C--C--N halves of the ligand. The nature of the N substituent explains the differences between the supramolecular stacking arrangements found for [Ni(acac){mu-C6H2(--NR)4}Ni(acac)] (9a; R = CH2-t-Bu; 9b, R = CH2Ph). The Ni complexes were evaluated as catalyst precursors for ethylene oligomerization in the presence of AlEtCl(2) or MAO as the cocatalyst, in particular in order to study possible cooperative effects resulting from electronic communication between the metal centers and to examine the influence of the N substituent on the activity and selectivity. These catalysts afforded mostly ethylene dimers and trimers.

  8. Comparative analysis of electron-density and electron-localization function for dinuclear manganese complexes with bridging boron- and carbon-centered ligands. (United States)

    Götz, Kathrin; Kaupp, Martin; Braunschweig, Holger; Stalke, Dietmar


    Bonding in borylene-, carbene-, and vinylidene-bridged dinuclear manganese complexes [MnCp(CO)(2)](2)X (X = B-tBu, B = NMe(2), CH(2), C=CH(2)) has been compared by analyses based on quantum theory of atoms in molecules (QTAIM), on the electron-localization function (ELF), and by natural-population analyses. All of the density functional theory based analyses agree on the absence of a significant direct Mn-Mn bond in these complexes and confirm a dominance of delocalized bonding via the bridging ligand. Interestingly, however, the topology of both charge density and ELF related to the Mn-bridge-Mn bonding depend qualitatively on the chosen density functional (except for the methylene-bridged complex, which exhibits only one three-center-bonding attractor both in -nabla(2)rho and in ELF). While gradient-corrected functionals provide a picture with localized two-center X-Mn bonding, increasing exact-exchange admixture in hybrid functionals concentrates charge below the bridging atom and suggests a three-center bonding situation. For example, the bridging boron ligands may be described either as substituted boranes (e.g., at BLYP or BP86 levels) or as true bridging borylenes (e.g., at BHLYP level). This dependence on the theoretical level appears to derive from a bifurcation between two different bonding situations and is discussed in terms of charge transfer between X and Mn, and in the context of self-interaction errors exhibited by popular functionals.

  9. Spin Crossover in Dinuclear N4S2 Iron(II) Thioether-Triazole Complexes: Access to [HS-HS], [HS-LS], and [LS-LS] States. (United States)

    Hogue, Ross W; Feltham, Humphrey L C; Miller, Reece G; Brooker, Sally


    Access to a new family of thioether-linked PSRT ligands, 4-substituted-3,5-bis{[(2-pyridylmethyl)sulfanyl]methyl}-4H-1,2,4-triazoles (analogues of the previously studied amino-linked PMRT ligands), has been established. Four such ligands have been prepared, PSPhT, PS(i)BuT, PS(t-Bu)PhT, and PS(Me)PhT, with R = Ph, (i)Bu, (t-Bu)Ph, and (Me)Ph, respectively. Three dinuclear colorless to pale green iron(II) complexes, [Fe(II)2(PSRT)2](BF4)4·solvent, featuring N4S2 donor sets, were prepared. Single-crystal structure determinations on [Fe(II)2(PSPhT)2](BF4)4·2MeCN·H2O, [Fe(II)2(PSPhT)2](BF4)4·2(1)/2MeCN·(1)/2H2O·THF, [Fe(II)2(PS(Me)PhT)2](BF4)4·2MeCN, and [Fe(II)2(PS(i)BuT)2](BF4)4·4MeCN reveal that all four are stabilized in the [HS-HS] state to 100 K and that both possible binding modes of the bis-terdentate ligands, cis- and trans-axial, are observed. Variable-temperature magnetic susceptibility studies of air-dried crystals (solvatomorphs of the single crystal samples) reveal the first examples of spin crossover (SCO) for a dinuclear iron(II) complex with N4S2 coordination. Specifically, [Fe(II)2(PSPhT)2](BF4)4·2(1)/2H2O undergoes a multistep but complete SCO from [HS-HS] to [LS-LS], whereas [Fe(II)2(PS(Me)PhT)2](BF4)4·1(1)/2MeCN·2H2O exhibits a half-SCO from [HS-HS] to [HS-LS]. In contrast, [Fe(II)2(PS(i)BuT)2](BF4)4·MeCN·H2O remains [HS-HS] down to 50 K. The reflectance spectrum of pale green [Fe(II)2(PSPhT)2](BF4)4·(1)/2CHCl3·2(1)/2H2O (solvatomorph A) reveals a trace of LS character (572 nm band (1)A1g → (1)T1g). Evans' (1)H NMR method and UV-vis spectroscopy studies revealed that on cooling dark green acetonitrile solutions of these complexes from 313 to 233 K, all three undergo SCO centered at or near room temperature. The tendency of the complexes to go LS in solution reflects the electronic impact of R on the σ-donor strength of the PSRT ligand, whereas the opposite trend in stabilization of the LS state is seen in the solid state, where

  10. Interaction of a dinuclear fluorescent Cd(II) complex of calix[4]arene conjugate with phosphates and its applicability in cell imaging. (United States)

    Sreenivasu Mummidivarapu, V V; Hinge, Vijaya Kumar; Rao, Chebrolu Pulla


    A triazole-linked hydroxyethylimino conjugate of calix[4]arene () and its cadmium complex have been synthesized and characterized, and their structures have been established. In the complex, both the Cd(2+) centers are bound by an N2O4 core, and one of it is a distorted octahedral, whereas the other is a trigonal anti-prism. The fluorescence intensity of the di-nuclear Cd(ii) complex is quenched only in the presence of phosphates and not with other anions studied owing to their binding affinities and the nature of the interaction of the phosphates with Cd(2+). These are evident even from their absorption spectra. Different phosphates exhibit changes in both their fluorescence as well as absorption spectra to varying extents, suggesting their differential interactions. Among the six phosphates, H2PO4(-) has higher fluorescence quenching even at low equivalents of this ion, whereas P2O7(4-) shows only 50% quenching even at 10 equivalents. The fluorescence quenching is considerable even at 20 ppb (0.2 μM) of H2PO4(-), whereas all other phosphates require a concentration of 50-580 ppb to exhibit the same effect on fluorescence spectra. Thus, the interaction of H2PO4(-) is more effective by ∼30 fold as compared to that of P2O7(4-). Fluorescence quenching by phosphate is due to the release of from its original cadmium complex via the formation of a ternary species followed by the capture of Cd(2+) by the phosphate, as delineated based on the combination of spectral techniques, such as absorption, emission, (1)H NMR and ESI MS. The relative interactive abilities of the six phosphates differ from each other. The removal of Cd(2+) is demonstrated to be reversible by the repeated addition of the phosphate followed by Cd(2+). The characteristics of the ternary species formed in each of these six phosphates have been computationally modeled using molecular mechanics. The computational study revealed that the coordination between cadmium and -CH2-CH2-OH breaks and new

  11. Biologically relevant mono- and di-nuclear manganese II/III/IV complexes of mononegative pentadentate ligands

    DEFF Research Database (Denmark)

    Baffert, Carole; Collomb, Marie-Nöelle; Deronzier, Alain


    ,2-diamine) have been prepared. The crystal structure of the Mn(II)-aqua complex of 1, shows it to be dimeric via (mu-kappaO)-bridging through one carboxylate oxygen atom of each of the two ligands. The non-coordinated carboxylate oxygen atoms are H-bonded to the water ligands on the adjacent Mn ion......Manganese(II) complexes of mononegative pentadentate N4O ligands [Mn2(mgbpen)(2)(H2O)(2)](ClO4)(2) (1), (mgbpen(-) = N-methyl-N'-glycyl-N,N'-bis(2-pyridylmethyl)ethane-1,2-diamine) and [Mn-2(bzgbpen)(2)(H2O)(2)](ClO4)(2) ( 2), (bzgbpen(-)=N-benzyl-N'-glycyl-N,N'-bis(2-pyridylmethyl)ethane-1......-bridged dimanganese(III) and di-mu-oxo-dimanganese(II) complexes, depending on solvent. The [Mn(III)-OR](+), R = H or CH3 complexes are generated in water or methanol, respectively, and are potentially useful spectroscopic models for active Mn-lipoxygenases. In acetonitrile, di-mu-oxo-dimanganese(II) complexes...

  12. Surface-Active Mononuclear and Dinuclear Ru(II) Complexes based on Thio-substituted Terpyridines Bearing Cyclodextrin Recognition Units


    Pikramenou, Zoe; Unwin, Patrick R


    Abstract Ruthenium(II) surface active complexes based on a tpySH ligand have been prepared and characterised, (1) [Ru(tpyada)(tpySH)](PF6)2, (2) [Ru(biptpy)(tpySH)](PF6)2 and (3) [Ru(pm-?-CD(ttp))(tpySH)](PF6)2. The complexes bear a surface active thiol group and a recognition unit which is either a ?-cyclodextrin or a hydrophobic tail (admantyl- or biphenyl) in order to utilise cyclodextrin recognition for the formation of supramolecular wires using bottom up approaches. Monolaye...

  13. A study of the effect of ammonia gas on the solid mono- and dinuclear oxorhenium(V complexes

    Directory of Open Access Journals (Sweden)



    Full Text Available The reaction of ammonia gas with the solid oxorhenium(V complexes [Re2 O3L2Cl4]·2H2O, [Re2O2L3Cl6]·2H2O, [ReOLCl(OH23]Cl2, [ReOL2(OH23]CCl3, [ReOLCl3(OH2], [ReOL(SCN2Cl(OH2]·H2O and [ReOL(SCNCl2(OH2] (where L = 2-benzimadazolethione, yielded the corresponding ammine and/or amine complexes, [Re2O3L2(NH32(NH22]Cl2 (I, [Re2O2L3(NH32(NH24]Cl2 (II, [Re2O3L2(NH32 (NH24]·H2O (III, [Re2O3L4(NH24] (IV, [Re2O3L2(NH32(NH24C (V, [Re2O3L2(SCN4(NH32] (VI and [Re2O3L2(Thio2(NH24] (VII, respectively, (Thio = thiourea where ammonia gas has replaced other ligands such as chlorine and water. In complex VII thiourea replaced the thiocyanate group in the start complex through its reaction with ammonia gas. The obtained ammine and/or amine of rhenium(V complexes have been observed to decompose through several isolatable, as well as non-isolatable complex species as intermediates during heating. [Re2O3L4], [Re2O3L2(NH24] and [Re2O3L2(SCN4], were synthesized pyrolytically in the solid state from the corresponding parent oxorhenium complexes. The electronic absorption spectra and magnetic moments of the complexes show that the Re(V cation has an octahedral configuration. IR,1H-NMR spectroscopy, conductivity measurements and thermal analysies show that ammonia and thiourea behave as neutral monodentate ligands, SCN- and NH2- as monodentate monoanionic ligands, the organic ligand (L as a neutral monodentate or bidentate ligand towards the metal cation.

  14. In vitro cytotoxic activities, DNA-, and BSA-binding studies of a new dinuclear copper(II) complex with N-[3-(dimethylamino)propyl]-N'-(2-carboxylatophenyl)-oxamide as ligand. (United States)

    Jiao, Jing; Jiang, Man; Li, Yan-Tuan; Wu, Zhi-Yong; Yan, Cui-Wei


    A new dinuclear copper(II) complex bridged by N-[3-(dimethylamino)propyl]-N'- (2-carbo-xylatophenyl)oxamide (H3 dmapob), and endcapped with 2,2'-diamino-4,4'-bithiazole (dabt), namely [Cu₂(dmapob)(dabt)(CH₃OH)(pic)]·(DMF)₀.₇₅ ·(CH₃OH)₀.₂₅ has been synthesized and characterized by elemental analysis, molar conductivity measurement, infrared and electronic spectra studies, and single-crystal X-ray diffraction. In the crystal structure, both copper(II) ions have square-pyramidal coordination geometries. The Cu···Cu separation through the oxamido bridge is 5.176(9) Å. A two-dimensional supramolecular framework is formed through hydrogen bonds and π-π stacking interactions. The reactivities toward herring sperm DNA and bovine serum albumin (BSA) show that the complex can interact with the DNA via intercalation mode and bind to the BSA responsible for quenching of tryptophan fluorescence by the static quenching mechanism. The in vitro anticancer activities suggest that the copper(II) complex is active against the selected tumor cell lines. The influence of different bridging ligands in dinuclear complexes on the DNA- and BSA-binding properties as well as anticancer activities is preliminarily discussed. © 2013 Wiley Periodicals, Inc.

  15. EPR and 55Mn cw-ENDOR study of an antiferrogmagnetically coupled dinuclear manganese (Mn III Mn IV) complex (United States)

    Zweygart, W.; Bittl, R.; Wieghardt, K.; Lubitz, W.


    X- and Q-band EPR and 55Mn cw-ENDOR experiments are reported on a binuclear oxo-bridged dimanganese Mn III Mn IV complex. Consistent simulations of spectra from both frequency bands using one parameter set for the orthorhombic g tensor and Mn III and Mn IV hyperfine tensors are achieved. Information on the manganese hyperfine couplings is independently obtained from 55Mn cw-ENDOR spectroscopy performed on both ions.

  16. Synthesis and structures of doubly-bridged dicyclopentadienyl dinuclear rhenium complexes, and their photochemical reactions with aromatic halides in benzene. (United States)

    Zhu, Bolin; Huang, Xinwei; Hao, Xiaoting


    Reaction of the doubly-bridged biscyclopentadienes (C5H4(EMe2))(C5H4(SiMe2)) (E = Si(1a), or C(1b)) with Re2(CO)10 in refluxing mesitylene gave the corresponding dirhenium carbonyl complexes [(η(5)-C5H3)2(EMe2)(SiMe2)][Re(CO)3]2 (trans-2a,b and cis-2a,b), and the desilylated products [(η(5)-C5H4)2(EMe2)][Re(CO)3]2 (3a,b). Photolysis of trans-2a,b with a series of aryl halides in benzene results in the formation of biphenyl, together with the corresponding rhenium dihalide complexes trans-[(η(5)-C5H3)2(EMe2)(SiMe2)][Re(CO)3][Re(CO)2X2] (X = Cl, Br, I) (4, 6, 8, or 10) and trans-[(η(5)-C5H3)2(EMe2)(SiMe2)][Re(CO)2X2]2 (5, 7, or 9). Additional experiments indicate that one phenyl ring in the resulting biphenyl comes from aryl halides and the other phenyl ring comes from the solvent benzene. However, photolysis of trans-2a with benzyl chloride and n-hexyl chloride in benzene afforded the corresponding bibenzyl and n-dodecane, as well as the rhenium dichlorides 8 and 9. In addition, complex trans-2a can also activate the C-F bond on C6F6 to form the pentafluorophenyl rhenium fluoride trans-[(η(5)-C5H3)2(SiMe2)2][Re(CO)3][Re(CO)2(C6F5)F] (11). Molecular structures of cis-2a, cis-2b, trans-2b, 3b, 6, 7, 8, 11, and 12 determined by X-ray diffraction are also presented.

  17. Tuning affinity and reversibility for O2 binding in dinuclear Co(II) complexes

    DEFF Research Database (Denmark)

    Vad, Mads Sørensen; Johansson, Frank Bartnik; Seidler-Egdal, Rune Kirk


    )]2+ and [Co2(bpbp)- (O2)(CCl3CO2)]2+. The O2 affinities can be qualitatively correlated with both the pKa value of the parent acetic or chloroacetic acid and the redox potential of the O2 2−/O2˙− couple measured for the peroxidebridged complexes. The redox potential varies between 510 mV (vs. Fc0...... qualitatively consistent with the expectation from the pKa of the parent 1-naphthoic acid. Introduction Reversible dioxygen binding is a life-supporting process for respiring organisms carried out by three classes of metalloproteins: hemoglobin, hemerythrin, and hemocyanin, the latter two...

  18. A luminescent dinuclear Eu(III) complex based on 2,8-bis(4',4',4',-trifluoro-1',3'-dioxobutyl)-dibenzothiophene for light-emitting diodes

    International Nuclear Information System (INIS)

    Liu Shenggui; He Pei; Wang Huihui; Shi Jianxin; Gong, Menglian


    A dinuclear Eu (III) complex Eu 2 (dbt) 3 .4H 2 O was synthesized, where H 2 dbt was 2,8-bis(4',4',4',-trifluoro-1',3'-dioxobutyl)-dibenzothiophene. The complex emits the characteristic red luminescence of Eu 3+ ion due to the 5 D 0 → 7 F J (J=0-4) transitions under 395 nm-light excitation with a luminescent quantum efficiency of 17%. The complex is thermally stable up to 280 deg. C. It was found that the complex can be effectively excited by a 395 nm-emitting InGaN chip. Bright red light was obtained using the complex as light color-conversion material.

  19. Structure of a dinuclear cadmium complex with 2,2′-bipyridine, monodentate nitrate and 3-carboxy-6-methylpyridine-2-carboxylate ligands: intramolecular carbonyl(lone pair...π(ring and nitrate(π...π(ring interactions

    Directory of Open Access Journals (Sweden)

    Juan Granifo


    Full Text Available The centrosymmetric dinuclear complex bis(μ-3-carboxy-6-methylpyridine-2-carboxylato-κ3N,O2:O2;κ3O2:N,O2-bis[(2,2′-bipyridine-κ2N,N′(nitrato-κOcadmium] methanol monosolvate, [Cd2(C8H6NO42(NO32(C10H8N22]·CH3OH, was isolated as colourless crystals from the reaction of Cd(NO32·4H2O, 6-methylpyridine-2,3-dicarboxylic acid (mepydcH2 and 2,2′-bipyridine in methanol. The asymmetric unit consists of a CdII cation bound to a μ-κ3N,O2:O2-mepydcH− anion, an N,N′-bidentate 2,2′-bipyridine group and an O-monodentate nitrate anion, and is completed with a methanol solvent molecule at half-occupancy. The Cd complex unit is linked to its centrosymmetric image through a bridging mepydcH− carboxylate O atom to complete the dinuclear complex molecule. Despite a significant variation in the coordination angles, indicating a considerable departure from octahedral coordination geometry about the CdII atom, the Cd—O and Cd—N distances in this complex are surprisingly similar. The crystal structure consists of O—H...O hydrogen-bonded chains parallel to a, further bound by C—H...O contacts along b to form planar two-dimensional arrays parallel to (001. The juxtaposed planes form interstitial columnar voids that are filled by the methanol solvent molecules. These in turn interact with the complex molecules to further stabilize the structure. A search in the literature showed that complexes with the mepydcH− ligand are rare and complexes reported previously with this ligand do not adopt the μ-κ3 coordination mode found in the title compound.

  20. Synthesis, characterization, crystal structure and antibacterial activity of new sulfur-bridged dinuclear silver(I) thiosemicarbazone complex [Ag.sub.2./sub.(PPh.sub.3./sub.).sub.2./sub.(μ-S-Brcatsc).sub.2./sub.(η.sup.1./sup.-S-Brcatsc).sub.2./sub.](NO.sub.3./sub.).sub.2./sub..

    Czech Academy of Sciences Publication Activity Database

    Shahsavani, E.; Khalaji, A.D.; Feizi, N.; Kučeráková, Monika; Dušek, Michal


    Roč. 429, Apr (2015), 61-66 ISSN 0020-1693 R&D Projects: GA ČR(CZ) GA14-03276S Institutional support: RVO:68378271 Keywords : sulfur-bridged dinuclear silver (I) * thiosemicarbazone complex * single-crystal * distorted tetrahedron * antibacterial activity Subject RIV: BM - Solid Matter Physics ; Magnetism Impact factor: 1.918, year: 2015

  1. Design, synthesis and physico-chemical investigation of a dinuclear ...

    Indian Academy of Sciences (India)

    Home; Journals; Journal of Chemical Sciences; Volume 113; Issue 4. Design, synthesis and physico-chemical investigation of a dinuclear zinc(II) complex with a novel 'end-off' compartmental ligand. Anil D Naik Vidyanand K Revankar. Inorganic Volume 113 Issue 4 August 2001 pp 285-290 ...

  2. Design, synthesis and physico-chemical investigation of a dinuclear ...

    Indian Academy of Sciences (India)


    Design, synthesis and physico-chemical investigation of a dinuclear zinc(II) complex with a novel 'end-off' compartmental ligand. ANIL D NAIK and VIDYANAND K REVANKAR*. Department of Chemistry, Karnatak University, Dharwad 580 003, India e-mail: MS received 17 March 2001; revised 9 ...

  3. A highly luminescent dinuclear Eu(III) complex based on 4,4'-bis (4'',4'',4''-trifluoro-1'',3''-dioxobutyl)-o-terphenyl for light-emitting diodes

    International Nuclear Information System (INIS)

    Liu Shenggui; He Pei; Wang Huihui; Shi Jianxin; Gong Menglian


    A dinuclear Eu(III) complex Eu 2 (btbt) 3 .4H 2 O.CH 3 CH 2 OH.N(CH 2 CH 3 ) 3 was synthesized, where H 2 (btbt) was 4,4'-bis (4'',4'',4'',-trifluoro-1'',3''-dioxobutyl)-o-terphenyl. The composition and structure of the complex were characterized by elemental analysis, IR, UV-vis and FAB-MS spectroscopy. The complex emits the characteristic red luminescence of Eu 3+ ion due to the 5 D 0 → 7 F J (J = 0-4) transitions under ∼395 nm-light excitation with good luminescent quantum efficiency (32%) and exhibits high thermal stability (337 deg. C). Bright red light-emitting diodes (LEDs) were fabricated by coating the complex onto a ∼395 nm-emitting InGaN chip. When the mass ratio of the red phosphor to the silicone is 1:30, the efficiency of the fabricated LEDs with the europium complex is 0.98 lm w -1 . The CIE chromaticity coordinates of the LEDs are x = 0.6057 and y = 0.3137, which are close to the National Television Standard Committee (NTSC) standard values for red color. The results indicate that the complex may act as a red component in the fabrication of near UV InGaN-based white light-emitting diodes with high color-rendering index.

  4. Dinuclear complexes of copper and zinc with m-xylene/cyclohexane-linked bis-aspartic acids: synthesis, characterization, dioxygen activation, and catalytic oxidation of nitrobenzene in pure aqueous solution. (United States)

    Zhu, Shourong; Qiu, Zhixiang; Ni, Tianjun; Zhao, Xiujuan; Yan, Shikai; Xing, Feifei; Zhao, Yongmei; Bai, Yueling; Li, Mingxing


    Two new m-xylene/cyclohexane-linked bis-aspartic acid ligands, L(b) and L(c), were synthesized via Michael addition in basic aqueous solution. Their structures were characterized by elemental analysis, NMR and MS spectrometry. Both ligands react with Cu(II) and Zn(II) to form dinuclear complexes, with M2L(OH)(-) the major species in neutral/weak basic aqueous solution. To quantify the relative interaction strength between a Lewis acid and base, a new parameter σ = log K/14 was proposed which compares the stability constant with the binding constant between H(+) and OH(-). The dinuclear copper complexes (L(b)-2Cu and L(c)-2Cu) react with H2O2 in aqueous solution. The reaction in 0.020 M phosphate buffer at pH 7.5 is first-order for [L(c)-2Cu], but second-order for [L(b)-2Cu]. The oxidation products are oxygenated and/or dehydrogenated species. Radical trapping tests indicate that both complexes slightly scavenge the OH˙ radical, but generate the H˙ radical. L(c)-2Cu generates the H˙ radical much more effectively than that of L(b)-2Cu when reacted with H2O2. Both complexes are excellent catalysts for the oxidation of nitrobenzene in the presence of H2O2 in weakly basic aqueous solution. The oxidation follows the rate-law v = k[complex][nitrobenzene][H2O2]. The k values in pH 8.0 phosphate buffer at 25 °C are 211.2 ± 0.3 and 607.9 ± 1.7 mol(-2) L(2) s(-1) for L(b)-2Cu and L(c)-2Cu, respectively. The Arrhenius activation energies are 69.4 ± 2.2 and 70.0 ± 4.3 kJ mol(-1) for L(b)-2Cu and L(c)-2Cu, respectively, while the Arrhenius pre-exponential factors are 2.62 × 10(14) and 1.06 × 10(15), respectively. The larger pre-exponential factor makes L(c)-2Cu more catalytically active than L(b)-2Cu. These complexes are some of the most effective oxidation catalysts known for the oxidation of nitrobenzene.

  5. Four new dinuclear Cu(ii) hydrazone complexes using various organic spacers: syntheses, crystal structures, DNA binding and cleavage studies and selective cell inhibitory effect towards leukemic and normal lymphocytes. (United States)

    Banerjee, Sambuddha; Mondal, Susmita; Sen, Soma; Das, Saurabh; Hughes, David L; Rizzoli, Corrado; Desplanches, Cédric; Mandal, Chitra; Mitra, Samiran


    Syntheses and crystal structures of four new hydrazone-based Cu(ii) complexes, [{Cu(L(1))(H(2)O)}(2)(mu-pyraz)](ClO(4))(2) (), [{Cu(L(1))(OClO(3))}(2)(mu-4,4'-bipy)] (), [{Cu(L(2)H)}(mu-pyraz){Cu(L(2)H)(OClO(3))}].(ClO(4)) () and [{Cu(L(2))}(2)(mu-bpe)] () [L(1)H = condensation product of benzhydrazide and pyridine-2-carbaldehyde and L(2)H(2) = condensation product of benzoyl acetone and benzhydrazide], bridged by various organic spacers [pyrazine (pyraz), 4,4'-bipyridine (4,4'-bipy) and 1,2-di(4-pyridyl)ethane (bpe)] are reported in this paper. The single-crystal X-ray crystallographic studies reveal that all are dinuclear units where and form strong intermolecular H-bonding to form sheets of interconnected ions, whereas forms sheets of dinuclear chains through pi-pi interactions; in , molecules are linked only through van der Waals interactions. The variable-temperature magnetic moment studies reveal that and show antiferromagnetic coupling between the Cu(ii) centers at lower temperatures. The binding ability of with calf thymus DNA [CT-DNA] is reported using various spectroscopic studies (UV-Vis titration, circular dichroism and fluorescence). The binding constants of with CT-DNA, as calculated by different methodologies, are of the order of 10(5) M(-1). The mode of interaction between and CT-DNA has been predicted using circular dichroic (CD) spectroscopy, where it has been shown that most probably interacts with DNA via intercalation between the base pairs leading to a change in B-DNA conformation. is also able to cleave supercoiled (SC) plasmid DNA pUC19 in a time and dose dependent manner as demonstrated by agarose gel electrophoresis, and also demonstrates its potential to cleave the SC plasmid DNA via both oxidative and hydrolytic mechanisms. Approximately 50% of leukemic cells are found to be dead when two representative leukemic cell lines are exposed to ( approximately 80 muM) even for 24 h as determined by different cell cytotoxicity assays

  6. Magnetic and Photo-Physical Properties of Lanthanide Dinuclear Complexes Involving the 4,5-Bis(2-Pyridyl-N-Oxidemethylthio-4′,5′-Dicarboxylic Acid-Tetrathiafulvalene-, Dimethyl Ester Ligand

    Directory of Open Access Journals (Sweden)

    Fabrice Pointillart


    Full Text Available The reaction between the 4,5-bis(2-pyridyl-N-oxidemethylthio-4′,5′-dicarboxylic acid-tetrathiafulvalene-, dimethyl ester ligand (L and the metallo-precursors Ln(hfac3·2H2O leads to the formation of two dinuclear complexes of formula [Ln2(hfac6(L]·(CH2Cl2·(C6H140.5 (LnIII = DyIII (1 and YbIII (2. The X-ray structure reveals a quite regular square anti-prism symmetry for the coordination sphere of the lanthanide ion. UV-visible absorption properties have been experimentally measured and rationalized by TD-DFT calculations. The functionalization of the tetrathiafulvalene (TTF core by two methyl ester moieties induces the appearance of an additional absorption band in the lowest-energy region of the spectrum. The latter has been identified as a HOMO (Highest Occupied Molecular Orbital→LUMO (Lowest Unoccupied Molecular Orbital Intra-Ligand Charge Transfer (ILCT transition in which the HOMO and LUMO are centred on the TTF and methyl ester groups, respectively. Irradiation at 22,222 cm−1 of this ILCT band induces an efficient sensitization of the YbIII-centred emission that can be correlated to the magnetic properties.

  7. Dinuclear PhosphoiminoBINOL-Pd Container for Malononitrile: Catalytic Asymmetric Double Mannich Reaction for Chiral 1,3-Diamine Synthesis. (United States)

    Arai, Takayoshi; Sato, Katsuya; Nakamura, Ayu; Makino, Hiroki; Masu, Hyuma


    A phosphoiminoBINOL ligand was designed to form a dinuclear metal complex that could hold a malononitrile molecule. The dinuclear bis(phosphoimino)binaphthoxy-Pd 2 (OAc) 2 complex catalyzed a double Mannich reaction of N-Boc-imines with malononitrile to give chiral 1,3-diamines with high enantioselectivity. The rational asymmetric catalyst, which smoothly introduces the first coupling product to the second coupling reaction while avoiding the reverse reaction, facilitates the over-reaction into a productive reaction process.

  8. Catechol oxidase activity of a series of new dinuclear copper(II) complexes with 3,5-DTBC and TCC as substrates: syntheses, X-ray crystal structures, spectroscopic characterization of the adducts and kinetic studies. (United States)

    Banu, Kazi Sabnam; Chattopadhyay, Tanmay; Banerjee, Arpita; Bhattacharya, Santanu; Suresh, Eringathodi; Nethaji, Munirathinam; Zangrando, Ennio; Das, Debasis


    A series of dinuclear copper(II) complexes has been synthesized with the aim to investigate their applicability as potential structure and function models for the active site of catechol oxidase enzyme. They have been characterized by routine physicochemical techniques as well as by X-ray single-crystal structure analysis: [Cu 2(H 2L2 (2))(OH)(H 2O)(NO 3)](NO 3) 3.2H 2O ( 1), [Cu(HL1 (4))(H 2O)(NO 3)] 2(NO 3) 2.2H 2O ( 2), [Cu(L1 (1))(H 2O)(NO 3)] 2 ( 3), [Cu 2(L2 (3))(OH)(H 2O) 2](NO 3) 2, ( 4) and [Cu 2(L2 (1))(N 3) 3] ( 5) [L1 = 2-formyl-4-methyl-6R-iminomethyl-phenolato and L2 = 2,6-bis(R-iminomethyl)-4-methyl-phenolato; for L1 (1) and L2 (1), R = N-propylmorpholine; for L2 (2), R = N-ethylpiperazine; for L2 (3), R = N-ethylpyrrolidine, and for L1 (4), R = N-ethylmorpholine]. Dinuclear 1 and 4 possess two "end-off" compartmental ligands with exogenous mu-hydroxido and endogenous mu-phenoxido groups leading to intermetallic distances of 2.9794(15) and 2.9435(9) A, respectively; 2 and 3 are formed by two tridentate compartmental ligands where the copper centers are connected by endogenous phenoxido bridges with Cu-Cu separations of 3.0213(13) and 3.0152(15) A, respectively; 5 is built by an end-off compartmental ligand having exogenous mu-azido and endogenous mu-phenoxido groups with a Cu-Cu distance of 3.133(2) A (mean of two independent molecules). The catecholase activity of all of the complexes has been investigated in acetonitrile and methanol medium by UV-vis spectrophotometric study using 3,5-di- tert-butylcatechol (3,5-DTBC) and tetrachlorocatechol (TCC) as substrates. In acetonitrile medium, the conversion of 3,5-DTBC to 3,5-di- tert-butylbenzoquinone (3,5-DTBQ) catalyzed by 1- 5 is observed to proceed via the formation of two enzyme-substrate adducts, ES1 and ES2, detected spectroscopically for the first time. In methanol medium no such enzyme-substrate adduct has been detected, and the 3,5-DTBC to 3,5-DTBQ conversion is observed to be catalyzed by 1- 5

  9. Synthesis, characterization, single crystal X-ray determination, fluorescence and electrochemical studies of new dinuclear nickel(II) and oxovanadium(IV) complexes containing double Schiff base ligands. (United States)

    Shafaatian, Bita; Ozbakzaei, Zahra; Notash, Behrouz; Rezvani, S Ahmad


    A series of new bimetallic complexes of nickel(II) and vanadium(IV) have been synthesized by the reaction of the new double bidentate Schiff base ligands with nickel acetate and vanadyl acetylacetonate in 1:1 M ratio. In nickel and also vanadyl complexes the ligands were coordinated to the metals via the imine N and enolic O atoms. The complexes have been found to possess 1:1 metals to ligands stoichiometry and the molar conductance data revealed that the metal complexes were non-electrolytes. The nickel and vanadyl complexes exhibited distorted square planar and square pyramidal coordination geometries, respectively. The emission spectra of the ligands and their complexes were studied in methanol. Electrochemical properties of the ligands and their metal complexes were also investigated in DMSO solvent at 150 mV s(-1) scan rate. The ligands and metal complexes showed both quasi-reversible and irreversible processes at this scan rate. The Schiff bases and their complexes have been characterized by FT-IR, 1H NMR, UV/Vis spectroscopies, elemental analysis and conductometry. The crystal structure of the nickel complex has been determined by single crystal X-ray diffraction. Copyright © 2014 Elsevier B.V. All rights reserved.

  10. Coupling of Electron Transfer and Bond Dissociation Processes in Dinuclear Complexes with Rhodium and Iridium Reaction Centers Bridged by 2,2'-Bipyrimidine

    Czech Academy of Sciences Publication Activity Database

    Kaim, W.; Reinhardt, R.; Greulich, S.; Sieger, M.; Klein, A.; Fiedler, Jan


    Roč. 66, č. 2 (2001), s. 291-306 ISSN 0010-0765 R&D Projects: GA MŠk OC D15.10 Institutional research plan: CEZ:AV0Z4040901 Keywords : EPR spectroscopy * iridium complexes * rhodium complexes Subject RIV: CG - Electrochemistry Impact factor: 0.778, year: 2001

  11. Thermally reversible single-crystal to single-crystal transformation of mononuclear to dinuclear Zn(II) complexes by [2+2] cycloaddition reaction. (United States)

    Medishetty, Raghavender; Yap, Terence Teck Sheng; Koh, Lip Lin; Vittal, Jagadese J


    Two Zn(II) complexes of trans-4-styrylpyridine ligands undergo [2+2] cycloaddition reaction forming Zn(II) complex dimers in a single-crystal to single-crystal (SCSC) manner which were thermally reversible. The dimers are presumed to be the stable intermediates in the formation of 1D coordination polymers upon prolonged exposure to UV light.

  12. Antitumor trans-N-heterocyclic carbene-amine-Pt(II) complexes: synthesis of dinuclear species and exploratory investigations of DNA binding and cytotoxicity mechanisms. (United States)

    Chtchigrovsky, Mélanie; Eloy, Laure; Jullien, Hélène; Saker, Lina; Ségal-Bendirdjian, Evelyne; Poupon, Joel; Bombard, Sophie; Cresteil, Thierry; Retailleau, Pascal; Marinetti, Angela


    A series of bimetallic [(NHC)PtX2]2(diamine) complexes have been prepared as a new chemotype for potential anticancer agents. These complexes display an uncommon set of structural features as far as they combine two bifunctional, trans-configured platinum centers. They display cytotoxic activities in the micromolar range on many cancerous cell lines and do not cross-react with cisplatin in A2780/DDP cell lines. They bind slowly to double-stranded DNAs, giving monoadducts as the major products. Pathways for cellular toxicity have been investigated for both mono- and bimetallic trans-(NHC)PtX2(amine) complexes. It has been highlighted that, unlike cisplatin, these complexes do not induce cell cycle arrest. They trigger apoptosis in A2780 cells by a pathway involving translocation of apoptosis-inducing factor and caspase 12 to the nucleus. Moreover, bimetallic complexes may induce necrosis.

  13. Phenoxo bridged dinuclear Zn(II) Schiff base complex as new precursor for preparation zinc oxide nanoparticles: Synthesis, characterization, crystal structures and photoluminescence studies

    International Nuclear Information System (INIS)

    Saeednia, S.; Iranmanesh, P.; Ardakani, M. Hatefi; Mohammadi, M.; Norouzi, Gh.


    Highlights: • A novel nano-scale Zn(II) complex was synthesized by solvothermal method. • Chemical structure of the nanostructures was characterized as well as bulk complex. • The photoluminescence property of the complex was investigated at room temperature. • The thermogravimetry and differential thermal analysis were carried out. • Thermal decomposition of the nanostructures was prepared zinc oxide nanoparticles. - Abstract: Nanoparticles of a novel Zn(II) Schiff base complex, [Zn(HL)NO 3 ] 2 (1), (H 2 L = 2-[(2-hydroxy-propylimino) methyl] phenol), was synthesized by using solvothermal method. Shape, morphology and chemical structure of the synthesized nanoparticles were characterized by scanning electron microscopy (SEM), X-ray powder diffraction (XRD), Fourier Transform Infrared Spectoscopy (FT-IR) and UV–vis spectroscopy. Structural determination of compound 1 was determined by single-crystal X-ray diffraction. The results were revealed that the zinc complex is a centrosymmetric dimer in which deprotonated phenolates bridge the two five-coordinate metal atoms and link the two halves of the dimer. The thermal stability of compound 1 was analyzed by thermal gravimetric analysis (TGA) and differential scanning calorimetry (DSC). The effect of the initial substrates concentration and reaction time on size and morphology of compound 1 nanostructure was investigated as well. Furthermore, the luminescent properties of the complex 1 were examined. ZnO nanoparticles with diameter between 15 and 20 nm were simply synthesized by solid-state transformation of compound 1 at 700 °C.

  14. Pincer-CNC mononuclear, dinuclear and heterodinuclear Au(III) and Pt(II) complexes supported by mono- and poly-N-heterocyclic carbenes: synthesis and photophysical properties. (United States)

    Gonell, S; Poyatos, M; Peris, E


    A family of cyclometallated Au(iii) and Pt(ii) complexes containing a CNC-pincer ligand (CNC = 2,6-diphenylpyridine) supported by pyrene-based mono- or bis-NHC ligands have been synthesized and characterized, together with the preparation of a Pt-Au hetero-dimetallic complex based on a Y-shaped tris-NHC ligand. The photophysical properties of all the new species and of two related Ru(ii)-arene complexes were studied and compared. Whereas the pyrene-based complexes only exhibit emission in solution, those containing the Y-shaped tris-NHC ligand are only luminescent when dispersed in poly(methyl methacrylate) (PMMA). In particular, the pyrene-based complexes were found to be emissive in the range of 373-440 nm, with quantum yields ranging from 3.1 to 6.3%, and their emission spectra were found to be almost superimposable, pointing to the fluorescent pyrene-centered nature of the emission. This observation suggests that the emission properties of the pyrene fragment may be combined with some of the numerous applications of NHCs as supporting ligands allowing, for instance, the design of biological luminescent agents.

  15. New μ-OAC bridged dinuclear copper(II) complex with tridentate Schiff base ligand: synthesis, characterization, crystal structure, and CuO nano-particles formation

    Czech Academy of Sciences Publication Activity Database

    Grivani, G.; Eigner, Václav; Dušek, Michal; Sadeghi, B.; Khalaji, A.D.


    Roč. 41, č. 7 (2015), s. 456-461 ISSN 1070-3284 R&D Projects: GA ČR(CZ) GA14-03276S Institutional support: RVO:68378271 Keywords : Schiff base * complex structure * x-ray crystallography * Jana2006 Subject RIV: BM - Solid Matter Physics ; Magnetism Impact factor: 0.516, year: 2015

  16. Toxicity in tumor cells, DNA binding mode, and resistance to decomposition by sulfur nucleophiles of new dinuclear bifunctional trans-Pt-II complexes containing long alkane linkers

    Czech Academy of Sciences Publication Activity Database

    Prachařová, J.; Nováková, Olga; Kašpárková, Jana; Gibson, J.; Brabec, Viktor


    Roč. 85, č. 2 (2013), s. 343-354 ISSN 0033-4545 R&D Projects: GA ČR(CZ) GD301/09/H004 Institutional support: RVO:68081707 Keywords : PLATINUM ANTITUMOR COMPLEXES * INTERSTRAND CROSS-LINKS * GEOMETRIC ISOMERISM Subject RIV: BO - Biophysics Impact factor: 3.112, year: 2013

  17. Magnetic interactions in dinuclear Mn(III)Mn(IV) complexes covalently tethered to organic radicals: spectroscopic models for the S(2)Y(z)(*) state of photosystem II. (United States)

    Marlin, Dana S; Bill, Eckhard; Weyhermüller, Thomas; Bothe, Eberhard; Wieghardt, Karl


    A series of isostructural dimeric manganese complexes of the type [(Me(4)dtne)Mn(2)(mu-O)(2)(mu-R)](2+)(X(-))(2) have been prepared and characterized. The dimanganese cores of these complexes are rigidly held together by the hexadentate ligand Me(4)dtne (Me(4)dtne = 1,2-bis(4,7-dimethyl-1,4,7-triazacyclonon-1-yl)ethane). Molecular structures for the entire series have been obtained by X-ray diffraction measurements, of which complexes 2 (R = (-)O(2)BPh), 3 (R = (-)O(2)C-PROXYL), 4 (R = (-)O(2)C-TEMPO), and 5 (R = (-)O(2)BPhNIT) are reported here (HO(2)C-PROXYL = 3-carboxy-2,2,5,5-tetramethylpyrrolidin-1-yloxy; HO(2)C-TEMPO = 4-carboxy-2,2,6,6-tetramethylpiperidin-1-yloxy; and HO(2)BPhNIT = 2-(4-(dihydroxyboranyl)-phenyl)-4,4,5,5-tetramethyl-3-oxyimidazolidin-1-oxide). The structures of 1 (R = (-)OAc) and 6 (R = (-)O(2)CPhNIT) have been reported previously (HO(2)CPhNIT = 2-(4-carboxyphenyl)-4,4,5,5-tetramethyl-3-oxyimidazolidin-1-oxide). All complexes exhibit several redox states, which have been investigated by electrochemistry. Complexes 1, 3, 4, and 6 contain a mixed-valent Mn(III)Mn(IV) core with an isolated magnetic ground state of S = 1/2. The exchange coupling between the manganese ions is strong throughout the series (J approximately -130 +/- 10 cm(-)(1), H = -2JS(1)S(2)). The radical complexes 3, 4, and 6 exhibit, in addition, long-range exchange interaction (6.9, 7.7, and 8.8 A, respectively) between the organic radical and the dimanganese core. The intramolecular anisotropic coupling was determined from cw-EPR line shape analyses at S-, X-, and Q-band frequencies and from the intensity of half-field signals detected in normal- and parallel-mode (J(d,)(z)() = -120 x 10(-)(4), -105 x 10(-)(4), and -140 x 10(-)(4) cm(-)(1), for 3, 4, and 6 respectively). Distance information was obtained for the dimanganese core and the organic radicals from these values by using a three-spin dipole model and local spin contributions for the manganese ions.

  18. Chiral tetranuclear and dinuclear copper(ii) complexes for TEMPO-mediated aerobic oxidation of alcohols: are four metal centres better than two? (United States)

    Zhang, Guoqi; Proni, Gloria; Zhao, Sherry; Constable, Edwin C; Housecroft, Catherine E; Neuburger, Markus; Zampese, Jennifer A


    The one-pot reaction of 3,5-di-tert-butyl-2-hydroxybenzaldehyde, (R)-2-aminoglycinol and Cu(OAc)2·2H2O in a 1 : 1 : 1 ratio in the presence of triethylamine led to the isolation of X-ray quality crystals of the chiral complex (R)- in high yield. The single crystal structure of (R)- reveals a tetranuclear copper(ii) complex that contains a {Cu4(μ-O)2(μ3-O)2N4O4} core. A reaction using (1S,2R)-2-amino-1,2-diphenylethanol as precursor under the same conditions generated the chiral complex (S,R)-; its structure was determined by single crystal X-ray crystallography and was found to contain a {Cu2(μ-O)2N2O2} core. Both (R)- and (S,R)- have been used for catalytic aerobic oxidation of benzylic alcohols in combination with the TEMPO (2,2,6,6-tetramethylpiperidinyl-1-oxyl) radical. (R)- selectively catalyses the conversion of various aromatic primary alcohols to the corresponding aldehydes with high yields (99%) and TONs (770) in the air, while (S,R)- exhibits less promising catalytic performance under the same reaction conditions. The role of the cluster structures in (R)- and (S,R)- in controlling the reactivity towards aerobic oxidation reactions is discussed.

  19. New discrete and polymeric supramolecular architectures derived from dinuclear Co(II), Ni(II) and Cu(II) complexes of aryl-linked bis-beta-diketonato ligands and nitrogen bases: synthetic, structural and high pressure studies. (United States)

    Clegg, Jack K; Hayter, Michael J; Jolliffe, Katrina A; Lindoy, Leonard F; McMurtrie, John C; Meehan, George V; Neville, Suzanne M; Parsons, Simon; Tasker, Peter A; Turner, Peter; White, Fraser J


    New examples of nitrogen base adducts of dinuclear Co(II), Ni(II) and Cu(II) complexes of the doubly deprotonated forms of 1,3-aryl linked bis-beta-diketones of type [RC(=O)CH(2)C(=O)C(6)H(4)C(=O)CH(2)C(=O)R] (L(1)H(2)) incorporating the mono- and difunctional amine bases pyridine (Py), 4-ethylpyridine (EtPy), piperidine (pipi), 1,4-piperazine (pip), N-methylmorpholine (mmorph), 1,4-dimethylpiperazine (dmpip) and N,N,N',N'-tetramethylethylenediamine (tmen) have been synthesised by reaction of the previously reported [Cu(2)(L(1))(2)].2.5THF (R = Me), [Cu(2)(L(1))(2)(THF)(2)] (R = t-Bu), [Ni(2)(L(1))(2)(Py)(4)] (R = t-Bu) and [Co(2)(L(1))(2)(Py)(4)] (R = t-Bu) complexes with individual bases of the above type. Comparative X-ray structural studies involving all ten base adduct derivatives have been obtained and reveal a range of interesting discrete and polymeric molecular architectures. The respective products have the following stoichiometries: [Cu(2)(L(1))(2)(Py)(2)].Py (R = Me), [Cu(2)(L(1))(2)(EtPy)(2)].2EtPy (R = t-Bu), [Cu(2)(L(1))(2)(pipi)(2)].2pipi (R = t-Bu), [Cu(2)(L(1))(2)(mmorph)(2)] (R = t-Bu), [Cu(2)(L(1))(2)(tmen)(2)] (R = t-Bu) and {[Cu(2)(L(1))(2)(pip)].pip.2THF}(n), [Co(2)(L(1))(2)(tmen)(2)] (R = t-Bu), [Ni(2)(L(1))(2)(Py)(4)].dmpip (R = t-Bu), [Ni(2)(L(1))(2)(pipi)(4)].pipi (R = t-Bu) and [Ni(2)(L(1))(2)(tmen)(2)] (R = t-Bu). The effect of pressure on the X-ray structure of [Cu(2)(L(1))(2)(mmorph)(2)] has been investigated. An increase in pressure from ambient to 9.1 kbar resulted in modest changes to the unit cell parameters as well as a corresponding decrease of 6.7 percent in the unit cell volume. While a small 'shearing' motion occurs between adjacent molecular units throughout the lattice, no existing bonds are broken or new bonds formed.

  20. Synthesis, spectroscopic and electrochemical properties of mononuclear and dinuclear bis(bipy)ruthenium(II) complexes containing dimethoxyphenyl(pyridin-2-yl)-1,2,4-triazole ligands

    NARCIS (Netherlands)

    Passaniti, Paolo; Browne, Wesley R.; Lynch, Fiona C.; Hughes, Donal; Nieuwenhuyzen, Mark; James, Paraic; Maestri, Mauro; Vos, Johannes G.


    The ligands HL1 and H(2)L2 and the complexes [Ru(bipy)(2)L1]PF6.2H(2)O 1, [(Ru(bipy)(2))(2)L2](PF6)(2).7H(2)O 2, {where HL1 = 3-(2', 5'-dimethoxyphenyl)-5-(pyridin-2"-yl)- 1H-1,2,4-triazole, H(2)L2 = 1,4- bis(5'-(pyridin-2"-yl)- 1'H- 1', 2', 4'-triazol-3'-yl)- 2,5-dimethoxybenzene and bipy =

  1. In Vitro DNA-Binding, Anti-Oxidant and Anticancer Activity of Indole-2-Carboxylic Acid Dinuclear Copper(II Complexes

    Directory of Open Access Journals (Sweden)

    Xiangcong Wang


    Full Text Available Indole-2-carboxylic acid copper complex (ICA-Cu was successfully prepared and characterized through elemental analysis, IR, UV-Vis, 1H-NMR, TG analysis, and molar conductance, and its molecular formula was [Cu2(C9H6O2N4(H2O2]·2H2O. The binding ability of ICA-Cu to calf thymus DNA (CT-DNA was examined by fluorescence spectrometry and the viscosity method. The results indicated that, upon the addition of increasing amounts of CT-DNA, the excitation and emission intensity of ICA-Cu decreased obviously and the excitation spectra shifted towards a long wavelength. ICA-Cu could displace ethidium bromide (EB from the EB-DNA system, making the fluorescence intensity of the EB-DNA system decrease sharply; the quenching constant KSV value was 3.99 × 104 M−1. The emission intensity of the ICA-Cu-DNA system was nearly constant, along with the addition of Na+ in a series of concentrations. The fluorescence of the complex could be protected after the complex interacted with DNA. A viscosity measurement further supported the result that the ICA-Cu complex may interact with DNA in an intercalative binding mode. The antioxidant activities of ICA-Cu were evaluated by a 2,2-diphenyl-1-picrylhydrazyl (DPPH assay, a hydroxyl radical (OH scavenging assay, and a 2,2′-azino-bis(3-ethylbenzothiazoline-6-sulphonic acid (ABTS assay. The ICA-Cu exhibited the highest inhibitory effects on the ABTS radical (94% inhibition at 60 µM, followed by OH and DPPH radicals (the degrees of inhibition being 71% and 56%, respectively. The in vitro cytotoxicity activity of ICA-Cu against two human breast cancer cell lines, MDA-MB-231 and MCF-7, was investigated by 3-[4,5-dimethyltiazol2-yl]-2.5-diphenyl-tetrazolium bromide (MTT assay and cellular morphological analysis. The results showed that, upon increasing the concentration of ICA-Cu, an increase was observed in growth-inhibitory activity and the inhibition percentage were greater than 90% at 20 µM in both cell lines. Also

  2. In Vitro DNA-Binding, Anti-Oxidant and Anticancer Activity of Indole-2-Carboxylic Acid Dinuclear Copper(II) Complexes. (United States)

    Wang, Xiangcong; Yan, Maocai; Wang, Qibao; Wang, Huannan; Wang, Zhengyang; Zhao, Jiayi; Li, Jing; Zhang, Zhen


    Indole-2-carboxylic acid copper complex (ICA-Cu) was successfully prepared and characterized through elemental analysis, IR, UV-Vis, ¹H-NMR, TG analysis, and molar conductance, and its molecular formula was [Cu₂(C₉H₆O₂N)₄(H₂O)₂]·2H₂O. The binding ability of ICA-Cu to calf thymus DNA (CT-DNA) was examined by fluorescence spectrometry and the viscosity method. The results indicated that, upon the addition of increasing amounts of CT-DNA, the excitation and emission intensity of ICA-Cu decreased obviously and the excitation spectra shifted towards a long wavelength. ICA-Cu could displace ethidium bromide (EB) from the EB-DNA system, making the fluorescence intensity of the EB-DNA system decrease sharply; the quenching constant K SV value was 3.99 × 10⁴ M -1 . The emission intensity of the ICA-Cu-DNA system was nearly constant, along with the addition of Na⁺ in a series of concentrations. The fluorescence of the complex could be protected after the complex interacted with DNA. A viscosity measurement further supported the result that the ICA-Cu complex may interact with DNA in an intercalative binding mode. The antioxidant activities of ICA-Cu were evaluated by a 2,2-diphenyl-1-picrylhydrazyl (DPPH) assay, a hydroxyl radical (OH) scavenging assay, and a 2,2'-azino-bis(3-ethylbenzothiazoline-6-sulphonic acid (ABTS) assay. The ICA-Cu exhibited the highest inhibitory effects on the ABTS radical (94% inhibition at 60 µM), followed by OH and DPPH radicals (the degrees of inhibition being 71% and 56%, respectively). The in vitro cytotoxicity activity of ICA-Cu against two human breast cancer cell lines, MDA-MB-231 and MCF-7, was investigated by 3-[4,5-dimethyltiazol2-yl]-2.5-diphenyl-tetrazolium bromide (MTT) assay and cellular morphological analysis. The results showed that, upon increasing the concentration of ICA-Cu, an increase was observed in growth-inhibitory activity and the inhibition percentage were greater than 90% at 20 µM in both cell

  3. Theoretical investigation of the reaction mechanism for the phosphate diester hydrolysis using an asymmetric dinuclear metal complex as a biomimetic model of the purple acid phosphatase enzyme. (United States)

    Ferreira, Dalva E C; De Almeida, Wagner B; Neves, Ademir; Rocha, Willian R


    In this work we have applied quantum mechanical calculations, at the density functional theory level, to investigate the phosphate diester hydrolysis promoted by a cationic heterodinuclear Fe(III)...Zn(II) complex that mimics the structural and functional properties of the purple acid phosphatase (PAP) enzymes. The hydrolysis of the dimethyl phosphate diester was investigated in the gas phase and in solution by means of the continuum PCM model, using the B3LYP hybrid exchange-correlation functional. Our computed results showed that the hydrolysis of the dimethyl phosphate ester takes place in two steps. The first step corresponds to a slow P-O bond formation through nucleophilic attack of the coordinated (Fe(III))-OH group. The second step consists of a proton transfer process followed by the release of a methanol molecule. The first step is rate determining with activation free energy of 12.3 kcal mol(-1), which is about 3 times lower than the activation free energy for the uncatalyzed reaction. We also show that the heterodinuclear site plays an important role favoring an associative mechanism for the phosphate diester hydrolysis, favoring the formation of a high energy intermediate phosphorane, and orienting the phosphate group to the nucleophilic attack.


    African Journals Online (AJOL)

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    Electrothermal IA 9200, Digital Melting Point Apparatus and elemental analyses were undertaken using a Flash EA ... the reaction mixture was kept in an ice bath. The stirring was continued for ca. ... of methanol and triethylamine and then 0.58 mmol of metal salt, dissolved in the same solvent, was added to the suspension.

  5. Enhanced reactivity of dinuclear Copper(I) acetylides in dipolar cycloadditions

    DEFF Research Database (Denmark)

    Ahlquist, Mårten Sten Gösta; Fokin, V.V.


    Dinuclear alkynyl copper(I) complexes exhibit superior reactivity toward organic azides compared to their monomeric analogues. DFT studies indicate that the second copper center facilitates the formation of the cupracycle in the rate-determining step and stabilizes the metallacycle intermediate...... itself. These findings support the experimentally determined rate law and shed light on the origin of high reactivity of the in situ generated copper acetylides....

  6. Synthesis, redox properties, and EPR spectroscopy of manganese(III) complexes of the ligand N,N-bis(2-hydroxybenzyl)-N'-2-hydroxybenzylidene-1,2-diaminoethane: formation of mononuclear, dinuclear, and even higher nuclearity complexes. (United States)

    Schmitt, Heimo; Lomoth, Reiner; Magnuson, Ann; Park, Jonathan; Fryxelius, Jacob; Kritikos, Mikael; Mårtensson, Jerker; Hammarström, Leif; Sun, Licheng; Akermark, Björn


    The synthesis and characterization of the title trisphenolate ligand are described. From its reaction with manganese(III) three complexes were isolated. The crystal structures revealed one pentacoordinate monomer and two similar dimers with different solvents of crystallization. In the dimers the metal ions are hexacoordinate and connected through bridging of two phenolates. A combination of electrochemistry and EPR spectroscopy showed that, in acetonitrile, the isolated batches were all identical and mainly monomeric, indicating that the mononuclear complex is in equilibrium with the dimer and perhaps also with complexes of higher nuclearity, as suggested by the detection of both the trimer and the tetramer by electrospray ionization mass spectrometry (ESI-MS). The successful use of the monomer batch as an epoxidation catalyst indicated that a high-valent manganese-oxo species can be formed, although it is probably short-lived. This is also suggested by EPR studies of the species formed by electrochemical oxidation of the complex. Upon one-electron oxidation, a manganese(IV) species was formed, which was at least partly converted to another species containing a phenoxy radical.

  7. Design of dinuclear manganese cofactors for bacterial reaction centers. (United States)

    Olson, Tien L; Espiritu, Eduardo; Edwardraja, Selvakumar; Simmons, Chad R; Williams, JoAnn C; Ghirlanda, Giovanna; Allen, James P


    A compelling target for the design of electron transfer proteins with novel cofactors is to create a model for the oxygen-evolving complex, a Mn4Ca cluster, of photosystem II. A mononuclear Mn cofactor can be added to the bacterial reaction center, but the addition of multiple metal centers is constrained by the native protein architecture. Alternatively, metal centers can be incorporated into artificial proteins. Designs for the addition of dinuclear metal centers to four-helix bundles resulted in three artificial proteins with ligands for one, two, or three dinuclear metal centers able to bind Mn. The three-dimensional structure determined by X-ray crystallography of one of the Mn-proteins confirmed the design features and revealed details concerning coordination of the Mn center. Electron transfer between these artificial Mn-proteins and bacterial reaction centers was investigated using optical spectroscopy. After formation of a light-induced, charge-separated state, the experiments showed that the Mn-proteins can donate an electron to the oxidized bacteriochlorophyll dimer of modified reaction centers, with the Mn-proteins having additional metal centers being more effective at this electron transfer reaction. Modeling of the structure of the Mn-protein docked to the reaction center showed that the artificial protein likely binds on the periplasmic surface similarly to cytochrome c2, the natural secondary donor. Combining reaction centers with exogenous artificial proteins provides the opportunity to create ligands and investigate the influence of inhomogeneous protein environments on multinuclear redox-active metal centers. This article is part of a Special Issue entitled Biodesign for Bioenergetics--the design and engineering of electronic transfer cofactors, proteins and protein networks, edited by Ronald L. Koder and J.L. Ross Anderson. Copyright © 2015 Elsevier B.V. All rights reserved.

  8. Copolymerisation of Propylene Oxide and Carbon Dioxide by Dinuclear Cobalt Porphyrins

    KAUST Repository

    Anderson, Carly E.


    Two dinuclear cobalt porphyrins comprising different structural tethering motifs at the porphyrin periphery were synthesised, along with a representative mononuclear cobalt porphyrin, and their catalytic activities tested towards carbon dioxide-propylene oxide copolymerisation in the presence of bis(triphenylphosphoranyl)ammonium chloride cocatalyst. The catalytic activities of the mononuclear and the bis-para-tethered dinuclear cobalt porphyrin with selective formation of poly(propylene carbonate) are largely comparable, showing no benefit of dinuclearity in contrast to the case of cobalt salen complexes and suggesting that polymer growth proceeds exclusively from one metal centre. The alternative bis-ortho-tethered porphyrin demonstrated considerably reduced activity, with dominant formation of cyclic propylene carbonate, as a result of hindered substrate approach at the metal centre. Time-resolved UV/Vis spectroscopic studies suggested a general intolerance of the cobalt(III) porphyrin catalysts towards the copolymerisation conditions in the absence of carbon dioxide pressure, leading to catalytically inactive cobalt(II) species. In the presence of carbon dioxide, the bis-ortho-tethered catalyst showed the fastest deactivation, which is related to an unfavourable steric arrangement of the linker fragment, as was also confirmed by NMR spectroscopic measurements. © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  9. Syntheses, structures and properties of two dinuclear mercury(II ...

    Indian Academy of Sciences (India)

    Syntheses, structures and properties of two dinuclear mercury(II) iodide compounds containing tetradentate tripodal amine/pentadentate. N-donor Schiff base: Control of molecular and crystalline architectures by varying ligand matrices. SUBHASIS ROYa, SOUMI CHATTOPADHYAYa, SOMNATH CHOUBEYa,. KISHALAY ...

  10. Collective dynamics of a dinuclear system

    Energy Technology Data Exchange (ETDEWEB)

    Mshelia, E.D. [Department of Theoretical Physics, National Mathematical Centre, Abuja (Nigeria); Scheid, W. [Institut fuer Theoretische Physik, Justus-Liebig-Universitaet, Giessen (Germany)


    There are theoretical and experimental evidences that show that the cluster model, consisting of a dinuclear system, is capable of explaining several features of deformed heavy nuclei. Examples are the fusion to super-heavy nuclei and the nuclear-structure effects arising from parity splitting in alternating rotational parity bands, especially of the actinide nuclei. The model developed by Shneidman et al. has been able to explain the parity splitting in the actinides using the cluster model in which oscillations in mass asymmetry and relative motion were considered. On the other hand, Hess and Greiner developed a model for nuclear molecules in which the degrees of freedom of butterfly, belly-dancer-type motions, {gamma}- and {beta}-vibrations of individual nuclei were incorporated. The purpose of this work is to extend the model of Shneidman et al. to include some of the degrees of freedom in the work of Hess et al. and, in addition, to consider nuclear molecular rotations and the coupling of these degrees of freedom among themselves, arising from mass asymmetry. (orig.)

  11. Glycine and metformin as new counter ions for mono and dinuclear vanadium(V)-dipicolinic acid complexes based on the insulin-enhancing anions: Synthesis, spectroscopic characterization and crystal structure (United States)

    Ghasemi, Fatemeh; Rezvani, Ali Reza; Ghasemi, Khaled; Graiff, Claudia


    Complexes [VO(dipic) (H2O)2]·2H2O (1), [H2Met][V2O4(dipic)2] (2) and [HGly][VO2(dipic)] (3), where H2dipic = 2,6-pyridinedicarboxylic acid, Met = Metformin (N,N-dimethylbiguanide) and Gly = glycine, were synthesized. The three complexes were characterized by elemental analysis, FTIR, 1H and 13C NMR, and UV-Vis spectroscopy. Solid-state structures of (2) and (3) were determined by single-crystal X-ray diffraction analysis. The coordination geometry around the vanadium atoms in 2 is octahedral, while the coordination geometry in 3 is between trigonal bipyramidal and squared pyramidal. In the binuclear complex 2 and mononuclear complex 3, metformin and glycine are diprotonated and monoprotonated respectively, and act as a counter ion. The redox behavior of the complexes was also investigated by cyclic voltammetry.

  12. Deprotonation induced ligand-to-metal electron transfer: Synthesis of a mixed-valence Rh(-I,I) dinuclear compound and its reaction with dioxygen

    NARCIS (Netherlands)

    Tejel, C.; Ciriano, M.A.; del Río, M.P.; van den Bruele, F.J.; Hetterscheid, D.G.H.; Tsichlis i Spithas, N.; de Bruin, B.


    Treatment of bis(2-picolyl)amine (bpa) with [{Rh(nbd)(mu-OMe))(2)] leads to unexpected and unique redox asymmetric dinuclear Rh-I, Rh+I complex [{Rh(ndb)}(2)(bpa-2H)] (2) with a pi-coordinating imine bound to a tetrahedral low valent rhodate(-I). Mono-oxygenation of the deprotonated bpa ligand in 2


    Directory of Open Access Journals (Sweden)

    Masahiro Mikuriya


    Full Text Available Dinuclear nickel(II complex, [Ni2{O2CC(CH33}4(OH2{HO2CC(CH33}4] (1, was synthesized and characterized by elemental analysis, IR and UV-Vis-NIR spectroscopy, and temperature dependence of magnetic susceptibilities (4.5—300 K. Single-crystal X-ray crystallography revealed a dinuclear core with µ-aqua and di-µ-pivalato bridges having monodentate pivalato and monodentate pivalic acid molecules. Magnetic data analysis showed a ferromagnetic interactions between the two nickel atoms with g = 2.251, J = 2.78 cm−1, D = 3.75 cm–1, and tip = 184 x 10–6 cm3 mol–1; g = 2.253, J = 2.73 cm−1, D = –3.26 cm–1, and tip = 176 x 10–6 cm3 mol–1.

  14. Syntheses, structures and properties of two dinuclear mercury (II ...

    Indian Academy of Sciences (India)

    Home; Journals; Journal of Chemical Sciences; Volume 126; Issue 3. Syntheses, structures and properties of two dinuclear mercury(II) iodide compounds containing tetradentate tripodal amine/pentadentate N-donor Schiff base: Control of molecular and crystalline architectures by varying ligand matrices. Subhasis Roy ...

  15. Two hybrids based on Keggin polyoxometalates and dinuclear ...

    Indian Academy of Sciences (India)



    Oct 13, 2017 ... paste electrode possesses high catalytic efficiency and selectivity towards reduction of H2O2, and thus 1 has potential to detect H2O2. Keywords. Polyoxometalate; Keggin; dinuclear copper; electrocatalysis. 1. Introduction. Polyoxometalates (POMs),1–5 transition metal oxide clusters of d0 or d1 metal ions ...

  16. Tetraaqua-1kappa4O-bis(epsilon -caprolactam-1kappa O)-mu-cyano-1:2kappa 2N:C-pentacyano-2kappa 5C-iron(III)yttrium(III), a novel cyano-bridged dinuclear complex. (United States)

    Zhou, Bei Chuan; Kou, Hui Zhong; He, Yi; Xiong, Ming; Wang, Ru Ji; Li, Yadong


    Using caprolactam as a ligand, the novel title cyano-bridged yttrium(III)-ferricyanide complex, [Y(caprolactam)(2)(H(2)O)(4)Fe(CN)(6)] or [FeY(CN)(6)(C(6)H(11)NO)(2)(H(2)O)(4)], has been synthesized and structurally characterized. The Y atom is seven-coordinate and has approximately pentagonal-bipyramidal stereochemistry, with water molecules occupying apical positions. Of the five ligands in equatorial positions, one is the N-bound bridging cyano group, and flanking this are two O-bound caprolactam moieties, which are markedly inclined towards the bridged ferricyanide moiety such that they partially envelop it. Water molecules occupy the remaining two equatorial positions. The Y-N-C-Fe-C-N sequence of atoms lies on a crystallographic twofold axis and is therefore perfectly linear, which has not been observed previously in cyano-bridged bimetallic complexes.

  17. The DFT Calculations of Structures and EPR Parameters for the Dinuclear Paddle-Wheel Copper(II) Complex {Cu2(μ2-O2CCH3)4}(OCNH2CH3) as Powder or Single Crystal (United States)

    Ding, Chang-Chun; Wu, Shao-Yi; Xu, Yong-Qiang; Zhang, Li-Juan; Zhang, Zhi-Hong; Zhu, Qin-Sheng; Wu, Ming-He; Teng, Bao-Hua


    Density functional theory (DFT) calculations of the structures and the Cu2+ g factors (gx, gy and gz ) and hyperfine coupling tensor A (Ax , Ay and Az ) were performed for the paddle-wheel (PW)-type binuclear copper(II) complex {Cu2(μ2-O2CCH3)4}(OCNH2CH3) powder and single crystal. Calculations were carried out with the ORCA software using the functionals BHandHlyp, B3P86 and B3LYP with five different basis sets: 6-311g, 6-311g(d,p), VTZ, def-2 and def2-TZVP. Results were tested by the MPAD analysis to find the most suitable functional and basis sets. The electronic structure and covalency between copper and oxygen were investigated by the electron localisation function and the localised orbital locator as well as the Mayer bond order for the [CuO5] group. The optical spectra were theoretically calculated by the time-dependent DFT module and plotted by the Multiwfn program for the [CuO5] group and reasonably associated with the local structure in the vicinity of the central ion copper. In addition, the interactions between the OCNH2CH3, NH3 and H2O molecules and the uncoordinated PW copper(II) complex were studied, and the corresponding adsorption energies, the frequency shifts with respect to the free molecules and the changes of the Cu-Cu distances were calculated and compared with the relevant systems.

  18. Crystal Structure and Characterization of the Dinuclear Cd(II Complex [Cd(H2O2(ο-HOC6H4COO2]2

    Directory of Open Access Journals (Sweden)

    Pusu Zhao


    Full Text Available The structure of a new binuclear cadmium (II complex, [Cd(H2O2(Sal2]2 (Sal= salicylate, has been determined by X-ray crystallography. It was also characterized byelemental analysis, its IR spectrum and thermogravimetric-differential scanningcalorimetry (TG-DSC. It crystallizes in the monoclinic system, space group P21/c, withlattice parameters a = 15.742(3 å, b = 12.451(3 å, c = 7.7225(15 å, β = 96.07(3o andZ = 4. Two cadmium (II ions are bridged by two μ2-carboxy oxygen atoms. Eachcadmium atom lies in a distorted capped octahedron coordination geometry. The thermalgravimetry (TG data indicate that there are four discrete decomposition steps with twoendothermic peaks and one exothermic peak. The final thermal decomposition product isCdO.

  19. A New Manganese Dinuclear Complex with Phenolate Ligands and a Single Unsupported Oxo Bridge. Storage of Two Positive Charges within Less than 500 mV. Relevance to Photosynthesis. (United States)

    Horner, Olivier; Anxolabéhère-Mallart, Elodie; Charlot, Marie-France; Tchertanov, Lyuba; Guilhem, Jean; Mattioli, Tony A.; Boussac, Alain; Girerd, Jean-Jacques


    The compound [Mn(III)(2)OL(2)](ClO(4))(2).2.23CHCl(3).0.65CH(2)Cl(2) where L(-) is the monoanionic N,N-bis(2-pyridylmethyl)-N'-salicyliden-1,2-diaminoethane ligand, has been synthesized. The complex dication [Mn(III)(2)OL(2)](2+) contains a linear Mn(III)-O-Mn(III) unit with a Mn-Mn distance of 3.516 Å. The pentadentate ligand L(-) wraps around the Mn(III) ion. Electrochemically, it is possible to prepare the one electron oxidized trication [Mn(2)OL(2)](3+) which crystallizes as [Mn(2)OL(2)](ClO(4))(2.37)(PF(6))(0.63).1.5CH(3)CN. The complex trication [Mn(2)OL(2)](3+) contains a Mn(III)-O-Mn(IV) unit with a Mn-Mn distance of 3.524 Å and a Mn-O-Mn angle of 178.7(2) degrees. The contraction of the coordination sphere around the Mn(IV) is clearly observed. The [Mn(2)OL(2)](2+) dication possesses a S = 0 electronic ground state with J = -216 cm(-)(1) (H = -JS(1)().S(2)()), whereas the [Mn(2)OL(2)](3+) trication shows a S = (1)/(2) ground state with J = -353 cm(-)(1). The UV-visible spectrum of [Mn(2)OL(2)](3+) exhibits an intense absorption band (epsilon = 3040 M(-)(1) cm(-)(1)) centered at 570 nm assigned to a phenolate --> Mn(IV) charge-transfer transition. The potentials of the redox couples determined by cyclic voltammetry are E degrees ([Mn(2)OL(2)](3+)/[Mn(2)OL(2)](2+)) = 0.54 V/saturated calomel electrode (SCE) and E degrees ([Mn(2)OL(2)](4+)/[Mn(2)OL(2)](3+)) = 0.99 V/SCE. Upon oxidation at 1.3 V/SCE, the band at 570 nm shifts to 710 nm (epsilon = 2500 M(-)(1) cm(-)(1)) and a well-defined band appears at 400 nm which suggests the formation of a phenoxyl radical. The [Mn(2)OL(2)](3+)( )()complex exhibits a 18-line X-band electron paramagnetic resonance (EPR) spectrum which has been simulated with rhombic tensors |A(1)(x)()| = 160 x 10(-)(4) cm(-)(1); |A(1)(y)()| = 130 x 10(-)(4) cm(-)(1); |A(1)(z)()| = 91 x 10(-)(4) cm(-)(1); |A(2)(x)()| = 62 x 10(-)(4) cm(-)(1); |A(2)(y)()| = 59 x 10(-)(4) cm(-)(1); |A(2)(z)()| = 62 x 10(-)(4) cm(-)(1) and g(x)() = 2.006; g

  20. A dinuclear manganese(II) complex with the [Mn(2)(mu-O(2)CCH(3))(3)](+) core: synthesis, structure, characterization, electroinduced transformation, and catalase-like activity. (United States)

    Romero, Isabel; Dubois, Lionel; Collomb, Marie-Noëlle; Deronzier, Alain; Latour, Jean-Marc; Pécaut, Jacques


    Reactions of Mn(II)(PF(6))(2) and Mn(II)(O(2)CCH(3))(2).4H(2)O with the tridentate facially capping ligand N,N-bis(2-pyridylmethyl)ethylamine (bpea) in ethanol solutions afforded the mononuclear [Mn(II)(bpea)](PF(6))(2) (1) and the new binuclear [Mn(2)(II,II)(mu-O(2)CCH(3))(3)(bpea)(2)](PF(6)) (2) manganese(II) compounds, respectively. Both 1 and 2 were characterized by X-ray crystallographic studies. Complex 1 crystallizes in the monoclinic system, space group P2(1)/n, with a = 11.9288(7) A, b = 22.5424(13) A, c =13.0773(7) A, alpha = 90 degrees, beta = 100.5780(10 degrees ), gamma = 90 degrees, and Z = 4. Crystals of complex 2 are orthorhombic, space group C222(1), with a = 12.5686(16) A, b = 14.4059(16) A, c = 22.515(3) A, alpha = 90 degrees, beta = 90 degrees, gamma = 90 degrees, and Z = 4. The three acetates bridge the two Mn(II) centers in a mu(1,3) syn-syn mode, with a Mn-Mn separation of 3.915 A. A detailed study of the electrochemical behavior of 1 and 2 in CH(3)CN medium has been made. Successive controlled potential oxidations at 0.6 and 0.9 V vs Ag/Ag(+) for a 10 mM solution of 2 allowed the selective and nearly quantitative formation of [Mn(III)(2)(mu-O)(mu-O(2)CCH(3))(2)(bpea)(2)](2+) (3) and [Mn(IV)(2)(mu-O)(2)(mu-O(2)CCH(3))(bpea)(2)](3+) (4), respectively. These results have shown that each substitution of an acetate group by an oxo group is induced by a two-electron oxidation of the corresponding dimanganese complexes. Similar transformations have been obtained if 2 is formed in situ either by direct mixing of Mn(2+) cations, bpea ligand, and CH(3)COO(-) anions with a 1:1:3 stoichiometry or by mixing of 1 and CH(3)COO(-) with a 1:1.5 stoichiometry. Associated electrochemical back-transformations were investigated. 2, 3, and the dimanganese [Mn(III)Mn(IV)(mu-O)(2)(mu-O(2)CCH(3))(bpea)(2)](2+) analogue (5) were also studied for their ability to disproportionate hydrogen peroxide. 2 is far more active compared to 3 and 5. The EPR monitoring of the

  1. Application of the dinuclear system model to fission process


    Andreev A. V.; Shneidman T. M.; Ventura A.


    A theoretical evaluation of the collective excitation spectra of nucleus at large deformations is possible within the framework of the dinuclear system model, which treats the wave function of the fissioning nucleus as a superposition of a mononucleus configuration and two-cluster configurations in a dynamical way, permitting exchange of nucleons between clusters. In this work the method of calculation of the potential energy and the collective spectrum of fissioning nucleus at scission point...

  2. New discrete and polymeric supramolecular architectures derived from dinuclear (bis-beta-diketonato)copper(II) metallocycles. (United States)

    Clegg, Jack K; Gloe, Karsten; Hayter, Michael J; Kataeva, Olga; Lindoy, Leonard F; Moubaraki, Boujemaa; McMurtrie, John C; Murray, Keith S; Schilter, David


    New examples of adducts between di- (and, in one instance, tetra-) functional nitrogen ligands and planar 'platform-like' dinuclear copper(II) complexes, [Cu2L2], incorporating the 1,3-aryl linked bis-beta-diketonato bridging ligand 1,1'-(1,3-phenylene)-bis(4,4-dimethylpentane-1,3-dione) (H2L) have been synthesised. The X-ray structures of six adduct species are reported. The interaction of [Cu2(L)2] with the ditopic ligand aminopyrazine (apyz) yielded the sandwich-like tetranuclear species [(Cu2L2(apyz))2]. A variable-temperature magnetochemical investigation of this product indicated weak antiferromagnetic coupling between the (five-coordinate) copper centres, mediated by the 2-aminopyrazine linkers. An analogous structure, [(Cu2L2(dabco))2] (dabco=1,4-diazabicyclo[2.2.2]octane), was generated when dabco was substituted for aminopyrazine while use of 4,4'-dipyridyl sulfide (dps) and 4,4'-(1,3-xylylene)-bis(3,5-dimethylpyrazole) (xbp) as the ditopic 'spacer' ligands resulted in polymeric species of type [Cu2L2(dps)]n and [Cu2L2(xbp)]n, respectively. These latter species exist as one-dimensional chain structures in which copper(II) centres on different dinuclear platforms are linked in a 'zigzag' fashion. In contrast, with 2,2'-dipyridylamine (dpa) a discrete complex of type [Cu2L2(dpa)2] formed in which one potential pyridyl donor from each 2,2'-dipyridylamine ligand remains uncoordinated. The use of the potentially quadruply-bridging hexamethylenetetramine (hmt) ligand as the linker unit was found to give rise to an unusual two-dimensional polymeric motif of type [(Cu2(L2)2)3(hmt)2]n. The product takes the form of a (6,3) network, incorporating triply bridging hexamethylenetetramine units.

  3. Application of the dinuclear system model to fission process (United States)

    Andreev, A. V.; Shneidman, T. M.; Ventura, A.


    A theoretical evaluation of the collective excitation spectra of nucleus at large deformations is possible within the framework of the dinuclear system model, which treats the wave function of the fissioning nucleus as a superposition of a mononucleus configuration and two-cluster configurations in a dynamical way, permitting exchange of nucleons between clusters. In this work the method of calculation of the potential energy and the collective spectrum of fissioning nucleus at scission point is presented. Combining the DNS model calculations and the statistical model of fission we calculate the mass, total kinetic energy, and angular distribution of fission fragments for the neutron-induced fission of 239Pu.

  4. Application of the dinuclear system model to fission process

    Directory of Open Access Journals (Sweden)

    Andreev A. V.


    Full Text Available A theoretical evaluation of the collective excitation spectra of nucleus at large deformations is possible within the framework of the dinuclear system model, which treats the wave function of the fissioning nucleus as a superposition of a mononucleus configuration and two-cluster configurations in a dynamical way, permitting exchange of nucleons between clusters. In this work the method of calculation of the potential energy and the collective spectrum of fissioning nucleus at scission point is presented. Combining the DNS model calculations and the statistical model of fission we calculate the mass, total kinetic energy, and angular distribution of fission fragments for the neutron–induced fission of 239Pu.

  5. New cobalt-mediated radical polymerization (CMRP of methyl methacrylate initiated by two single-component dinuclear β-diketone cobalt (II catalysts.

    Directory of Open Access Journals (Sweden)

    Feng Bao

    Full Text Available Two dinuclear cobalt complexes based on bis-diketonate ligands (ligand 1: 3,3'-(1,3-phenylenebis(1-phenylpropane-1,3-dione; ligand 2: 3,3'-(1,4-phenylenebis(1-phenylpropane-1,3-dione were successfully synthesized. The two neutral catalysts all showed satisfactory activities in the cobalt-mediated radical polymerization (CMRP of methyl methacrylate (MMA with the common initiator of azodiisobutyronitrile (AIBN. The resulting polymerizations have all of the characteristics of a living polymerization and displayed linear semilogarithmic kinetic plots, a linear correlation between the number-average molecular weight and the monomer conversion, and low polydispersities. Mono- or dicomponent low polydispersity polymers could be obtained by using the two dinuclear catalysts under proper reaction conditions. All these improvements facilitate the implementation of the acrylate CMRP and open the door to the scale-up of the syntheses and applications of the multicomponent low polydispersity polymers.

  6. Elucidation of Dual Magnetic Relaxation Processes in Dinuclear Dysprosium(III) Phthalocyaninato Triple-Decker Single-Molecule Magnets Depending on the Octacoordination Geometry. (United States)

    Katoh, Keiichi; Aizawa, Yu; Morita, Takaumi; Breedlove, Brian K; Yamashita, Masahiro


    When applying single-molecule magnets (SMMs) to spintronic devices, control of the quantum tunneling of the magnetization (QTM) as well as a spin-lattice interactions are important. Attempts have been made to use not only coordination geometry but also magnetic interactions between SMMs as an exchange bias. In this manuscript, dinuclear dysprosium(III) (Dy III ) SMMs with the same octacoordination geometry undergo dual magnetic relaxation processes at low temperature. In the dinuclear Dy III phthalocyaninato (Pc 2- ) triple-decker type complex [(Pc)Dy(ooPc)Dy(Pc)] (1) (ooPc 2- =2,3,9,10,16,17,23,24-octakis(octyloxy)phthalocyaninato) with a square-antiprismatic (SAP) geometry, the ground state is divided by the Zeeman effect, and level intersection occurs when a magnetic field is applied. Due to the ground state properties of 1, since the Zeeman diagram where the levels intersect in an H dc of 2500 Oe, two kinds of QTM and direct processes occur. However, dinuclear Dy III -Pc systems with C 4 geometry, which have a twist angle (ϕ) of less than 45° do not undergo dual magnetic relaxation processes. From magnetic field and temperature dependences, the dual magnetic relaxation processes were clarified. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  7. Cleavage of a RNA analog containing uridine by a bifunctional dinuclear Zn(II) catalyst. (United States)

    Rossiter, Clifford S; Mathews, Ryan A; del Mundo, Imee Marie A; Morrow, Janet R


    The macrocyclic ligand, 1,4-bis((1-oxa-4,7,10-triazacyclododecan-7-yl)methyl)benzene (L1) is prepared. L1 binds two Zn(II) ions at neutral pH to form Zn(2)(L1) as studied by using pH-potentiometric titrations. Zn(2)(L1) binds two uridines at pH 7.0, I=0.100M (NaCl) and the mononuclear analog Zn(L2) (L2=1-oxa-4,7,10-triazacyclododecane) binds a single uridine; dissociation constants for both complexes are in the millimolar range. Both complexes promote the cleavage of a simple RNA analog lacking a nucleobase (HpPNP=2-hydroxypropyl-4-nitrophenylphosphate), and a uridine containing RNA analog UpPNP (uridine-3'-4-nitrophenylphosphate). Plots of the first-order rate constant for cleavage of HpPNP as a function of Zn(L2) concentration from 0.5mM to 20.0mM are linear, consistent with weak complexation to substrate K(d)>20mM. In contrast, first-order rate constants for cleavage of UpPNP by Zn(L2) or Zn(2)(L1) over similar concentration ranges exhibit a downward curvature, consistent with the formation of a complex between catalyst and UpPNP. Comparison of second-order rate constants (k(2)=k(cat)/K(d)) shows that the dinuclear complex Zn(2)(L1) is a better catalyst than Zn(L2) for both HpPNP and UpPNP cleavage.

  8. Quantum Refinement Does Not Support Dinuclear Copper Sites in Crystal Structures of Particulate Methane Monooxygenase. (United States)

    Cao, Lili; Caldararu, Octav; Rosenzweig, Amy C; Ryde, Ulf


    Particulate methane monooxygenase (pMMO) is one of the few enzymes that can activate methane. The metal content of this enzyme has been highly controversial, with suggestions of a dinuclear Fe site or mono-, di-, or trinuclear Cu sites. Crystal structures have shown a mono- or dinuclear Cu site, but the resolution was low and the geometry of the dinuclear site unusual. We have employed quantum refinement (crystallographic refinement enhanced with quantum-mechanical calculations) to improve the structure of the active site. We compared a number of different mono- and dinuclear geometries, in some cases enhanced with more protein ligands or one or two water molecules, to determine which structure fits two sets of crystallographic raw data best. In all cases, the best results were obtained with mononuclear Cu sites, occasionally with an extra water molecule. Thus, we conclude that there is no crystallographic support for a dinuclear Cu site in pMMO. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  9. Parent di-nuclear quasimolecular states as exotic resonant states

    International Nuclear Information System (INIS)

    Grama, N.; Grama, C.; ZamfirescuI, I.


    An approach to bound and resonant states in the scattering by a central potential gV(r) with a barrier, based on the global method for all S-matrix poles analysis is presented. The Riemann surface R g (l) over the g-plane, on which the pole function k=k l (g) is single-valued and analytic is constructed. This method provides a new quantum number n with topological significance: it is the label of the sheets of the Riemann surface. New classes of poles and resonant states (exotic) are identified and their properties are studied. One shows that the parent di-nuclear quasimolecular state is an exotic resonant state that corresponds to a S-matrix pole in the neighbourhood of an attractor in the k-plane in the case of a potential made of a well and a Coulomb barrier. The properties of the parent quasimolecular states (energies, widths, deviation from the linear dependence of the energy on l(l + 1), doorway character and criteria for observability) result naturally from general properties of the exotic resonant states. (authors)

  10. Dynamical restriction for a growing neck due to mass parameters in a dinuclear system

    Energy Technology Data Exchange (ETDEWEB)

    Adamian, G.G.; Antonenko, N.V.; Diaz-Torres, A.; Scheid, W


    Mass parameters for collective variables of a dinuclear system and strongly deformed mononucleus are microscopically formulated with the linear response theory making use of the width of single-particle states and the fluctuation-dissipation theorem. For the relative motion of the nuclei and for the degree of freedom describing the neck between the nuclei, we calculate mass parameters with basis states of the adiabatic and diabatic two-center shell model. Microscopic mass parameters are found larger than the ones obtained with the hydrodynamical model and give a strong hindrance for a melting of the dinuclear system along the internuclear distance into a compound system. Therefore, the dinuclear system lives long enough compared to the reaction time for fusion by nucleon transfer. Consequences of this effect for the complete fusion process are discussed.

  11. Dynamical restriction for a growing neck due to mass parameters in a dinuclear system (United States)

    Adamian, G. G.; Antonenko, N. V.; Diaz-Torres, A.; Scheid, W.


    Mass parameters for collective variables of a dinuclear system and strongly deformed mononucleus are microscopically formulated with the linear response theory making use of the width of single-particle states and the fluctuation-dissipation theorem. For the relative motion of the nuclei and for the degree of freedom describing the neck between the nuclei, we calculate mass parameters with basis states of the adiabatic and diabatic two-center shell model. Microscopic mass parameters are found larger than the ones obtained with the hydrodynamical model and give a strong hindrance for a melting of the dinuclear system along the internuclear distance into a compound system. Therefore, the dinuclear system lives long enough compared to the reaction time for fusion by nucleon transfer. Consequences of this effect for the complete fusion process are discussed.

  12. Electronic structures of ruthenium complexes encircling non ...

    Indian Academy of Sciences (India)

    Electronic structural forms of selected mononuclear and dinuclear ruthenium complexes encompassing redox non-innocent terminal as well as bridging ligands have been addressed. The sensitive valence and spin situations of the complexes have been established in the native and accessible redox states via detailed ...

  13. Description of light charged particle multiplicities in the framework of dinuclear system model

    Directory of Open Access Journals (Sweden)

    Antonenko N.V.


    Full Text Available In the framework of dinuclear system (DNS model we calculate the light charged particle (LCP multiplicities produced in fusion and quasifission reactions and their kinetic energy spectra. Calculations indicate that with increasing bombarding energy the ratio of LCP multiplicity from fragments MFF to corresponding LCP multiplicity from compound nucleus (CN MCN strongly increases.

  14. Dinuclear bis-beta-diketonato ligand derivatives of iron(III) and copper(II) and use of the latter as components for the assembly of extended metallo-supramolecular structures. (United States)

    Clegg, Jack K; Lindoy, Leonard F; McMurtrie, John C; Schilter, David


    A range of 1,3-aryl linked, bis-beta-diketone derivatives (LH2) has been employed to synthesise neutral bis(ligand), dinuclear complexes incorporating square-planar copper(II) and tris(ligand) dinuclear helical derivatives containing octahedral iron(III). The 1H NMR spectra of the free ligands contain singlet peaks at ca. 16.2 ppm, indicative of enolic protons, confirming that the (bis) enol tautomer is present in solution. An X-ray structure of a ligand from the series incorporating tert-butyl terminal substituents confirms that the same tautomer persists in the solid and that the relative orientation of the bis-beta-diketone fragments is such that the coordination vectors lie at approximately 120 degrees to each other. The planar, dinuclear copper complexes form 1 : 2 adducts with pyridine and 4-(dimethylamino)pyridine, confirmed by X-ray structures, that incorporate five-coordinate metal centres. Based on this behaviour, the prospect of linking copper centres in the dinuclear complexes using the difunctional heterocyclic bases, 4,4'-bipyridine, 4,4'-trans-azopyridine and pyrazine as co-ligands has been probed. However, 4,4'-bipyridine was observed to coordinate through only one of its heterocyclic nitrogen atoms in the solid state to form a 1 : 2 ([Cu2(L)2]: 4,4'-bipyridine) adduct, analogous to the structures obtained with the above mono-functional nitrogen bases. Nevertheless, an X-ray structure determination shows that the related difunctional base, 4,4'-trans-azopyridine, coordinates in a bridging fashion via both its heterocyclic nitrogen atoms on alternate sides of each planar [Cu2(L)2] unit to produce an infinite one dimensional metallo chain. In contrast, with pyrazine, a new neutral, discrete assembly of type [Cu4(L)4(pyrazine)2] is formed. The X-ray structure shows that two planar dinuclear complexes are linked by two pyrazine molecules in a sandwich arrangement such that the coordination environment of each copper ion is approximately square pyramidal

  15. Photo-catalytic oxidation of a di-nuclear manganese centre in an engineered bacterioferritin 'reaction centre'. (United States)

    Conlan, Brendon; Cox, Nicholas; Su, Ji-Hu; Hillier, Warwick; Messinger, Johannes; Lubitz, Wolfgang; Dutton, P Leslie; Wydrzynski, Tom


    Photosynthesis involves the conversion of light into chemical energy through a series of electron transfer reactions within membrane-bound pigment/protein complexes. The Photosystem II (PSII) complex in plants, algae and cyanobacteria catalyse the oxidation of water to molecular O2. The complexity of PSII has thus far limited attempts to chemically replicate its function. Here we introduce a reverse engineering approach to build a simple, light-driven photo-catalyst based on the organization and function of the donor side of the PSII reaction centre. We have used bacterioferritin (BFR) (cytochrome b1) from Escherichia coli as the protein scaffold since it has several, inherently useful design features for engineering light-driven electron transport. Among these are: (i.) a di-iron binding site; (ii.) a potentially redox-active tyrosine residue; and (iii.) the ability to dimerise and form an inter-protein heme binding pocket within electron tunnelling distance of the di-iron binding site. Upon replacing the heme with the photoactive zinc-chlorin e6 (ZnCe6) molecule and the di-iron binding site with two manganese ions, we show that the two Mn ions bind as a weakly coupled di-nuclear Mn2II,II centre, and that ZnCe6 binds in stoichiometric amounts of 1:2 with respect to the dimeric form of BFR. Upon illumination the bound ZnCe6 initiates electron transfer, followed by oxidation of the di-nuclear Mn centre possibly via one of the inherent tyrosine residues in the vicinity of the Mn cluster. The light dependent loss of the MnII EPR signals and the formation of low field parallel mode Mn EPR signals are attributed to the formation of MnIII species. The formation of the MnIII is concomitant with consumption of oxygen. Our model is the first artificial reaction centre developed for the photo-catalytic oxidation of a di-metal site within a protein matrix which potentially mimics water oxidation centre (WOC) photo-assembly.


    African Journals Online (AJOL)

    The molar conductance of 10-3 M solutions of the metal complexes ... conductivity cell. Room temperature magnetic susceptibilities of the powdered samples. {calibrant Hg[Co(SCN)4]} were measured using a Johnson Mattey scientific ..... 2 and 4) complexes and the dinuclear complex 3 are neutral and non-electrolyte [21].

  17. Ruthenium, osmium and rhodium complexes of polypyridyl ligands ...

    Indian Academy of Sciences (India)


    (L→M σdonation) is the predominant factor, rather than angular strain, that is responsible for metal-promoted reactivities. Electrochemical properties of all of these complexes have been investigated, Rh(III) complexes are excellent catalysts for electrocatalytic reduction of CO2, and dinuclear Ru(II) and Os(II) complexes ...

  18. Dynamical restriction for a growing neck due to mass parameters in a dinuclear system


    Adamian, G. G.; Antonenko, N. V.; Diaz-Torres, A.; Scheid, W.


    Mass parameters for collective variables of a dinuclear system and strongly deformed mononucleus are microscopically formulated with the linear response theory making use of the width of single particle states and the fluctuation-dissipation theorem. For the relative motion of the nuclei and for the degree of freedom describing the neck between the nuclei, we calculate mass parameters with basis states of the adiabatic and diabatic two-center shell model. Microscopical mass parameters are fou...

  19. The DFT calculations of structures and EPR parameters for the dinuclear paddle-wheel copper(II) complex {Cu_2(μ_2-O_2CCH_3)_4}(OCNH{sub 2}CH{sub 3}) as powder or single crystal

    Energy Technology Data Exchange (ETDEWEB)

    Ding, Chang-Chun; Wu, Shao-Yi; Xu, Yong-Qiang; Zhang, Li-Juan; Zhang, Zhi-Hong; Zhu, Qin-Sheng; Wu, Ming-He; Teng, Bao-Hua [Univ. of Electronic Science and Technology of China, Chengdu (China). School of Physical Electronics


    Density functional theory (DFT) calculations of the structures and the Cu{sup 2+} g factors (g{sub x}, g{sub y} and g{sub z}) and hyperfine coupling tensor A (A{sub x}, A{sub y} and A{sub z}) were performed for the paddle-wheel (PW)-type binuclear copper(II) complex {Cu_2(μ_2-O_2CCH_3)_4}(OCNH{sub 2}CH{sub 3}) powder and single crystal. Calculations were carried out with the ORCA software using the functionals BHandHlyp, B3P86 and B3LYP with five different basis sets: 6-311g, 6-311g(d,p), VTZ, def-2 and def2-TZVP. Results were tested by the MPAD analysis to find the most suitable functional and basis sets. The electronic structure and covalency between copper and oxygen were investigated by the electron localisation function and the localised orbital locator as well as the Mayer bond order for the [CuO{sub 5}] group. The optical spectra were theoretically calculated by the time-dependent DFT module and plotted by the Multiwfn program for the [CuO{sub 5}] group and reasonably associated with the local structure in the vicinity of the central ion copper. In addition, the interactions between the OCNH{sub 2}CH{sub 3}, NH{sub 3} and H{sub 2}O molecules and the uncoordinated PW copper(II) complex were studied, and the corresponding adsorption energies, the frequency shifts with respect to the free molecules and the changes of the Cu-Cu distances were calculated and compared with the relevant systems.

  20. Two 3D supramolecular frameworks assembled from the dinuclear ...

    Indian Academy of Sciences (India)

    Home; Journals; Journal of Chemical Sciences; Volume 126; Issue 4. Two 3D ... Volume 126 Issue 4 July 2014 pp 1153-1161 ... Two new complexes of Mn(II) and Zn(II) have been synthesized using a mixed ligand system and characterized by IR spectroscopy, elemental analysis, single crystal x-ray diffraction and variable ...

  1. Two hybrids based on Keggin polyoxometalates and dinuclear ...

    Indian Academy of Sciences (India)



    Oct 13, 2017 ... per(II) complex as a model for dopamine β-hydroxylase. J. Chem. Soc. Dalton Trans. 1395. 48. Xi X D, Wang G, Liu B F and Dong S J 1995 Elec- trochemical behavior of Bis(2: 17-arsenotungstate) lan- thanates and their electrocatalytic reduction for Nitrite. Electrochim. Acta 40 1025. 49. Fay N, Dempsey E ...

  2. Iron and cobalt complexes of 4, 4, 9, 9-tetramethyl-5, 8 ...

    Indian Academy of Sciences (India)

    Complexes 1 and 2 react with dioxygen at ambient condition to form the corresponding hydroxo- or oxo-bridged dinuclear cobalt(III) or iron(III) complexes. On the other hand, the iron(III)-catecholate complex (3) activate dioxygen to undergo oxidative C-C bond cleavage of catechol. The selective formation of extradiol ...

  3. Cu(II) complexes of glyco-imino-aromatic conjugates in DNA binding ...

    Indian Academy of Sciences (India)

    Metal complexes have shown toxicity to the HeLa and MCF–7 cell lines. Morphological studies, western blot and FACS analysis are suggestive of apoptotic cell death induced by the metal complexes. Di-nuclear copper complexes were found to be better as compared to the mononuclear ones in binding, plasmid cleavage ...

  4. Silver(I) based dinuclear metallacycles with free thiophenyl ...

    Indian Academy of Sciences (India)

    sample. The 1H NMR spectrum of metallacycle 2 was largely similar to that of the free L2 (figure S2). The composition of the complexes was further supported by ESI-MS data (figures S8-S15). The molecular ion peaks for metallacycles 2 and 3 were observed at m/z = 1369.0192 and 1225.0182, respectively, which confirm.

  5. Synthesis and structural studies of Cp{sup *} rhodium and Cp{sup *} iridium complexes of picolinic hydrazine ligand

    Energy Technology Data Exchange (ETDEWEB)

    Palepu, Narasinga Rao; Kollipara, Mohan Rao [Centre for Advanced Studies in Chemistry, North-Eastern Hill University, Shillong (India); Kaminsky Werner [Dept. of Chemistry, University of Washington, Seattle (United States)


    A series of Cp{sup *}Rh and Cp{sup *}Ir complexes of picolinic hydrazine ligand are synthesized and characterized. Picolinic hydrazine has yielded only dinuclear complexes in the case of rhodium metal whereas both mono and dinuclear complexes with iridium metal. Iridium complexes are formed as quaternary salts by the migration of the N–H proton onto the adjacent amine group of the hydrazine after binding to the metal. Picolinic hydrazine acts as nitrogen and oxygen donor ligand in the form of bi and tetradentate bonding modes.

  6. Mechanistic insights into toxic effects of a benzotriazolate-bridged dinuclear platinum(II) compound in tumor cells

    Czech Academy of Sciences Publication Activity Database

    Olivová, R.; Štěpánková, Jana; Muchová, T.; Novohradský, V.; Nováková, Olga; Vrána, Oldřich; Kašpárková, Jana; Brabec, Viktor


    Roč. 393, DEC (2012), s. 204-211 ISSN 0020-1693 R&D Projects: GA ČR(CZ) GAP301/10/0598 Institutional research plan: CEZ:AV0Z50040702 Institutional support: RVO:68081707 Keywords : Dinuclear platinum * Antitumor * DNA binding Subject RIV: BO - Biophysics Impact factor: 1.687, year: 2012

  7. Study of half-sandwich mono and dinuclear complexes of platinum ...

    Indian Academy of Sciences (India)

    Davies D L, -Duaij O A, Fawcett J, Giardiello M, Hilton. S T and Russell D R 2003 Dalton Trans. 4132. 30. Lalrempuia R, Carroll P J and Rao K M 2003 Polyhe- dron 22 605. 31. Davies D L, Fawcett J, Krafczyk R and Russell D R 1997. J. Organomet. Chem. 545–546 581. 32. Govindaswamy P, Mozharivskyj Y A and Rao K M ...

  8. Mechanistic insights into antitumor effects of new dinuclear cis PtII complexes containing aromatic linkers

    Czech Academy of Sciences Publication Activity Database

    Zerzánková, Lenka; Kostrhunová, Hana; Vojtíšková, Marie; Nováková, Olga; Suchánková, T.; Lin, M.; Guo, Z.; Kašpárková, Jana; Brabec, Viktor


    Roč. 80, č. 3 (2010), s. 344-351 ISSN 0006-2952 R&D Projects: GA MŠk(CZ) LC06030; GA MŠk(CZ) ME08017; GA MŠk(CZ) ME10066; GA MŠk(CZ) OC08003; GA AV ČR(CZ) IAA400040803; GA ČR(CZ) GD301/09/H004; GA ČR(CZ) GAP301/10/0598 Grant - others:GA MŠk(CZ) OC09018; GA AV ČR(CZ) KAN200200651 Program:KA Institutional research plan: CEZ:AV0Z50040507; CEZ:AV0Z50040702 Keywords : DNA * platinum * cancer Subject RIV: BO - Biophysics Impact factor: 4.889, year: 2010

  9. A novel dinuclear schiff base copper complex as an efficient and ...

    Indian Academy of Sciences (India)

    IR, UV-visible spectra, mass spectrometry, and powder x-ray diffraction (PXRD). ... pounds is a vital prerequisite in the pharmaceutical, fragrance, flavoring and fine chemicals industries.1,2. These reactions are performed at present using ...

  10. A novel dinuclear schiff base copper complex as an efficient and ...

    Indian Academy of Sciences (India)

    98166 Messina, Italy e-mail: MS received 22 November 2014; revised 17 April 2015; accepted 21 April 2015. Abstract. An environmentally friendly protocol is described for an economic, practical laboratory-scale oxi- dation of primary and secondary alcohols to aldehydes and ketones, using a ...

  11. Ligand Self-Sorting and Nonlinear Effects in Dinuclear Asymmetric Hydrogenation: Complexity in Catalysis

    NARCIS (Netherlands)

    Terrade, F.G.; Lutz, M.; Reek, J.N.H.


    Nature has been a source of inspiration for scientists as billion years of evolution have resulted in magnificent examples of how processes can be controlled efficiently. In the field of supramolecular catalysis, enzymes have been the major source of inspiration. As such, many synthetic systems have

  12. A novel dinuclear schiff base copper complex as an efficient and ...

    Indian Academy of Sciences (India)

    Home; Journals; Journal of Chemical Sciences; Volume 127; Issue 7 ... Schiff base; Oxidation; DFT calculations; Peroxide; Green chemistry ... the efficiency, selectivity and stability of this new catalyst in the oxidation of alcohols in ethanol and tert-butyl hydroperoxide (tBuOOH) as a green solvent and oxidant, respectively.

  13. Dinuclear ruthenium(II) and/or osmium(II) complexes of bipyridyl ...

    Indian Academy of Sciences (India)


    Discipline of Silicates and Catalysis, Central Salt & Marine Chemicals. Research Institute, G.B. Marg, Bhavnagar 364 002, India. Supramolecular Ru(II) and Os(II) polypyridyl chemistry gained considerable interest due to their rich electrochemical and photophysical properties and potential use in a variety of energy/electron ...

  14. Variable coordinating activity of sulfur in silver(I) complexes with ...

    Indian Academy of Sciences (India)

    Variable coordinating activity of sulfur in silver(I) complexes with thiophene based N. 1. -substituted thiosemicarbazones: First case of thiopheneyl-thione sulfur bridging in a dinuclear complex. REKHA SHARMAa,b, TARLOK S LOBANAa,∗, MANVIR KAURa, NEERAJ THATHAIa,. GEETA HUNDALa, JERRY P JASINSKIc ...

  15. Metal-Organic Framework of Lanthanoid Dinuclear Clusters Undergoes Slow Magnetic Relaxation

    Directory of Open Access Journals (Sweden)

    Hikaru Iwami


    Full Text Available Lanthanoid metal-organic frameworks (Ln-MOFs can adopt a variety of new structures due to the large coordination numbers of Ln metal ions, and Ln-MOFs are expected to show new luminescence and magnetic properties due to the localized f electrons. In particular, some Ln metal ions, such as Dy(III and Tb(III ions, work as isolated quantum magnets when they have magnetic anisotropy. In this work, using 4,4′,4″-s-triazine-2,4,6-triyl-tribenzoic acid (H3TATB as a ligand, two new Ln-MOFs, [Dy(TATB(DMF2] (1 and [Tb(TATB(DMF2] (2, were obtained. The Ln-MOFs contain Ln dinuclear clusters as secondary building units, and 1 underwent slow magnetic relaxation similar to single-molecule magnets.

  16. Reactivity of uranium(IV) bridged chalcogenido complexes UIV–E–UIV (E = S, Se) with elemental sulfur and selenium: synthesis of polychalcogenido-bridged uranium complexes


    Franke, Sebastian M.; Heinemann, Frank W.; Meyer, Karsten


    We report the syntheses, electronic properties, and molecular structures of a series of polychalcogenido-bridged dinuclear uranium species. These complexes are supported by the sterically encumbering but highly flexible, single N-anchored tris(aryloxide) chelator (AdArO)3N3−. Reaction of an appropriate uranium precursor, either the U(III) starting material, [((AdArO)3N)U(DME)], or the dinuclear mono-chalcogenido-bridged uranium(IV/IV) compounds [{((AdArO)3N)U(DME)}2(μ-E)] (E = S, Se), with el...

  17. Comparison of the Magnetic Anisotropy and Spin Relaxation Phenomenon of Dinuclear Terbium(III) Phthalocyaninato Single-Molecule Magnets Using the Geometric Spin Arrangement. (United States)

    Morita, Takaumi; Damjanović, Marko; Katoh, Keiichi; Kitagawa, Yasutaka; Yasuda, Nobuhiro; Lan, Yanhua; Wernsdorfer, Wolfgang; Breedlove, Brian K; Enders, Markus; Yamashita, Masahiro


    Herein we report the synthesis and characterization of a dinuclear Tb III single-molecule magnet (SMM) with two [TbPc 2 ] 0 units connected via a fused-phthalocyaninato ligand. The stable and robust complex [(obPc)Tb(Fused-Pc)Tb(obPc)] (1) was characterized by using synchrotron radiation measurements and other spectroscopic techniques (ESI-MS, FT-IR, UV). The magnetic couplings between the Tb III ions and the two π radicals present in 1 were explored by means of density functional theory (DFT). Direct and alternating current magnetic susceptibility measurements were conducted on magnetically diluted and nondiluted samples of 1, indicating this compound to be an SMM with improved properties compared to those of the well-known [TbPc 2 ] -/0/+ and the axially symmetric dinuclear Tb III phthalocyaninato triple-decker complex (Tb 2 (obPc) 3 ). Assuming that the probability of quantum tunneling of the magnetization (QTM) occurring in one TbPc 2 unit is P QTM , the probability of QTM simultaneously occurring in 1 is P QTM 2 , meaning that QTM is effectively suppressed. Furthermore, nondiluted samples of 1 underwent slow magnetic relaxation times (τ ≈ 1000 s at 0.1 K), and the blocking temperature (T B ) was determined to be ca. 16 K with an energy barrier for spin reversal (U eff ) of 588 cm -1 (847 K) due to D 4d geometry and weak inter- and intramolecular magnetic interactions as an exchange bias (H bias ), reducing QTM. Four hyperfine steps were observed by micro-SQUID measurement. Furthermore, solution NMR measurements (one-dimensional, two-dimensional, and dynamic) were done on 1, which led to the determination of the high rotation barrier (83 ± 10 kJ/mol) of the obPc ligand. A comparison with previously reported Tb III triple-decker compounds shows that ambient temperature NMR measurements can indicate improvements in the design of coordination environments for SMMs. A large U eff causes strong uniaxial magnetic anisotropy in 1, leading to a χ ax value (1.39

  18. Copper(II) and zinc(II) dinuclear enzymes model compounds: The nature of the metal ion in the biological function (United States)

    Ferraresso, L. G.; de Arruda, E. G. R.; de Moraes, T. P. L.; Fazzi, R. B.; Da Costa Ferreira, A. M.; Abbehausen, C.


    First series transition metals are used abundantly by nature to perform catalytic transformations of several substrates. Furthermore, the cooperative activity of two proximal metal ions is common and represents a highly efficient catalytic system in living organisms. In this work three dinuclear μ-phenolate bridged metal complexes were prepared with copper(II) and zinc(II), resulting in a ZnZn, CuCu and CuZn with the ligand 2-ethylaminodimethylamino phenol (saldman) as model compounds of superoxide dismutase (CuCu and CuZn) and metallo-β-lactamases (ZnZn). Metals are coordinated in a μ-phenolate bridged symmetric system. Cu(II) presents a more distorted structure, while zinc is very symmetric. For this reason, [CuCu(saldman)] shows higher water solubility and also higher lability of the bridge. The antioxidant and hydrolytic beta-lactamase-like activity of the complexes were evaluated. The lability of the bridge seems to be important for the antioxidant activity and is suggested to because of [CuCu(saldman)] presents a lower antioxidant capacity than [CuZn(saldman)], which showed to present a more stable bridge in solution. The hydrolytic activity of the bimetallic complexes was assayed using nitrocefin as substrate and showed [ZnZn(saldman)] as a better catalyst than the Cu(II) analog. The series demonstrates the importance of the nature of the metal center for the biological function and how the reactivity of the model complex can be modulated by coordination chemistry.

  19. Water oxidation catalyzed by molecular di- and nonanuclear Fe complexes: importance of a proper ligand framework. (United States)

    Das, Biswanath; Lee, Bao-Lin; Karlsson, Erik A; Åkermark, Torbjörn; Shatskiy, Andrey; Demeshko, Serhiy; Liao, Rong-Zhen; Laine, Tanja M; Haukka, Matti; Zeglio, Erica; Abdel-Magied, Ahmed F; Siegbahn, Per E M; Meyer, Franc; Kärkäs, Markus D; Johnston, Eric V; Nordlander, Ebbe; Åkermark, Björn


    The synthesis of two molecular iron complexes, a dinuclear iron(iii,iii) complex and a nonanuclear iron complex, based on the dinucleating ligand 2,2'-(2-hydroxy-5-methyl-1,3-phenylene)bis(1H-benzo[d]imidazole-4-carboxylic acid) is described. The two iron complexes were found to drive the oxidation of water by the one-electron oxidant [Ru(bpy)3](3+).

  20. Stable iridium dinuclear heterogeneous catalysts supported on metal-oxide substrate for solar water oxidation. (United States)

    Zhao, Yanyan; Yang, Ke R; Wang, Zechao; Yan, Xingxu; Cao, Sufeng; Ye, Yifan; Dong, Qi; Zhang, Xizi; Thorne, James E; Jin, Lei; Materna, Kelly L; Trimpalis, Antonios; Bai, Hongye; Fakra, Sirine C; Zhong, Xiaoyan; Wang, Peng; Pan, Xiaoqing; Guo, Jinghua; Flytzani-Stephanopoulos, Maria; Brudvig, Gary W; Batista, Victor S; Wang, Dunwei


    Atomically dispersed catalysts refer to substrate-supported heterogeneous catalysts featuring one or a few active metal atoms that are separated from one another. They represent an important class of materials ranging from single-atom catalysts (SACs) and nanoparticles (NPs). While SACs and NPs have been extensively reported, catalysts featuring a few atoms with well-defined structures are poorly studied. The difficulty in synthesizing such structures has been a critical challenge. Here we report a facile photochemical method that produces catalytic centers consisting of two Ir metal cations, bridged by O and stably bound to a support. Direct evidence unambiguously supporting the dinuclear nature of the catalysts anchored on α-Fe 2 O 3 is obtained by aberration-corrected scanning transmission electron microscopy (AC-STEM). Experimental and computational results further reveal that the threefold hollow binding sites on the OH-terminated surface of α-Fe 2 O 3 anchor the catalysts to provide outstanding stability against detachment or aggregation. The resulting catalysts exhibit high activities toward H 2 O photooxidation.

  1. Reinvestigating 2,5-di(pyridin-2-yl)pyrazine ruthenium complexes : Selective deuteration and Raman spectroscopy as tools to probe ground and excited-state electronic structure in homo- and heterobimetallic complexes

    NARCIS (Netherlands)

    Schulz, M.; Hirschmann, J.; Draksharapu, A.; Singh Bindra, G.; Soman, S.; Paul, A.; Groarke, R.; T. Pryce, M.; Rau, S.; R. Browne, W.; Vos, J.


    The mono- (1) and dinuclear (2) ruthenium(II) bis(2,2'-bipyridine) complexes of 2,5-di(pyridin-2-yl)pyrazine (2,5-dpp), for which the UV/Vis absorption and emission as well as electrochemical properties have been described earlier, are reinvestigated here by resonance, surface enhanced and transient

  2. The multi-layered structure of Dps with a novel di-nuclear ferroxidase center. (United States)

    Ren, Bin; Tibbelin, Gudrun; Kajino, Tsutomu; Asami, Osamu; Ladenstein, Rudolf


    The crystallization of cellular components represents a unique survival strategy for bacterial cells under stressed conditions. A highly ordered, layered structure is often formed in such a process, which may involve one or more than one type of bio-macromolecules. The main advantage of biocrystallization has been attributed to the fact that it is a physical process and thus is independent of energy consumption. Dps is a protein that crystallizes to form a multi-layered structure in starved cells in order to protect DNA against oxidative damage and other detrimental factors. The multi-layered crystal structure of a Dps protein from Bacillus brevis has been revealed for the first time at atomic resolution in the absence of DNA. Inspection of the structure provides the first direct evidence for the existence of a di-nuclear ferroxidase center, which possesses unique features among all the di-iron proteins identified so far. It constitutes the structural basis for the ferroxidase activity of Dps in the crystalline state as well as in solution. This finding proves that the enzymatic process of detoxification of metal ions, which may cause severe oxidative damage to DNA, is the other important aspect of the defense mechanism performed by Dps. In the multi-layered structure, Dps dodecamers are organized in a highly ordered manner. They adopt the classic form of hexagonal packing in each layer of the structure. Such arrangement results in reinforced structural features that would facilitate the attraction and absorption of metal ions from the environment. The highly ordered layered structure may provide an ideal basis for the accommodation of DNA between the layers so that it can be isolated and protected from harmful factors under stress conditions.

  3. 2,3-Bis(1-methylimidazol-2-yl)quinoxaline (bmiq), a new ligand with decoupled electron transfer and metal coordination sites: the very different redox behaviour of isoelectronic complexes with [PtCl2] and [AuCl2](+)

    Czech Academy of Sciences Publication Activity Database

    Bulak, E.; Varnali, T.; Schwederski, B.; Sarkar, B.; Hartenbach, I.; Fiedler, Jan; Kaim, W.


    Roč. 40, č. 12 (2011), s. 2757-2763 ISSN 1477-9226 R&D Projects: GA MŠk LD11086; GA MŠk(CZ) LD11082 Institutional research plan: CEZ:AV0Z40400503 Keywords : plainum(II) diimine complexes * polypyridyl ligands * dinuclear complexes Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 3.838, year: 2011

  4. Butterfly Deformation Modes in a Photoexcited Pyrazolate-Bridged Pt Complex Measured by Time-Resolved X-Ray Scattering in Solution

    DEFF Research Database (Denmark)

    Haldrup, Kristoffer; Dohn, Asmus Ougaard; Shelby, Megan L.


    Pyrazolate-bridged dinuclear Pt(II) complexes represent a series of molecules with tunable absorption and emission properties that can be directly modulated by structural factors, such as the Pt-Pt distance. However, direct experimental information regarding the structure of the emissive triplet ...

  5. A novel homobimetallic nickel complex for the asymmetric direct Mannich reaction of imines: a practical method on a multi-gram scale. (United States)

    Zhang, Shixiong; Deng, Ping; Zhou, Jing; Liu, Mouxiong; Liang, Guojuan; Xiong, Yan; Zhou, Hui


    A novel dinuclear Ni complex has been developed for the direct Mannich reaction of malonates with N-tosyl aryl imines with a low catalyst loading (0.1-0.05 mol%) on a preparative scale (5-50 mmol). The structure of the active species was verified via control experiments, ESI-HRMS, and DFT calculations.

  6. Iron and cobalt complexes of 4,4,9,9-tetramethyl-5,8-diazadodecane ...

    Indian Academy of Sciences (India)

    and a biomimetic iron(III)-catecholate complex [FeIII(HL)(DBC)] (3) of a dioxime ligand (H2L = 4,4,9,9- tetramethyl-5,8-diazadodecane-2,11-dione dioxime and DBCH2 = 3,5-di-tert-butylcatechol) were synthesized and characterized. X-ray single-crystal structures of both the dinuclear complexes exhibit an out-of-plane oxi-.

  7. A stable gold(i)-enyne species obtained by alkyne carboauration in a complex rearrangement. (United States)

    Cámara, Jéssica; Blanco, M Carmen; Laguna, Antonio; Naumov, Panče; Gimeno, M Concepción


    An unprecedented tetranuclear gold derivative with unusual gold-enyne moieties is prepared by a mild and neat rearrangement of a dinuclear gold complex with a bridging bis(diphenylphosphino)alkyne and terminal alkynyl ligands. The complex originates as a consequence of an intramolecular addition of the AuC[triple bond, length as m-dash]CTol fragment to the internal diphosphine triple bond Ph 2 PC[triple bond, length as m-dash]CPPh 2 . The crystal structure of the tetranuclear complex shows a dinuclear metallacycle with a very short AuAu bond interaction and bridging phosphino-enyne ligands. This disposition clearly stabilises the elusive vinyl gold species omnipresent as intermediates in gold-catalysed reactions.

  8. Correspondence of RuIIIRuII and RuIVRuIII Mixed Valent States in a Small Dinuclear Complex

    Czech Academy of Sciences Publication Activity Database

    Agarwala, H.; Scherer, T. M.; Maji, S.; Mondal, T. K.; Mobin, S. M.; Fiedler, Jan; Urbanos, F. A.; Jimenez-Aparicio, R.; Kaim, W.; Lahiri, G. K.


    Roč. 18, č. 18 (2012), s. 5667-5675 ISSN 0947-6539 R&D Projects: GA MŠk(CZ) ME10124 Institutional research plan: CEZ:AV0Z40400503 Keywords : density functional calculations * EPR spectroscopy * magnetic properties Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 5.831, year: 2012

  9. Spin and isospin fluctuations in heavy ion collisions and their dependence upon the shape of the dinuclear complex

    International Nuclear Information System (INIS)

    Moretto, L.G.


    The relevance of higher multipoles of giant isovector modes in the charge distribution of deep inelastic fragments is discussed and found to depend strongly on mass asymmetry. The sources of angular momentum fluctuations are investigated. Quantal effects are considered as well as effects arising from non-equilibrium and equilibrium statistical fluctuations. A model based upon equilibrium statistical mechanics is considered in detail, and used to predict both 2nd moments of the angular momentum distributions and the angular momentum misalignment. Analytical expressions are derived to calculate the angular distributions of sequentially emitted particles, fission fragments, as well as gamma rays in terms of the angular momentum misalignment. Recent data on the angular distributions of sequential alphas, fission and gamma rays are analyzed in terms of the model. 29 figures, 1 table

  10. Unique structural properties of DNA interstrand cross-links formed by a new antitumor dinuclear Pt(II) complex

    Czech Academy of Sciences Publication Activity Database

    Hrabina, O.; Kašpárková, J.; Suchánková, Tereza; Novohradský, Vojtěch; Guo, Z.; Brabec, Viktor


    Roč. 9, č. 5 (2017), s. 494-500 ISSN 1756-5901 Institutional support: RVO:68081707 Keywords : cisplatin-modified dna * nucleotide excision-repair * hmg domain proteins Subject RIV: CE - Biochemistry OBOR OECD: Biochemistry and molecular biology Impact factor: 3.975, year: 2016

  11. Ground- and excited-state electronic structure of an emissive pyrazine-bridged Ruthenium(II) dinuclear complex

    NARCIS (Netherlands)

    Browne, Wesley R.; O’Boyle, Noel M.; Henry, William; Guckian, Adrian L.; Horn, Sabine; Fett, Thomas; O’Connor, Christine M.; Duati, Marco; Cola, Luisa De; Coates, Colin G.; Ronayne, Kate L.; McGarvey, John J.; Vos, Johannes G.


    The synthesis, characterization, and electrochemical, photophysical, and photochemical properties of the binuclear compounds [(Ru(H-8-bpy)(2))(2)((Metr)(2)Pz)](PF6)(2) (1) and [(Ru(D-8-bpy)(2))(2)((Metr)(2)Pz)](PF6)(2) (2), where bpy is 2,2'-bipyridine and H-2(Metr)(2)Pz is the planar ligand

  12. Spin and isospin fluctuations in heavy ion collisions and their dependence upon the shape of the dinuclear complex

    Energy Technology Data Exchange (ETDEWEB)

    Moretto, L.G.


    The relevance of higher multipoles of giant isovector modes in the charge distribution of deep inelastic fragments is discussed and found to depend strongly on mass asymmetry. The sources of angular momentum fluctuations are investigated. Quantal effects are considered as well as effects arising from non-equilibrium and equilibrium statistical fluctuations. A model based upon equilibrium statistical mechanics is considered in detail, and used to predict both 2nd moments of the angular momentum distributions and the angular momentum misalignment. Analytical expressions are derived to calculate the angular distributions of sequentially emitted particles, fission fragments, as well as gamma rays in terms of the angular momentum misalignment. Recent data on the angular distributions of sequential alphas, fission and gamma rays are analyzed in terms of the model. 29 figures, 1 table.

  13. DNA conformation and repair of polymeric natural DNA damaged by antitumor azolato-bridged dinuclear PtII complex

    Czech Academy of Sciences Publication Activity Database

    Mlčoušková, J.; Kašpárková, Jana; Suchánková, Tereza; Komeda, S.; Brabec, Viktor


    Roč. 114, SEP 2012 (2012), s. 15-23 ISSN 0162-0134 R&D Projects: GA ČR(CZ) GAP301/10/0598; GA ČR(CZ) GD301/09/H004 Institutional research plan: CEZ:AV0Z50040702 Keywords : DNA * platinum * DNA repair Subject RIV: BO - Biophysics Impact factor: 3.197, year: 2012

  14. Dual triggering of DNA binding and fluorescence via photoactivation of a dinuclear ruthenium(II) arene complex

    Czech Academy of Sciences Publication Activity Database

    Magennis, S.W.; Habtemariam, A.; Nováková, Olga; Henry, J.B.; Meier, S.; Parsons, S.; Oswald, D.H.; Brabec, Viktor; Sadler, P.J.


    Roč. 46, č. 12 (2007), s. 5059-5068 ISSN 0020-1669 R&D Projects: GA ČR(CZ) GA203/06/1239; GA ČR(CZ) GA305/05/2030; GA AV ČR(CZ) 1QS500040581; GA AV ČR(CZ) KAN200200651 Institutional research plan: CEZ:AV0Z50040507; CEZ:AV0Z50040702 Keywords : DNA * ruthenium * fluorescence Subject RIV: BO - Biophysics Impact factor: 4.123, year: 2007

  15. Synthesis and characterization of dinuclear complexes containing the Fe(III)-F...(H2O)M(II) motif

    DEFF Research Database (Denmark)

    Ghiladi, M; Jensen, K.B.; Jiang, Jianzhong


    the general formulation [(bpbp)Fe(F)2M(H2O)n]-[BF4]2, M=Zn or Cu, n=1; M=Co or Fe, n=2. Two terminal fluoride ions are bound to the iron(III) ion and one or two water ligands to the adjacent divalent metal ion. The fluoride ligands are derived from the hydrolysis of tetrafluoroborate. In the crystal structure...

  16. Biologically relevant mono- and di-nuclear manganese II/III/IV complexes of mononegative pentadentate ligands

    DEFF Research Database (Denmark)

    Baffert, Carole; Collomb, Marie-Nöelle; Deronzier, Alain


    were characterised by UV-visible spectroscopy, ESI mass spectrometry and cyclic voltammetry. In addition, III-IV and II-III species were electrochemically generated. Thus the new mononegative pentadentate ligand systems display significant flexibility in the range of Mn oxidation states and species...

  17. 2,2/-Dipyridylketone (dpk) as Ancillary Acceptor and Reporter Ligand in Complexes [(dpk)(Cl)Ru(.mu.-tppz)Ru(Cl)(dpk)]n+ where tppz = 2,3,5,6-Tetrakis(2-pyridyl)pyrazine

    Czech Academy of Sciences Publication Activity Database

    Ghumaan, S.; Sarkar, B.; Chanda, N.; Sieger, M.; Fiedler, Jan; Kaim, W.; Lahiri, G. K.


    Roč. 45, č. 19 (2006), s. 7955-7961 ISSN 0020-1669 R&D Projects: GA MŠk OC 139; GA MŠk OC 140 Institutional research plan: CEZ:AV0Z40400503 Keywords : dinuclear Ru complexes * Creutz-Taube ion * mixed -valence system Subject RIV: CG - Electrochemistry Impact factor: 3.911, year: 2006

  18. X-ray absorption spectroscopic studies of the dinuclear iron center in methane monooxygenase and the sulfure and chlorine centers in photographic materials

    Energy Technology Data Exchange (ETDEWEB)

    DeWitt, Jane G. [Stanford Univ., CA (United States)


    The dinuclear iron center of the hydroxylase component of soluble methane monooxygenase (MMO) from Methylococcus capsulatus and Methylosinus trichosporiwn has been studied by X-ray absorption spectroscopy. Analysis of the Fe K-edge EXAFS revealed that the first shell coordination of the Fe(HI)Fe(IH) oxidized state of the hydroxylase from M. capsulatus consists of approximately 6 N and 0 atoms at an average distance of 2.04 Å. The Fe-Fe distance was determined to be 3.4 Å. No evidence for the presence of a short oxo bridge in the iron center of the oxidized hydroxylase was found, suggesting that the active site of MMO is significantly different from the active sites of the dinuclear iron proteins hemery and ribonucleotide reductase. In addition, the results of the first shell fits suggest that there are more oxygen than nitrogen donor ligands.

  19. X-ray absorption spectroscopic studies of the dinuclear iron center in methane monooxygenase and the sulfure and chlorine centers in photographic materials

    Energy Technology Data Exchange (ETDEWEB)

    DeWitt, J.G.


    The dinuclear iron center of the hydroxylase component of soluble methane monooxygenase (MMO) from Methylococcus capsulatus and Methylosinus trichosporiwn has been studied by X-ray absorption spectroscopy. Analysis of the Fe K-edge EXAFS revealed that the first shell coordination of the Fe(HI)Fe(IH) oxidized state of the hydroxylase from M. capsulatus consists of approximately 6 N and 0 atoms at an average distance of 2.04 [Angstrom]. The Fe-Fe distance was determined to be 3.4 [Angstrom]. No evidence for the presence of a short oxo bridge in the iron center of the oxidized hydroxylase was found, suggesting that the active site of MMO is significantly different from the active sites of the dinuclear iron proteins hemery and ribonucleotide reductase. In addition, the results of the first shell fits suggest that there are more oxygen than nitrogen donor ligands.

  20. Bimetallic Nickel/Ruthenium Catalysts Synthesized by Atomic Layer Deposition for Low-Temperature Direct Methanol Solid Oxide Fuel Cells. (United States)

    Jeong, Heonjae; Kim, Jun Woo; Park, Joonsuk; An, Jihwan; Lee, Tonghun; Prinz, Fritz B; Shim, Joon Hyung


    Nickel and ruthenium bimetallic catalysts were heterogeneously synthesized via atomic layer deposition (ALD) for use as the anode of direct methanol solid oxide fuel cells (DMSOFCs) operating in a low-temperature range. The presence of highly dispersed ALD Ru islands over a porous Ni mesh was confirmed, and the Ni/ALD Ru anode microstructure was observed. Fuel cell tests were conducted using Ni-only and Ni/ALD Ru anodes with approximately 350 μm thick gadolinium-doped ceria electrolytes and platinum cathodes. The performance of fuel cells was assessed using pure methanol at operating temperatures of 300-400 °C. Micromorphological changes of the anode after cell operation were investigated, and the content of adsorbed carbon on the anode side of the operated samples was measured. The difference in the maximum power density between samples utilizing Ni/ALD Ru and Pt/ALD Ru, the latter being the best catalyst for direct methanol fuel cells, was observed to be less than 7% at 300 °C and 30% at 350 °C. The improved electrochemical activity of the Ni/ALD Ru anode compared to that of the Ni-only anode, along with the reduction of the number of catalytically active sites due to agglomeration of Ni and carbon formation on the Ni surface as compared to Pt, explains this decent performance.

  1. Structures and metal-binding properties of Helicobacter pylori neutrophil-activating protein with a di-nuclear ferroxidase center. (United States)

    Yokoyama, Hideshi; Fujii, Satoshi


    Helicobacter pylori causes severe diseases, such as chronic gastritis, peptic ulcers, and stomach cancers. H. pylori neutrophil-activating protein (HP-NAP) is an iron storage protein that forms a dodecameric shell, promotes the adhesion of neutrophils to endothelial cells, and induces the production of reactive oxygen radicals. HP-NAP belongs to the DNA-protecting proteins under starved conditions (Dps) family, which has significant structural similarities to the dodecameric ferritin family. The crystal structures of the apo form and metal-ion bound forms, such as iron, zinc, and cadmium, of HP-NAP have been determined. This review focused on the structures and metal-binding properties of HP-NAP. These metal ions bind at the di-nuclear ferroxidase center (FOC) by different coordinating patterns. In comparison with the apo structure, metal loading causes a series of conformational changes in conserved residues among HP-NAP and Dps proteins (Trp26, Asp52, and Glu56) at the FOC. HP-NAP forms a spherical dodecamer with 23 symmetry including two kinds of pores. Metal ions have been identified around one of the pores; therefore, the negatively-charged pore is suitable for the passage of metal ions.

  2. The dapE-encoded N-succinyl-l,l-diaminopimelic acid desuccinylase from Haemophilus influenzae is a dinuclear metallohydrolase. (United States)

    Cosper, Nathaniel J; Bienvenue, David L; Shokes, Jacob E; Gilner, Danuta M; Tsukamoto, Takashi; Scott, Robert A; Holz, Richard C


    The Zn K-edge extended X-ray absorption fine structure (EXAFS) spectra, of the dapE-encoded N-succinyl-l,l-diaminopimelic acid desuccinylase (DapE) from Haemophilus influenzae have been recorded in the presence of one or two equivalents of Zn(II) (i.e. [Zn_(DapE)] and [ZnZn(DapE)]). The Fourier transforms of the Zn EXAFS are dominated by a peak at ca. 2.0 A, which can be fit for both [Zn_(DapE)] and [ZnZn(DapE)], assuming ca. 5 (N,O) scatterers at 1.96 and 1.98 A, respectively. A second-shell feature at ca. 3.34 A appears in the [ZnZn(DapE)] EXAFS spectrum but is significantly diminished in [Zn_(DapE)]. These data show that DapE contains a dinuclear Zn(II) active site. Since no X-ray crystallographic data are available for any DapE enzyme, these data provide the first glimpse at the active site of DapE enzymes. In addition, the EXAFS data for DapE incubated with two competitive inhibitors, 2-carboxyethylphosphonic acid and 5-mercaptopentanoic acid, are also presented.

  3. Hydride Reactivity of Ni-II-X-Ni-II Entities : Mixed-Valent Hydrido Complexes and Reversible Metal Reduction

    NARCIS (Netherlands)

    Gehring, Henrike; Metzinger, Ramona; Herwig, Christian; Intemann, Julia; Harder, Sjoerd; Limberg, Christian

    After the lithiation of PYR-H2 (PYR2-=[{NC(Me)C(H)C(Me)NC6H3(iPr)2}2(C5H3N)]2-), which is the precursor of an expanded beta-diketiminato ligand system with two binding pockets, its reaction with [NiBr2(dme)] led to a dinuclear nickel(II)bromide complex, [(PYR)Ni(mu-Br)NiBr] (1). The bridging bromide

  4. Unsymmetrical dizinc complexes as models for the active sites of phosphohydrolases. (United States)

    Jarenmark, Martin; Csapó, Edit; Singh, Jyoti; Wöckel, Simone; Farkas, Etelka; Meyer, Franc; Haukka, Matti; Nordlander, Ebbe


    The unsymmetrical dinucleating ligand 2-(N-isopropyl-N-((2-pyridyl)methyl)aminomethyl)-6-(N-(carboxylmethyl)-N-((2-pyridyl)methyl)aminomethyl)-4-methylphenol (IPCPMP or L) has been synthesized to model the active site environment of dinuclear metallohydrolases. It has been isolated as the hexafluorophosphate salt H(4)IPCPMP(PF(6))(2) x 2 H(2)O (H(4)L), which has been structurally characterized, and has been used to form two different Zn(II) complexes, [{Zn(2)(IPCPMP)(OAc)}(2)][PF(6)](2) (2) and [{Zn(2)(IPCPMP)(Piv)}(2)][PF(6)](2) (3) (OAc = acetate; Piv = pivalate). The crystal structures of and show that they consist of tetranuclear complexes with very similar structures. Infrared spectroscopy and mass spectrometry indicate that the tetranuclear complexes dissociate into dinuclear complexes in solution. Potentiometric studies of the Zn(II):IPCPMP system in aqueous solution reveal that a mononuclear complex is surprisingly stable at low pH, even at a 2:1 Zn(II):L ratio, but a dinuclear complex dominates at high pH and transforms into a dihydroxido complex by a cooperative deprotonation of two, probably terminally coordinated, water molecules. A kinetic investigation indicates that one of these hydroxides is the active nucleophile in the hydrolysis of bis(2,4-dinitrophenyl)phosphate (BDNPP) enhanced by complex 2, and mechanistic proposals are presented for this reaction as well as the previously reported transesterification of 2-hydroxypropyl p-nitrophenyl phosphate (HPNP) promoted by Zn(II) complexes of IPCPMP.

  5. A comparison of DNA binding profiles of dinuclear platinum compounds with polyamine linkers and the trinuclear platinum phase II clinical agent BBR3464

    Czech Academy of Sciences Publication Activity Database

    McGregor, T. D.; Hegmans, A.; Kašpárková, Jana; Neplechová, Kamila; Nováková, Olga; Peňázová, Hana; Vrána, Oldřich; Brabec, Viktor; Farrel, N.


    Roč. 7, 4/5 (2002), s. 397-404 ISSN 0949-8257 R&D Projects: GA ČR GA305/99/0695; GA ČR GA301/00/0556; GA ČR GA301/98/P231; GA AV ČR IAA5004101; GA AV ČR IAA7004805 Institutional research plan: CEZ:AV0Z5004920 Keywords : unwinding * dinuclear platinum * hydrogen bonding Subject RIV: BO - Biophysics Impact factor: 3.911, year: 2002

  6. Antimony(V) and Bismuth(V) Complexes of Lapachol: Synthesis, Crystal Structure and Cytotoxic Activity


    Cynthia Demicheli; Carlos A. de Simone; Frédéric Frézard; Eufrânio N. da Silva Júnior; Cláudio L. Donnici; Elene C. Pereira-Maia; Ludmila G. de Oliveira; Meiriane M. Silva; Flávia C. S. de Paula


    Antimony(V) and bismuth(V) complexes of lapachol have been synthesized by the reaction of Ph3SbCl2 or Ph3BiCl2 with lapachol (Lp) and characterized by several physicochemical techniques such as IR, and NMR spectroscopy and X-ray crystallography. The compounds contain six-coordinated antimony and bismuth atoms. The antimony(V) complex is a monomeric derivative, (Lp)(Ph3Sb)OH, and the bismuth(V) complex is a dinuclear compound bridged by an oxygen atom, (Lp)2(Ph3Bi)2O. Both compounds inhibited ...

  7. RNA and DNA binding of inert oligonuclear ruthenium(II) complexes in live eukaryotic cells. (United States)

    Li, Xin; Gorle, Anil K; Ainsworth, Tracy D; Heimann, Kirsten; Woodward, Clifford E; Collins, J Grant; Keene, F Richard


    Confocal microscopy was used to study the intracellular localisation of a series of inert polypyridylruthenium(II) complexes with three eukaryotic cells lines - baby hamster kidney (BHK), human embryonic kidney (HEK-293) and liver carcinoma (Hep-G2). Co-staining experiments with the DNA-selective dye DAPI demonstrated that the di-, tri- and tetra-nuclear polypyridylruthenium(II) complexes that are linked by the bis[4(4'-methyl-2,2'-bipyridyl)]-1,12-dodecane bridging ligand ("bb12") showed a high degree of selectivity for the nucleus of the eukaryotic cells. Additional co-localisation experiments with the general nucleic acid stain SYTO 9 indicated that the ruthenium complexes showed a considerable preference for the RNA-rich nucleolus, rather than chromosomal DNA. No significant differences were observed in the intracellular localisation between the ΔΔ and ΛΛ enantiomers of the dinuclear complex. Cytotoxicity assays carried out over 72 hours indicated that the ruthenium complexes, particularly the tri- and tetra-nuclear species, were significantly toxic to the eukaryotic cells. However, when the activity of the least cytotoxic compound (the ΔΔ enantiomer of the dinuclear species) was determined over a 24 hour period, the results indicated that the ruthenium complex was approximately a 100-fold less toxic to liver and kidney cells than to Gram positive bacteria. Circular dichroism (CD) spectroscopy was used to examine the effect of the ΔΔ and ΛΛ enantiomers of the dinuclear complex on the solution conformations of RNA and DNA. The CD experiments indicated that the RNA maintained the A-type conformation, and the DNA the B-type structure, upon binding by the ruthenium complexes.

  8. Studies of the polynuclear complexes of labile ligands of vitamin B1 and Zn(II), Cd(II) and Hg(II) with Fe(III)

    International Nuclear Information System (INIS)

    Ojo, J.O.


    The ligands (complex salts) of vitamin B/sub 1/ (H Vit.) and the chlorides of Zn, Cd and Hg with the general formula, [H Vit]/sup +2/ [MCl/sub 4/]/sup -2/ were prepared and their interactions with iron (III) investigated. It was found that the complex salts of Zn and Cd produced the dinuclear complexes and that of mercury produced a complex without the thiamine moiety. The possible reason for the absence of a Hg complex similar to those of Zn and Cd may be that large size of mercury ion. The complexes were characterized by elementary analyses, infrared and visible spectra, magnetic moment and conductivity measurements.(author)

  9. [AuHg(o-C6H4PPh22I]: A Dinuclear Heterometallic Blue Emitter

    Directory of Open Access Journals (Sweden)

    José M. López-de-Luzuriaga


    Full Text Available The heteronuclear AuI/HgII complex [AuHg(o-C6H4PPh22I] (1 was prepared by reacting of [Hg(2-C6H4PPh22] with [Au(tht2]ClO4 (1:1 and NaI in excess. The heterometallic compound 1 has been structurally characterized and shows an unusual blue luminescent emission in the solid state. Theoretical calculations suggest that that the origin of the emission arises from the iodide ligand arriving at metal-based orbitals in a Ligand to Metal-Metal Charge Transfer transition.

  10. Structural Study of Mismatched Disila-Crown Ether Complexes

    Directory of Open Access Journals (Sweden)

    Kirsten Reuter


    Full Text Available Mismatched complexes of the alkali metals cations Li+ and Na+ were synthesized from 1,2-disila[18]crown-6 (1 and 2 and of K+ from 1,2,4,5-tetrasila[18]crown-6 (4. In these alkali metal complexes, not all crown ether O atoms participate in the coordination, which depicts the coordination ability of the C-, Si/C-, and Si-bonded O atoms. Furthermore, the inverse case—the coordination of the large Ba2+ ion by the relatively small ligand 1,2-disila[15]crown-5—was investigated, yielding the dinuclear complex 5. This structure represents a first outlook on sandwich complexes based on hybrid crown ethers.

  11. DNA Cleavage and Condensation Activities of Mono- and Binuclear Hybrid Complexes and Regulation by Graphene Oxide

    Directory of Open Access Journals (Sweden)

    Shuo Li


    Full Text Available Hybrid complexes with N,N′-bis(2-benzimidazolylmethylamine and cyclen moieties are novel enzyme mimics and controlled DNA release materials, which could interact with DNA through three models under different conditions. In this paper, the interactions between plasmid DNA and seven different complexes were investigated, and the methods to change the interaction patterns by graphene oxide (GO or concentrations were also investigated. The cleavage of pUC19 DNA promoted by target complexes were via hydrolytic or oxidative mechanisms at low concentrations ranging from 3.13 × 10−7 to 6.25 × 10−5 mol/L. Dinuclear complexes 2a and 2b can promote the cleavage of plasmid pUC19 DNA to a linear form at pH values below 7.0. Furthermore, binuclear hybrid complexes could condense DNA as nanoparticles above 3.13 × 10−5 mol/L and partly release DNA by graphene oxide with π-π stacking. Meanwhile, the results also reflected that graphene oxide could prevent DNA from breaking down. Cell viability assays showed dinuclear complexes were safe to normal human hepatic cells at relative high concentrations. The present work might help to develop novel strategies for the design and synthesis of DNA controllable releasing agents, which may be applied to gene delivery and also to exploit the new application for GO.

  12. Synthesis and crystal structure of a homoleptic diruthenium complex containing tetra-2-pyridyl-1,4-pyrazine (tppz)

    Energy Technology Data Exchange (ETDEWEB)

    Graf, Marion; Mayer, Peter; Boettcher, Hans-Christian [Muenchen Univ. (Germany). Dept. Chemie


    Treatment of hydrated ruthenium(III) chloride with tetra-2-pyridyl-1,4-pyrazine (tppz) in refluxing ethoxyethanol afforded the homoleptic dinuclear complex [(tppz)Ru(μ-tppz)Ru(tppz)]{sup 4+} (1) besides small amounts of the species [Ru(tppz){sub 2}]{sup 2+}. The title complex 1 was obtained as purple crystals and characterized as its hexafluoridophosphate salt by NMR spectroscopy, mass spectrometry and microanalyses. The molecular structure of 1(PF{sub 6}){sub 4} has been established by X-ray crystallography.

  13. Synthesis, crystal structure and luminescent properties of lanthanide extended structure with asymmetrical dinuclear units based on 2-(methylthio)benzoic acid

    Energy Technology Data Exchange (ETDEWEB)

    Oliveira, Cristiane K.; Souza, Viviane P. de; Luz, Leonis L. da [Departamento de Química Fundamental, UFPE, 50.740-560 Recife, PE (Brazil); Menezes Vicenti, Juliano R. de [Escola de Química e Alimento, FURG, 96203-900 Rio Grande, RS (Brazil); Burrow, Robert A. [Departamento de Química, UFSM, 97105-900 Santa Maria, RS (Brazil); Severino Alves; Longo, Ricardo L. [Departamento de Química Fundamental, UFPE, 50.740-560 Recife, PE (Brazil); Malvestiti, Ivani, E-mail: [Departamento de Química Fundamental, UFPE, 50.740-560 Recife, PE (Brazil)


    The extended structures [Ln{sub 2}(L){sub 6}(OH{sub 2}){sub 4}] with L=2-(methylthio)benzoato (2-CH{sub 3}S–C{sub 6}H{sub 4}COO{sup −}) and Ln=Tb (1), Eu (2) and Gd (3) were successfully synthesized and characterized. The single crystal structure of compound 1 was determined and showed an extended structure made up of asymmetrical dinuclear units with the formula catena-poly[{Tb(H_2O)_4}-(μ-L-1κO:2κO'){sub 2}-{Tb(L-κO,O')_2}-(μ-L-1κO:2κO'){sub 2}]. In the molecule of 1, there are two distinct metal sites. The Tb atom in site 1 is bound to four coordinated water molecules and four oxygen atoms from four different benzoate ligands, two of which bridge to site 2 Tb atoms on one side and two to site 2 Tb atoms on the other side. The site 2 Tb atom is bound to four oxygen atoms from two chelating benzoate ligands and four oxygen atoms from four different benzoate ligands, two of which bridge to site 1 Tb atoms on one side and two to site 1 Tb atoms on the other side. The bridging benzoate ligands extend the framework in one-dimension with alternating site 1/site 2 Tb atoms. The luminescent properties of these asymmetric dinuclear extended structures are quite peculiar and showed a single emitting lanthanide center. The quantum yields of 1 (ca. 50–55%) is practically independent of the excitation energy, whereas those of 2 are vanishing small (<1%) when excited at the ligand states and become sizable (ca. 10–20%) upon excitation at the intra-4f manifold. To reconcile these experimental observations in conjunction with the spectral data for compounds 1 and 3, a strong interaction between the lanthanide emitting states at sites 1 and 2 was proposed. For compound 1, the numerical solutions of the rate equations provided evidences that when the transition rates between the emitting states at both sites are larger than the highest decaying rate of these states, the system becomes an effective single emitter. This establishes, for the first time

  14. Design of magnetic coordination complexes for quantum computing. (United States)

    Aromí, Guillem; Aguilà, David; Gamez, Patrick; Luis, Fernando; Roubeau, Olivier


    A very exciting prospect in coordination chemistry is to manipulate spins within magnetic complexes for the realization of quantum logic operations. An introduction to the requirements for a paramagnetic molecule to act as a 2-qubit quantum gate is provided in this tutorial review. We propose synthetic methods aimed at accessing such type of functional molecules, based on ligand design and inorganic synthesis. Two strategies are presented: (i) the first consists in targeting molecules containing a pair of well-defined and weakly coupled paramagnetic metal aggregates, each acting as a carrier of one potential qubit, (ii) the second is the design of dinuclear complexes of anisotropic metal ions, exhibiting dissimilar environments and feeble magnetic coupling. The first systems obtained from this synthetic program are presented here and their properties are discussed.

  15. Synthesis and characterization of some new molybdenum(V) complexes

    International Nuclear Information System (INIS)

    Kamenar, Boris; Korpar-Choling, Branka; Cindrich, Marina; Matkovich-Chalogovich, Dubravka; Penavich, Maja


    The molybdenium(V) complexes of the types Mo 2 O 3 L 4 (L = acetylacetone or dibenzolymethane), Mo 2 O 4 L 2 L' 2 solvated with L' (L = dibenzolymethane, L' = morpholine or thiomorpholine), and NR-morphH)[Mo 8 O 2 0LL' 3 ] (R = methyl or ethyl, L = dibenzolymethane, L' = NR-morpholine) have been synthesized for the first time. All were characterized by chemical analyses, IR spectra and magnethochemical measurements. Crystal structure of [Mo 2 O 4 (dbm) 2 (morph) 2 ].(morph) has been determined by X-ray diffraction technique. Complex is dinuclear containing the molybdenium atoms in a distorted octahedral geometry. Each molybdenium atom is surrounded by two bridging oxo-oxygen atoms, two oxygen atoms from one bidentately coordinated dibenzolymethane ligand, one nitrogen atom from morpholine molecule and one terminal oxo-oxygen atom. The solvated morpholine molecule is disordered around the diad axis. (author)

  16. Transferring the Concept of Multinuclearity to Ruthenium Complexes for Improvement of Anticancer Activity (United States)

    Mendoza-Ferri, Maria G.; Hartinger, Christian G.; Mendoza, Marco A.; Groessl, Michael; Egger, Alexander E.; Eichinger, Rene E.; Mangrum, John B.; Farrell, Nicholas P.; Maruszak, Magdalena; Bednarski, Patrick J.; Klein, Franz; Jakupec, Michael A.; Nazarov, Alexey A.; Severin, Kay; Keppler, Bernhard K.


    Multinuclear platinum anticancer complexes are a proven option to overcome resistance of established anticancer compounds. Transferring this concept to ruthenium complexes led to the synthesis of dinuclear Ru(II)–arene compounds containing a bis(pyridinone)alkane ligand linker. A pronounced influence of the spacer length on the in vitro anticancer activity was found, which is correlated to the lipophilicity of the complexes. IC50 values in the same dimension as for established platinum drugs were found in human tumor cell lines. No cross-resistance to oxoplatin, a cisplatin prodrug, was observed for the most active complex in three resistant cell lines; in fact, a 10-fold reversal of sensitivity in two of the oxoplatin-resistant lines was found. (Bio)analytical characterization of the representative examples showed that the ruthenium complexes hydrolyze rapidly, forming predominantly diaqua species that exhibit affinity toward transferrin and DNA, indicating that both proteins and nucleobases are potential targets. PMID:19170599

  17. Antimony(V) and bismuth(V) complexes of lapachol: synthesis, crystal structure and cytotoxic activity. (United States)

    Oliveira, Ludmila G de; Silva, Meiriane M; Paula, Flávia C S de; Pereira-Maia, Elene C; Donnici, Cláudio L; Simone, Carlos A de; Frézard, Frédéric; Silva, Eufrânio N da; Demicheli, Cynthia


    Antimony(V) and bismuth(V) complexes of lapachol have been synthesized by the reaction of Ph₃SbCl₂ or Ph₃BiCl₂ with lapachol (Lp) and characterized by several physicochemical techniques such as IR, and NMR spectroscopy and X-ray crystallography. The compounds contain six-coordinated antimony and bismuth atoms. The antimony(V) complex is a monomeric derivative, (Lp)(Ph₃Sb)OH, and the bismuth(V) complex is a dinuclear compound bridged by an oxygen atom, (Lp)₂(Ph₃Bi)₂O. Both compounds inhibited the growth of a chronic myelogenous leukemia cell line and the complex of Bi(V) was about five times more active than free lapachol. This work provides a rare example of an organo-Bi(V) complex showing significant cytotoxic activity.

  18. Antimony(V and Bismuth(V Complexes of Lapachol: Synthesis, Crystal Structure and Cytotoxic Activity

    Directory of Open Access Journals (Sweden)

    Cynthia Demicheli


    Full Text Available Antimony(V and bismuth(V complexes of lapachol have been synthesized by the reaction of Ph3SbCl2 or Ph3BiCl2 with lapachol (Lp and characterized by several physicochemical techniques such as IR, and NMR spectroscopy and X-ray crystallography. The compounds contain six-coordinated antimony and bismuth atoms. The antimony(V complex is a monomeric derivative, (Lp(Ph3SbOH, and the bismuth(V complex is a dinuclear compound bridged by an oxygen atom, (Lp2(Ph3Bi2O. Both compounds inhibited the growth of a chronic myelogenous leukemia cell line and the complex of Bi(V was about five times more active than free lapachol. This work provides a rare example of an organo-Bi(V complex showing significant cytotoxic activity.

  19. Energetics, conformation, and recognition of DNA duplexes containing a major adduct of an anticancer azolato-bridged dinuclear PtII complex

    Czech Academy of Sciences Publication Activity Database

    Mlčoušková, J.; Malina, Jaroslav; Novohradský, V.; Kašpárková, J.; Komeda, S.; Brabec, Viktor


    Roč. 1820, č. 10 (2012), s. 1502-1511 ISSN 0304-4165 R&D Projects: GA ČR(CZ) GAP205/11/0856 Institutional research plan: CEZ:AV0Z50040702 Keywords : DNA * platinum * DNA repair Subject RIV: BO - Biophysics Impact factor: 3.848, year: 2012

  20. Thermodynamic stability and energetics of DNA duplexes containing major intrastrand cross-links of second-generation antitumor dinuclear Pt-II complexes

    Czech Academy of Sciences Publication Activity Database

    Florian, Jakub; Kašpárková, Jana; Farell, N.P.; Brabec, Viktor


    Roč. 17, č. 2 (2012), s. 187-196 ISSN 0949-8257 R&D Projects: GA ČR(CZ) GD301/09/H004; GA ČR(CZ) GAP301/10/0598; GA MŠk(CZ) ME10066 Institutional support: RVO:68081707 Keywords : NUCLEOTIDE EXCISION-REPAIR * PLATINUM ANTICANCER DRUGS * GROUP DOMAIN PROTEINS Subject RIV: BO - Biophysics Impact factor: 3.353, year: 2012

  1. Sequence Specificity, Corformation, and Recognition by HMG1 Protein of Major DNA Interstrand Cross-links of Antitumor Dinuclear Platinum Complexes

    Czech Academy of Sciences Publication Activity Database

    Kašpárková, Jana; Farrell, N.; Brabec, Viktor


    Roč. 275, - (2000), s. 15789-15798 ISSN 0021-9258 R&D Projects: GA ČR GA305/99/0695; GA ČR GA307/97/P029; GA AV ČR IAA5004702; GA MŠk ME 152 Institutional research plan: CEZ:A17/98:Z5-004-9-ii Subject RIV: BO - Biophysics Impact factor: 7.368, year: 2000

  2. Crystal structure of di-μ-chlorido-bis[dichloridobis(methanol-κOiridium(III] dihydrate: a surprisingly simple chloridoiridium(III dinuclear complex with methanol ligands

    Directory of Open Access Journals (Sweden)

    Joseph S. Merola


    Full Text Available The reaction between IrCl3·xH2O in methanol led to the formation of small amounts of the title compound, [Ir2Cl6(CH3OH4]·2H2O, which consists of two IrCl4O2 octahedra sharing an edge via chloride bridges. The molecule lies across an inversion center. Each octahedron can be envisioned as being comprised of four chloride ligands in the equatorial plane with methanol ligands in the axial positions. A lattice water molecule is strongly hydrogen-bonded to the coordinating methanol ligands and weak interactions with coordinating chloride ligands lead to the formation of a three-dimensional network. This is a surprising structure given that, while many reactions of iridium chloride hydrate are carried out in alcoholic solvents, especially methanol and ethanol, this is the first structure of a chloridoiridium compound with only methanol ligands.

  3. Magnetic interactions in oxide-bridged dichromium(III) complexes. Computational determination of the importance of non-bridging ligands

    DEFF Research Database (Denmark)

    Morsing, Thorbjørn Juul; Sauer, Stephan P. A.; Weihe, Høgni


    The magnetic susceptibility of the dinuclear chromium(III) complex [(CH3CN)5CrOCr(NCCH3)5](BF4)4 · 2 CH3CN has been measured and analyzed. With a fitted value of the triplet energy J = 650 cm-1, the antiferromagnetic coupling is the strongest hitherto determined for an unsupported linear oxide-br...... relative errors typically of less than 10 % ranging from the strongest coupled systems to systems with moderately strong couplings. A significant influence (>20%) of the chemical nature of the peripheral, non-bridging ligands on the exchange coupling was found and rationalized....

  4. Model synthetic complexes of the hydrogenase with different protonation sites

    International Nuclear Information System (INIS)

    Capon, J.F.; Gloaguen, F.; Morvan, D.; Schollhammer, Ph.; Talarmin, J.; Yaouanc, J.J.


    The data obtained until now seem to indicate that the hydrogen production by hydrogenases induces a proton-hydride coupling. In taking the structures of theses enzymes active sites (determined by X-ray diffraction) as a basis, it can be thought that this proton-hydride coupling is facilitated by the juxtaposition of two protonation sites, the metallic center M and the basic group of an E ligand of the coordination sphere. Contrarily to the supposed running of the hydrogenases enzymes, the homogeneous catalysts of the protons reduction, described in the literature, present a reactivity which is either on an alone metallic site or on a metal-metal bond. This work deals then with the preparation of complexes having two juxtaposed protonation sites. Some iron dinuclear compounds have been synthesized and their properties studied. (O.M.)

  5. Mechanistic Links in the in-situ Formation of Dinuclear Manganese Catalysts, H2O2 Disproportionation, and Alkene Oxidation

    NARCIS (Netherlands)

    Angelone, Davide; Abdolahzadeh, Shaghayegh; de Boer, Johannes W.; Browne, Wesley R.

    The oxidation of substrates, such as alkenes, with H2O2 and the catalyst [Mn-2(IV)(mu-O)(3)(tmtacn)(2)](2+) (1; tmtacn = 1,4,7-tri-methyl-1,4,7-triazacyclononane) is promoted by the addition of carboxylic acids through the in situ formation of bis-(carboxylato) complexes of the type

  6. London penetration depth measurements in Barium(Iron1-xTx)2Arsenic2 (T=Cobalt, Nickel,Ruthenium, Rhodium, Palladium, Platinum, Cobalt+Copper) superconductors (United States)

    Gordon, Ryan T.


    The London penetration depth has been measured in various doping levels of single crystals of Ba(Fe1-xTx )2As2 (T=Co,Ni,Ru,Rh,Pd,Pt,Co+Cu) superconductors by utilizing a tunnel diode resonator (TDR) apparatus. All in-plane penetration depth measurements exhibit a power law temperature dependence, indicating the existence of low-temperature, normal state quasiparticles all the way down to the lowest measured temperature, which was typically 500 mK. Several different doping concentrations from the Ba(Fe1- xTx)2As2 (T=Co,Ni) systems have been measured and the doping dependence of the power law exponent, n, is compared to results from measurements of thermal conductivity and specific heat. In addition, a novel method has been developed to allow for the measurement of the zero temperature value of the in-plane penetration depth by using TDR frequency shifts. By using this technique, the doping dependence of the zero temperature value of the penetration depth has been measured in the Ba(Fe 1-xTx)2As 2 series, which has allowed also for the construction of the doping-dependent superfluid phase stiffness. By studying the effects of disorder on these superconductors using heavy ion irradiation, it has been determined that the observed power law temperature dependence likely arises from pair-breaking impurity scattering contributions, which is consistent with the proposed s+/- symmetry of the superconducting gap in the dirty scattering limit. This hypothesis is supported by the measurement of an exponential temperature dependence of the penetration depth in the intrinsically clean LiFeAs, indicative of a nodeless superconducting gap.

  7. A dinuclear end-on azide-bridged copper(II) compound with weak antiferromagnetic interaction - Synthesis, characterization, magnetism and X-ray structure of bis[(μ-azido-κN1)-(azido-κN1)(1,3-bis(benzimidazol-2-yl)-2-methylpropane)copper(II) (United States)

    van Albada, Gerard A.; Mutikainen, Ilpo; Roubeau, Olivier; Reedijk, Jan


    The centrosymmetric dinuclear compound of formula [Cu(μ-N3-κN1)(N3-κN1)(bbmp)]2 is reported. Synthesis, characterization, physical properties are determined in detail, together with its 3D structure. The dinuclear end-on azide-bridged copper(II) compound displays a weak antiferromagnetic interaction, despite the fact that the magnetic orbitals overlap. The Cu-Cu contact distance is 3.1867(8) Å, while the Cu-Nazide-Cu angle is 103.41(14)°. The IR spectra of the azido ligands are as expected for such coordinated azides.

  8. Mononuclear and binuclear lanthanide complexes of the macrocyclic polyamine polycarboxylic ligands H8OTEC and H8OHEC

    International Nuclear Information System (INIS)

    Schumann, H.; Boettger, U.; Zschunke, A; Weisshoff, H.


    Full text: In recent years there is a growing interest in design and synthesis of macrocyclic ligands and of their dinuclear complexes, owing to their relevance in basic and applied chemistry.1 Our studies are aimed to synthesize ligands based on the DOTA or DTPA backbone which can at least bind two trivalent lanthanide ions, to study their stereochemical properties and to determine the stability of such complexes in aqueous solution. We have recently reported the successful synthesis and characterization of two new hexadecadentate macrocyclic polyaza polycarboxylate ligands OTEC (1,4,7,10,13,16,19,22 - octaazacyclotetracosane - 1,4,7,10,13,16,19,22-octaacetic acid) and OHEC (1,4,7,10,14,17,20,-23 - octaazacyclohexacosane - 1,4,7,10,14,17,20,23 - octaacetic acid) and some of their mono- and dinuclear lanthanide(III) chelate complexes which are highly stable and watersoluble. The acid-base properties of these ligands were characterized by using potentiometry and NMR titration techniques. The determination of the thermodynamic stability constants governing the formation of the complexes with Ca(II), Mg(II) and Gd(III) are in progress. The solid structure of four homodinuclear lanthanide(III)chelates (La(III), Eu(III), Gd(III) and Y(III)) of the ligand OHEC was investigated by X-ray crystal structure analysis. In the isostructural complexes the lanthanide ions are nine coordinated by eight donors provided by the ligand and one oxygen of a water molecule. This results in an unusual coordination polyhedron different from that found in the lanthanide complexes of the ligand DOTA and TETA. The conformation of the macrocycles in these complexes was compared to those of the parent compound 1,4,7,10,14,17,20,23-octaazacyclohex-acosane and its dinuclear copper complex. Due to NMR investigations the environment of the lanthanide cation is probably identical in solution and in the solid state. There is nearly a quantitative fit between the crystal structure and the major

  9. Chlorodiethylaluminum supported on silica: A dinuclear aluminum surface species with bridging μ2-Cl-ligand as a highly efficient co-catalyst for the Ni-catalyzed dimerization of ethene

    KAUST Repository

    Kermagoret, Anthony


    Silica-supported chloro alkyl aluminum co-catalysts (DEAC@support) were prepared via Surface Organometallic Chemistry by contacting diethylaluminum chloride (DEAC) and high specific surface silica materials, i.e. SBA-15, MCM-41, and Aerosil SiO2. Such systems efficiently activate NiCl 2(PBu3)2 for catalytic ethene dimerization, with turnover frequency (TOF) reaching up to 498,000 molC2H4/ (molNi h) for DEAC@MCM-41. A detailed analysis of the DEAC@SBA-15 co-catalyst structure by solid-state aluminum-27 NMR at high-field (17.6 T and 20.0 T) and ultrafast spinning rates allows to detect six sites, characterized by a distribution of quadrupolar interaction principal values CQ and isotropic chemical shifts δiso. Identification of the corresponding Al-grafted structures was possible by comparison of the experimental NMR signatures with these calculated by DFT on a wide range of models for the aluminum species (mono- versus di-nuclear, mono- versus bis-grafted with bridging Cl or ethyl). Most of the sites were identified as dinuclear species with retention of the structure of DEAC, namely with the presence of μ2-Cl-ligands between two aluminum, and this probably explains the high catalytic performance of this silica-supported co-catalysts. © 2014 Elsevier Inc. All rights reserved.

  10. A Density Functional Study for the Bridged Dinuclear Center Based on a High Resolution X-ray Crystal Structure of ba3 Cytochrome c Oxidase from Thermus thermophilus (United States)

    Du, Wen-Ge Han; Noodleman, Louis


    Strong electron density for a peroxide type dioxygen species bridging the Fea3 and CuB dinuclear center (DNC) was observed in the high resolution (1.8 Å) X-ray crystal structures (PDB entries: 3S8G and 3S8F) of ba3 cytochrome c oxidase (CcO) from Thermus thermophilus (Tiefenbrunn et al. PLos ONE 2011, 7, e22348). The crystals represent the as-isolated X-ray photoreduced CcO structures. The bridging peroxide was proposed to arise from the recombination of two radiation produced HO· radicals formed either very near to or even in the space between the two metals of the DNC. It is unclear whether this peroxide species is in the O22−, O2·−, HO2−, or in the H2O2 form, and what is the detailed electronic structure and binding geometry including the DNC. In order to answer what form of this dioxygen species was observed in the DNC of the 1.8 Å X-ray CcO crystal structure (3S8G), we have applied broken-symmetry density functional theory (BS-DFT) geometric and energetic calculations (using OLYP potential) on large DNC cluster models with different Fea3-CuB oxidation and spin states and with either O22−, O2·−, HO2−, or H2O2 in the bridging position. By comparing the DFT optimized geometries with the X-ray crystal structure (3S8G), we propose that the bridging peroxide is HO2−. The X-ray crystal structure is likely to represent the superposition of the Fea32+-(HO2−)-CuB1+ DNC’s in different states (Fe2+ in low-spin (LS), intermediate-spin (IS), or high-spin (HS)) with the majority species having the proton of the HO2− residing on the oxygen atom (O1) which is closer to the Fea32+ site in the Fea32+-(HO-O)−-CuB1+ conformation. Our calculations show that the sidechain of Tyr237 is likely trapped in the deprotonated Tyr237− anion form in the 3S8G X-ray crystal structure. PMID:24262070

  11. Density functional study for the bridged dinuclear center based on a high-resolution X-ray crystal structure of ba3 cytochrome c oxidase from Thermus thermophilus. (United States)

    Du, Wen-Ge Han; Noodleman, Louis


    Strong electron density for a peroxide type dioxygen species bridging the Fea3 and CuB dinuclear center (DNC) was observed in the high-resolution (1.8 Å) X-ray crystal structures (PDB entries 3S8G and 3S8F) of ba3 cytochrome c oxidase (CcO) from Thermus thermophilus. The crystals represent the as-isolated X-ray photoreduced CcO structures. The bridging peroxide was proposed to arise from the recombination of two radiation-produced HO(•) radicals formed either very near to or even in the space between the two metals of the DNC. It is unclear whether this peroxide species is in the O2(2-), O2(•)(-), HO2(-), or the H2O2 form and what is the detailed electronic structure and binding geometry including the DNC. In order to answer what form of this dioxygen species was observed in the DNC of the 1.8 Å X-ray CcO crystal structure (3S8G), we have applied broken-symmetry density functional theory (BS-DFT) geometric and energetic calculations (using OLYP potential) on large DNC cluster models with different Fea3-CuB oxidation and spin states and with O2(2-), O2(•)(-), HO2(-), or H2O2 in the bridging position. By comparing the DFT optimized geometries with the X-ray crystal structure (3S8G), we propose that the bridging peroxide is HO2(-). The X-ray crystal structure is likely to represent the superposition of the Fea3(2+)-(HO2(-))-CuB(+) DNC's in different states (Fe(2+) in low spin (LS), intermediate spin (IS), or high spin (HS)) with the majority species having the proton of the HO2(-) residing on the oxygen atom (O1) which is closer to the Fea3(2+) site in the Fea3(2+)-(HO-O)(-)-CuB(+) conformation. Our calculations show that the side chain of Tyr237 is likely trapped in the deprotonated Tyr237(-) anion form in the 3S8G X-ray crystal structure.

  12. Metal Complexes with a Hexadentate Macrocyclic Diamine-Tetracarbene Ligand. (United States)

    Lu, Taotao; Yang, Chu-Fan; Zhang, Li-Yi; Fei, Fan; Chen, Xue-Tai; Xue, Zi-Ling


    A hexadentate macrocyclic N-heterocyclic carbene (NHC) ligand precursor (H 4 L)(PF 6 ) 4 containing four benzimidazolium and two secondary amine groups, has been synthesized and characterized. Coordination chemistry of this new macrocyclic diamine-tetracarbene ligand has been studied by the synthesis of its Ag(I), Au(I), Ni(II), and Pd(II) complexes. Reactions of (H 4 L)(PF 6 ) 4 with different equiv of Ag 2 O result in Ag(I) complexes [Ag(H 2 L)](PF 6 ) 3 (1) and [Ag 2 (H 2 L)](PF 6 ) 4 (2). A mononuclear Au(I) complex [Au(H 2 L)](PF 6 ) 3 (3) and a trinuclear Au(I) complex [Au 3 (H 2 L)(Cl) 2 ](PF 6 ) (4) are obtained by transmetalation of 1 and 2 with AuCl(SMe 2 ), respectively. Reactions of (H 4 L)(PF 6 ) 4 with Ni(OAc) 2 and Pd(OAc) 2 in the presence of NaOAc yield [Ni(L)](PF 6 ) 2 (5) and [Pd(L)](PF 6 ) 2 (6), respectively, containing one Ni(II) and Pd(II) ion with distorted square-planar geometry. Using more NaOAc results in the formation of unusual dinuclear complexes [Ni 2 (L-2H)](PF 6 ) 2 (7) and [Pd 2 (L-2H)](PF 6 ) 2 (8) (L-2H = deprotonated ligand after removing two H + ions from two secondary amine groups in L), respectively, featuring a rare M 2 N 2 core formed by two bridging amides. 7 is also formed by the reaction of 5 with 1.0 equiv of Ni(OAc) 2 ·4H 2 O in the presence of NaOAc. Transmetalation of 2 with 2.0 equiv of Ni(PPh 3 ) 2 Cl 2 gives [Ni 2 (L)(μ-O)](PF 6 ) 2 (9), the first example of a dinuclear Ni(II) complex with a singly bridging oxo group. 9 is converted to 7 in good yield through the treatment with NaOAc.

  13. Coupling of Carbon Dioxide with Epoxides Efficiently Catalyzed by Thioether-Triphenolate Bimetallic Iron(III) Complexes: Catalyst Structure-Reactivity Relationship and Mechanistic DFT Study

    KAUST Repository

    Della Monica, Francesco


    A series of dinuclear iron(III)I complexes supported by thioether-triphenolate ligands have been prepared to attain highly Lewis acidic catalysts. In combination with tetrabutylammonium bromide (TBAB) they are highly active catalysts in the synthesis of cyclic organic carbonates through the coupling of carbon dioxide to epoxides with the highest initial turnover frequencies reported to date for the conversion of propylene oxide to propylene carbonate for iron-based catalysts (5200h-1; 120°C, 2MPa, 1h). In particular, these complexes are shown to be highly selective catalysts for the coupling of carbon dioxide to internal oxiranes affording the corresponding cyclic carbonates in good yield and with retention of the initial stereochemical configuration. A density functional theory (DFT) investigation provides a rational for the relative high activity found for these Fe(III) complexes, showing the fundamental role of the hemilabile sulfur atom in the ligand skeleton to promote reactivity. Notably, in spite of the dinuclear nature of the catalyst precursor only one metal center is involved in the catalytic cycle. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  14. Synthesis and characterization of multiferrocenyl-substituted group 4 metallocene complexes. (United States)

    Kaleta, Katharina; Strehler, Frank; Hildebrandt, Alexander; Beweries, Torsten; Arndt, Perdita; Rüffer, Tobias; Spannenberg, Anke; Lang, Heinrich; Rosenthal, Uwe


    The reaction of different metallocene fragments [Cp(2)M] (Cp=η(5)-cyclopentadienyl, M=Ti, Zr) with diferrocenylacetylene and 1,4-diferrocenylbuta-1,3-diyne is described. The titanocene complexes form the highly strained three- and five-membered ring systems [Cp(2)Ti(η(2)-FcC(2)Fc)] (1) and [Cp(2)Ti(η(4)-FcC(4)Fc)](2) (Fc=[Fe(η(5)-C(5)H(4))(η(5)-C(5)H(5))]) by addition of the appropriate alkyne or diyne to Cp(2)Ti. Zirconocene precursors react with diferrocenyl- and ferrocenylphenylacetylene under C-C bond coupling to yield the metallacyclopentadienes [Cp(2)Zr(C(4)Fc(4))](3) and [Cp(2)Zr(C(4)Fc(2)Ph(2))](5), respectively. The exchange of the zirconocene unit in 3 by hydrogen atoms opens the route to the super-crowded ferrocenyl-substituted compound tetraferrocenylbutadiene (4). On the other hand, the reaction of 1,4-diferrocenylbuta-1,3-diyne with zirconocene complexes afforded a cleavage of the central C-C bond, and thus, dinuclear [{Cp(2)Zr(μ-η(1):η(2)-C≡CFc)}(2)] (6) that consists of two zirconocene acetylide groups was formed. Most of the complexes were characterized by single-crystal X-ray crystallography, showing attractive multinuclear molecules. The redox properties of 3, 5, and 6 were studied by cyclic voltammetry. Upon oxidation to 3(n+), 5(n+), and 6(n+) (n=1-3), decomposition occured with in situ formation of new species. The follow-up products from 3 and 5 possess two or four reversible redox events pointing to butadiene-based molecules. However, the dinuclear complex 6 afforded ethynylferrocene under the measurement conditions. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  15. Kinetic studies of the impact of thiocyanate moiety on the catalytic properties of Cu(II) and Fe(III) complexes of a new Mannich base (United States)

    Ayeni, Ayowole O.; Watkins, Gareth M.


    Four new metal complexes of a novel Mannich base 5-methyl-2-((4-(pyridin-2-yl)piperazin-1-yl)methyl)phenol (HL) have been prepared. The compounds were characterized by an array of analytical and spectroscopic methods including Nuclear Magnetic Resonance, Infra-red and UV-Visible spectroscopy. Compounds 1-4 behaved as effective catalysts towards the oxidation of 3,5-di-tert-butylcatechol (3,5-DTBC) to its corresponding quinone in the presence of molecular oxygen in DMF solution while compound 4 proved to be the best catalyst with a turnover rate of 17.93 ± 1.10 h-1 as other complexes showed lower rates of oxidation. Also with the exception of dinuclear iron complex (4); thiocyanate containing Cu(II) complex exhibited lower catecholase activity compared to the Cu(II) complex without it.

  16. Synthesis, characterization and antibacterial activity of a tridentate Schiff base derived from cephalothin and sulfadiazine, and its transition metal complexes (United States)

    Anacona, J. R.; Noriega, Natiana; Camus, Juan


    Metal(II) coordination compounds of a cephalothin Schiff base (H2L) derived from the condensation of cephalothin antibiotic with sulfadiazine were synthesized. The Schiff base ligand, mononuclear [ML(H2O)3] (M(II) = Mn, Co, Ni, Zn) complexes and magnetically diluted dinuclear copper(II) complex [CuL(H2O)3]2 were characterized by several techniques, including elemental and thermal analysis, molar conductance and magnetic susceptibility measurements, electronic, FT-IR, EPR and 1H NMR spectral studies. The cephalothin Schiff base ligand H2L behaves as a dianionic tridentate NOO chelating agent. The biological applications of complexes have been studied on two bacteria strains (Escherichia coli and Staphylococcus aureus) by agar diffusion disc method.

  17. Model synthetic complexes of the hydrogenase with different protonation sites; Complexes synthetiques modeles de l'hydrogenase avec differents sites de protonation

    Energy Technology Data Exchange (ETDEWEB)

    Capon, J.F.; Gloaguen, F.; Morvan, D.; Schollhammer, Ph.; Talarmin, J.; Yaouanc, J.J. [Universite de Bretagne Occidentale, UMR CNRS 6521, Chimie, Electrochimie Moleculaires et Chimie Analytique, Faculte des Sciences, 29 - Brest (France)


    The data obtained until now seem to indicate that the hydrogen production by hydrogenases induces a proton-hydride coupling. In taking the structures of theses enzymes active sites (determined by X-ray diffraction) as a basis, it can be thought that this proton-hydride coupling is facilitated by the juxtaposition of two protonation sites, the metallic center M and the basic group of an E ligand of the coordination sphere. Contrarily to the supposed running of the hydrogenases enzymes, the homogeneous catalysts of the protons reduction, described in the literature, present a reactivity which is either on an alone metallic site or on a metal-metal bond. This work deals then with the preparation of complexes having two juxtaposed protonation sites. Some iron dinuclear compounds have been synthesized and their properties studied. (O.M.)

  18. Synthesis, structure and spectroscopic properties of Re(I) complexes incorporating 5-arylazo-8-hydroxyquinoline: a density functional theory/time-dependent density functional theory investigation. (United States)

    Sarkar, Rupa; Mondal, Pallab; Rajak, Kajal Krishna


    Dinuclear rhenium(I) complexes having a fac-[Re(CO)3](+) moiety of general formula fac-[Re2(CO)6(hq)2] have been synthesized in excellent yield by reacting [Re(CO)5Cl] with Hhq in a ratio of 1 : 1 in toluene in an argon atmosphere. Here hq(-) is the deprotonated form of 5-phenylazo-8-hydroxyquinoline (Hhq(1)), 5-(2-naphthylazo)-8-hydroxyquinoline (Hhq(2)) and 5-(2-fluorineazo)-8-hydroxyquinoline (Hhq(3)). The reaction of synthesized dinuclear complexes with imidazole (Im) and N-methylimidazole (N-MeIm) in dry dichloromethane under argon atmosphere afforded the mononuclear complexes of general formula fac-[Re(CO)3(hq)(Im)] and fac-[Re(CO)3(hq)(N-MeIm)] respectively in high yield. The elemental analysis and ESI mass spectroscopic measurements confirm the formation of the desired complexes. Molecular structures of fac-[Re(CO)3(hq(1))(Im)] and fac-[Re(CO)3(hq(1))(N-MeIm)] were confirmed by single-crystal X-ray diffraction. The complexes were also characterized by different spectroscopic techniques. The complexes displayed bathochromically shifted intramolecular charge transfer (CT) bands as compared to complexes with unsubstituted 8-hydroxyquinoline complexes. The ground and excited-state geometries, NMR, absorption, and phosphorescence properties of nine Re(i) complexes were examined by DFT and TDDFT methods. The natural transition orbital (NTO) and spin density difference map analysis reveals the nature of excitations. The lowest lying triplet excited is associated with the (3)IL excited state (ligand-localized) having a cis conformation of the pendant arylazo moiety. The emission-like transition is consistent with the strong (3)ILCT character.

  19. Synthesis and reactivity of NHC-supported Ni2(μ(2)-η(2),η(2)-S2)-bridging disulfide and Ni2(μ-S)2-bridging sulfide complexes. (United States)

    Olechnowicz, Frank; Hillhouse, Gregory L; Jordan, Richard F


    The (IPr)Ni scaffold stabilizes low-coordinate, mononuclear and dinuclear complexes with a diverse range of sulfur ligands, including μ(2)-η(2),η(2)-S2, η(2)-S2, μ-S, and μ-SH motifs. The reaction of {(IPr)Ni}2(μ-Cl)2 (1, IPr = 1,3-bis(2,6-diisopropylphenyl)imidazolin-2-ylidene) with S8 yields the bridging disulfide species {(IPr)ClNi}2(μ(2)-η(2),η(2)-S2) (2). Complex 2 reacts with 2 equiv of AdNC (Ad = adamantyl) to yield a 1:1 mixture of the terminal disulfide compound (IPr)(AdNC)Ni(η(2)-S2) (3a) and trans-(IPr)(AdNC)NiCl2 (4a). 2 also reacts with KC8 to produce the Ni-Ni-bonded bridging sulfide complex {(IPr)Ni}2(μ-S)2 (6). Complex 6 reacts with H2 to yield the bridging hydrosulfide compound {(IPr)Ni}2(μ-SH)2 (7), which retains a Ni-Ni bond. 7 is converted back to 6 by hydrogen atom abstraction by 2,4,6-(t)Bu3-phenoxy radical. The 2,6-diisopropylphenyl groups of the IPr ligand provide lateral steric protection of the (IPr)Ni unit but allow for the formation of Ni-Ni-bonded dinuclear species and electronically preferred rather than sterically preferred structures.

  20. Influence of Tuned Linker Functionality on Modulation of Magnetic Properties and Relaxation Dynamics in a Family of Six Isotypic Ln2(Ln = Dy and Gd) Complexes. (United States)

    Mukherjee, Soumya; Lu, Jingjing; Velmurugan, Gunasekaran; Singh, Shweta; Rajaraman, Gopalan; Tang, Jinkui; Ghosh, Sujit K


    A coordination complex family comprising of six new dinuclear symmetric lanthanide complexes, namely, [Ln 2 (L x ) 2 (L') 2 (CH 3 OH) 2 ]·yG (H 2 L x : three related yet distinct Schiff-base linkers; x = 1-3, according to the nomenclature of the Schiff-base linker employed herein. HL': 2,6-dimethoxyphenol. yG refers to crystallographically assigned guest solvent species in the respective complexes; y = number of solvent molecules; Ln III = Dy/Gd) were isolated employing a mixed-ligand strategy stemming out of a strategic variation of the functionalities introduced among the constituent Schiff-base linkers. The purposeful introduction of three diverse auxiliary groups with delicate differences in their electrostatic natures affects the local anisotropy and magnetic coupling of Ln III ion-environment in the ensuing Ln 2 dinuclear complexes, consequentially resulting into distinctly dynamical magnetic behaviors among the investigated new-fangled family of isotypic Ln 2 complexes. Among the entire family, subtle alterations in the chemical moieties render two of the Dy 2 analogues to behave as single molecule magnets, while the other Dy 2 congener merely exhibits slow relaxation of the magnetization. The current observation marks one of the rare paradigms, wherein magnetic behavior modulation was achieved by virtue of the omnipresent influence of subtly tuned linker functionalities among the constituent motifs of the lanthanide nanomagnets. To rationalize the observed difference in the magnetic coupling, density functional theory and ab initio calculations (CASSCF/RASSI-SO/POLY_ANISO) were performed on all six complexes. Subtle difference in the bond angles leads to difference in the J values observed for Gd 2 complexes, while difference in the tunnel splitting associated with the structural alterations lead to variation in the magnetization blockade in the Dy 2 complexes.

  1. Spectroscopic investigation of new water soluble Mn(II)(2) and Mg(II)(2) complexes for the substrate binding models of xylose/glucose isomerases. (United States)

    Patra, Ayan; Bera, Manindranath


    In methanol, the reaction of stoichiometric amounts of Mn(OAc)(2)·4H(2)O and the ligand H(3)hpnbpda [H(3)hpnbpda=N,N'-bis(2-pyridylmethyl)-2-hydroxy-1,3-propanediamine-N,N'-diacetic acid] in the presence of NaOH, afforded a new water soluble dinuclear manganese(II) complex, [Mn2(hpnbpda)(μ-OAc)] (1). Similarly, the reaction of Mg(OAc)(2)·4H(2)O and the ligand H3hpnbpda in the presence of NaOH, in methanol, yielded a new water soluble dinuclear magnesium(II) complex, [Mg2(hpnbpda)(μ-OAc)(H2O)2] (2). DFT calculations have been performed for the structural optimization of complexes 1 and 2. The DFT optimized structure of complex 1 shows that two manganese(II) centers are in a distorted square pyramidal geometry, whereas the DFT optimized structure of complex 2 reveals that two magnesium(II) centers adopt a six-coordinate distorted octahedral geometry. To understand the mode of substrate binding and the mechanistic details of the active site metals in xylose/glucose isomerases (XGI), we have investigated the binding interactions of biologically important monosaccharides d-glucose and d-xylose with complexes 1 and 2, in aqueous alkaline solution by a combined approach of FTIR, UV-vis, fluorescence, and (13)C NMR spectroscopic techniques. Fluorescence spectra show the binding-induced gradual decrease in emission of complexes 1 and 2 accompanied by a significant blue shift upon increasing the concentration of sugar substrates. The binding modes of d-glucose and d-xylose with complex 2 are indicated by their characteristic coordination induced shift (CIS) values in (13)C NMR spectra for C1 and C2 carbon atoms. Copyright © 2013 Elsevier Ltd. All rights reserved.

  2. Time-resolved luminescence imaging of intracellular oxygen levels based on long-lived phosphorescent iridium(III) complex. (United States)

    Liu, Shujuan; Zhang, Yangliu; Liang, Hua; Chen, Zejing; Liu, Ziyu; Zhao, Qiang


    Time-resolved luminescence imaging of intracellular oxygen levels has been demonstrated based on long-lived phosphorescent signal. A phosphorescent dinuclear iridium(III) complex Ir1 has been designed and synthesized, which exhibits excellent optical properties, such as high quantum yields, large Stokes shift, high photostability and long emission lifetime. The phosphorescent intensity and lifetime of complex are very sensitive to oxygen levels. Thus, the application of Ir1 for monitoring intracellular oxygen levels has been realized successfully. Especially, utilizing the advantageous long emission lifetime of Ir1, the background fluorescence interference could be eliminated effectively by using the photoluminescence lifetime imaging and time-gated luminescence imaging techniques, improving the signal-to-noise ratios in bioimaging.

  3. Syntheses, crystal structures, anticancer activities of three reduce Schiff base ligand based transition metal complexes (United States)

    Chang, Hui-Qin; Jia, Lei; Xu, Jun; Zhu, Tao-Feng; Xu, Zhou-Qing; Chen, Ru-Hua; Ma, Tie-Liang; Wang, Yuan; Wu, Wei-Na


    Three nickel(II) complexes, [Ni2(L1)2(tren)2(H2O)](ClO4)3 (1), [NiL2(tren)2](ClO4)·2.5H2O (2), [NiL2(tren)2]I·1.5H2O·CH3OH (3) based on amino acid reduced Schiff ligands are synthesized and characterized by physico-chemical and spectroscopic methods. The results show that in all complexes, the amino acid ligand is deprotonated and acts as an anionic ligand. In the dinuclear complex 1, each Ni(II) atom has a distorted octahedron geometry while with different coordination environment. However, the complexes 2 and 3 are mononuclear, almost with the same coordination environment. Furthermore, in vitro experiments are carried out, including MTT assay, Annexin V/PI flow cytometry and western blotting, to assess whether the complexes have antitumor effect. And the results show that all the three complexes have moderate anticancer activity towards human hepatic cancer (HepG2), human cervical cancer (HeLa) and human prostate (PC3) cell lines, in a concentration dependent way. The complex 1 exhibit higher cytotoxicity than the other two complexes and can induce human hepatic cancer cell (HepG2) to cell apoptosis by activating caspase 3.

  4. Mixed chloride/phosphine complexes of the dirhenium core. 10. Redox reactions of an edge-sharing dirhenium(III) non-metal-metal-bonded complex, Re(2)(mu-Cl)(2)Cl(4)(PMe(3))(4). (United States)

    Cotton, F A; Dikarev, E V; Petrukhina, M A


    Reduction and oxidation reactions of the dirhenium(III) non-metal-metal-bonded edge-sharing complex, Re(2)(mu-Cl)(2)Cl(4)(PMe(3))(4) (1), have been studied. Several new mono- and dinuclear rhenium compounds have been isolated and structurally characterized in the course of this study. Reductions of 1 with 1 and 2 equiv of KC(8) result in an unusual face-sharing complex having an Re(2)(5+) core, Re(2)(mu-Cl)(3)Cl(2)(PMe(3))(4) (2), and a triply bonded Re(II) compound, 1,2,7,8-Re(2)Cl(4)(PMe(3))(4) (3), respectively. Two-electron reduction of 1 in the presence of tetrabutylammonium chloride affords a new triply bonded complex of the Re(2)(4+) core, [Bu(n)()(4)N][1,2,7-Re(2)Cl(5)(PMe(3))(3)] (4). Oxidation of 1 with NOBF(4) yields a Re(IV) mononuclear compound, trans-ReCl(4)(PMe(3))(2) (5). Two isomers of the monomeric Re(III) anion, [ReCl(4)(PMe(3))(2)](-) (6, 7), have been isolated as side products. The crystal structures of compounds 2 and 4-7 have been determined by X-ray crystallography. The Re-Re distance in the face-sharing complex 2 of 2.686(1) A is relatively short. The metal-metal bond length in anion 4 of 2.2354(7) A is consistent with the usual values for the triply bonded Re(2)(4+) core compounds. In addition, a cis arrangement of trimethylphosphine ligands in the starting material 1 is retained upon reduction in the dinuclear products 2-4.

  5. A novel dinuclear bismuth(III) coordination compound: bis(μ-pyridine-2,6-dicarboxylato)-κ4O2,N,O6:O6′;κ4O2:O2′,N,O6-bis[(azido-κN)(1,10-phenanthroline-κ2N,N')bismuth(III)] tetrahydrate. (United States)

    Zhang, Wei; Feng, Yu-Quan


    A novel dinuclear bismuth(III) coordination compound, [Bi2(C7H3NO4)2(N3)2(C12H8N2)2]·4H2O, has been synthesized by an ionothermal method and characterized by elemental analysis, energy-dispersive X-ray spectroscopy, IR, X-ray photoelectron spectroscopy and single-crystal X-ray diffraction. The molecular structure consists of one centrosymmetric dinuclear neutral fragment and four water molecules. Within the dinuclear fragment, each Bi(III) centre is seven-coordinated by three O atoms and four N atoms. The coordination geometry of each Bi(III) atom is distorted pentagonal-bipyramidal (BiO3N4), with one azide N atom and one bridging carboxylate O atom located in axial positions. The carboxylate O atoms and water molecules are assembled via O-H···O hydrogen bonds, resulting in the formation of a three-dimensional supramolecular structure. Two types of π-π stacking interactions are found, with centroid-to-centroid distances of 3.461 (4) and 3.641 (4) Å.

  6. Moessbauer spectroscopy-nuclear hyperfine technique for studying dynamic chemical states of iron complexes

    International Nuclear Information System (INIS)

    Maeda, Y.


    A brief introduction of Moessbauer spectroscopy will be presented, followed by a discussion of the Moessbauer parameters, isomer shifts, quadrupole splittings, and spectral shapes of complexes in the presence of relaxation of the electronic states of the iron atoms. The usefulness of Moessbauer spectroscopy to demonstrate the dynamic phenomena of electronic states will be discussed in this lecture. (1) The Moessbauer spectra of mixed valence dinuclear and trinuclear iron complexes will be discussed in connection with the chemical structure of the complexes: The values of the quadrupole splittings and isomer shifts of [Fe II Fe III (bpmp) (ppa) 2 ](BF 4 ) 2 increase on raising the temperature, where Hbpmp represents 2,6-bis[bis(2- pyridylmethyl)aminoethyl]-4-methylphenol and ppa is 3-n-phenylpropionic acid. The spectra can be accounted for by postulating intramolecular electron exchange between two energetically inequivalent vibronic states Fe A 2+ Fe B 3+ and Fe A 3+ Fe B 2+ : The apparent time averaged valence states of the iron atoms are 2.2 and 2.8 on the Moessbauer time scale at 293 K. (2) The Moessbauer spectra of iron(III) spin-crossover complexes will be discussed in connection with the spin-transition rate and chemical structure of the complexes. The Moessbauer spectra of spin-crossover iron(III) complexes with LIESST (Light Induced Electronic Spin-State Transition) and of metallomesogens will be discussed to illustrate the extension of this research area by the use of Moessbauer spectroscopy.

  7. Thermodynamic parameters of the complexation of uranyl(VI) by diethylenetriamine in dimethyl sulfoxide

    International Nuclear Information System (INIS)

    Cassol, A.; Bernardo, P. di; Portanova, R.; Tolazzi, M.; Tomat, G.; Zanonato, P.L.


    The changes in free energy, enthalpy, and entropy for the complex formation reactions between uranyl(VI) ion and diethylenetriamine (dien) in dimethyl sulfoxide have been determined by potentiometric and calorimetric measurements at 25 C in a medium of ionic strength 0.1 mol dm -3 . The amine forms a very stable 1:1 complex which results stabilized only by the highly favourable enthalpy change. Entropy change is negative and opposes the reaction. The comparison of the thermodynamic data concerning complexation of uranyl(VI) by charged and uncharged ligands reveals that in this case (uncharged ligand) the enthalpy contribution is mainly related to the formation of the metal-ligand bonds while the entropy term might be associated with the decrease in the translational and conformational entropy occurring in the complexation of the ligand. FTIR and calorimetric measurements have been carried out to study the effect of traces of water on the equilibria in solution. It has been found that water can interfere in the complexation reaction giving rise to the formation of a dinuclear hydroxo complex in which probably two μ 2 -OH bridges link two monomer moieties. (orig.)

  8. Complexity explained

    CERN Document Server

    Erdi, Peter


    This book explains why complex systems research is important in understanding the structure, function and dynamics of complex natural and social phenomena. Readers will learn the basic concepts and methods of complex system research.

  9. Complex chemistry

    International Nuclear Information System (INIS)

    Kim, Bong Gon; Kim, Jae Sang; Kim, Jin Eun; Lee, Boo Yeon


    This book introduces complex chemistry with ten chapters, which include development of complex chemistry on history coordination theory and Warner's coordination theory and new development of complex chemistry, nomenclature on complex with conception and define, chemical formula on coordination compound, symbol of stereochemistry, stereo structure and isomerism, electron structure and bond theory on complex, structure of complex like NMR and XAFS, balance and reaction on solution, an organo-metallic chemistry, biology inorganic chemistry, material chemistry of complex, design of complex and calculation chemistry.

  10. Residual dipolar couplings in sup 3 sup 1 P MAS spectra of PPh sub 3 substituted cobalt complexes

    CERN Document Server

    Szalontai, G


    Residual dipolar couplings between sup 3 sup 1 P- sup 5 sup 9 Co spin pairs were studied in sup 3 sup 1 P MAS spectra of mono- and dinuclear cobalt-triphenylphosphine complexes. These spectra can provide important information such as the scalar coupling between the dipolar phosphorus and the quadrupolar cobalt nuclei normally not available from solution phase studies. In case of complementary (NQR or x-ray) data even the relative orientation of the interacting shielding, dipolar, scalar couplings, and electric field gradient tensors or internuclear distances can be determined. Examples are shown both for well resolved and practically unresolved cases, factors which possibly control the spectral resolution are discussed in detail. (author)

  11. Fluorescent copper(II complexes: The electron transfer mechanism, interaction with bovine serum albumin (BSA and antibacterial activity

    Directory of Open Access Journals (Sweden)

    Madhumita Hazra


    Full Text Available Dinuclear copper(II complexes with formula [Cu2(L2(N32] (1 and [Cu2(L2(NCS2] (2 HL = (1-[(3-methyl-pyridine-2-ylimino-methyl]-naphthalen-2-ol were synthesized by controlling the molar ratio of Cu(OAC2·6H2O, HL, sodium azide (1 and ammonium thiocyanate (2. The end on bridges appear exclusively in azide and thiocyanate to copper complexes. The electron transfer mechanism of copper(II complexes is examined by cyclic voltammetry indicating copper(II complexes are Cu(II/Cu(I couple. The interactions of copper(II complexes towards bovine serum albumin (BSA were examined with the help of absorption and fluorescence spectroscopic tools. We report a superficial solution-based route for the synthesis of micro crystals of copper complexes with BSA. The antibacterial activity of the Schiff base and its copper complexes were investigated by the agar disc diffusion method against some species of pathogenic bacteria (Escherichia coli, Vibrio cholerae, Streptococcus pneumonia and Bacillus cereus. It has been observed that the antibacterial activity of all complexes is higher than the ligand.

  12. Synthesis and coordination behavior of a bipyridine platinum(II) complex with thioglucose. (United States)

    Tsuji, Takaaki; Kuwamura, Naoto; Yoshinari, Nobuto; Konno, Takumi


    A mononuclear platinum(II) complex with two monodentate-S H4tg(-) ligands, [Pt(H4tg-κS)2(bpy)] (1), was newly synthesized by the reaction of [PtCl2(bpy)] (bpy = 2,2'-bipyridyl) with NaH4tg (NaH4tg =1-thio-β-d-glucose sodium salt) in water. Complex 1 reacted with additional [PtCl2(bpy)] in water to give an S-bridged dinuclear complex, [Pt2(μ2-H4tg-κ(1)S:κ(1)S)2(bpy)2](2+) ([2](2+)), in which a square-planar [Pt(H4tg)2(bpy)] unit binds to a [Pt(bpy)](2+) moiety through two thiolato groups. Treatments of 1 with Cu(2+) and Ni(2+) in water in the presence of bpy produced S-bridged dinuclear complexes [PtCu(μ2-H4tg-κ(1)S:κ(2)O,S)2(bpy)2](2+) ([3](2+)) and [PtNi(μ2-H4tg-κ(1)S:κ(2)O,S)2(bpy)2](2+) ([4](2+)), respectively, in which a square-planar [Pt(H4tg)2(bpy)] unit binds to a [M(bpy)](2+) (M = Cu(II), Ni(II)) moiety through two thiolato and two hydroxyl groups to form a chiral [M(N)2(O)2(S)2] octahedron with the Δ configuration. On the other hand, similar treatment with Cd(2+) in the presence of bpy resulted in the formation of an S-bridged trinuclear complex, [Cd{Pt(μ2-H4tg-κ(1)S:κ(2)O,S)(μ2-H4tg-κ(1)S:κ(1)S)(bpy)}2](2+) ([5](2+)), in which each of two square-planar [Pt(H4tg)2(bpy)] units binds to a Cd(II) ion through two thiolato groups and one hydroxyl group to form a chiral [Cd(O)2(S)4] octahedron with the Λ configuration. Of two geometrical configurations, syn and anti, which arise from the relative arrangement of two β-D-pyranose moieties, [2](2+) adopts the syn configuration with symmetric bridging sulfur atoms, while [3](2+), [4](2+), and [5](2+) all have the anti configuration with R configurational bridging sulfur atoms. All of the complexes were fully characterized by electronic absorption, CD, and NMR spectroscopies, along with single-crystal X-ray crystallography.

  13. Bioreduction of Uranium(VI) Complexed with Citric Acid by Clostridia Affects its Structure and Mobility

    International Nuclear Information System (INIS)

    Francis, A.; Dodge, C.


    Uranium contamination of the environment from mining and milling operations, nuclear-waste disposal, and ammunition use is a widespread global problem. Natural attenuation processes such as bacterial reductive precipitation and immobilization of soluble uranium is gaining much attention. However, the presence of naturally occurring organic ligands can affect the precipitation of uranium. Here, we report that the anaerobic spore-forming bacteria Clostridia, ubiquitous in soils, sediments, and wastes, capable of reduction of Fe(III) to Fe(II), Mn(IV) to Mn(II), U(VI) to U(IV), Pu(IV) to Pu(III), and Tc(VI) to Tc(IV); reduced U(VI) associated with citric acid in a dinuclear 2:2 U(VI):citric acid complex to a biligand mononuclear 1:2 U(IV):citric acid complex, which remained in solution, in contrast to reduction and precipitation of uranium. Our findings show that U(VI) complexed with citric acid is readily accessible as an electron acceptor despite the inability of the bacterium to metabolize the complexed organic ligand. Furthermore, it suggests that the presence of organic ligands at uranium-contaminated sites can affect the mobility of the actinide under both oxic and anoxic conditions by forming such soluble complexes.

  14. Synthesis, characterization and thermal properties of palladium(II complexes containing phenyltetrazole. Crystal structure of trans-[C40H64N8 O2PdCl2

    Directory of Open Access Journals (Sweden)

    Gallardo Hugo


    Full Text Available The new 5-(n-alkoxyphenyl-2-n-alkyltetrazole (L¹ and alpha,omega-bis-[5-(4-pentoxyphenyl-2-alkanetetrazoles] (L² ligands and their Pd(II complexes have been synthesized. The X-ray diffraction study of the palladium complex with L¹ reveals a mononuclear structure in which the geometry of the Pd(L¹2Cl2 chromophore is planar as required by the inversion center at the palladium atom, where each molecule of phenyltetrazole binds to the metal ion in a monodentate fashion via a Pd-N1 sigma-bond. For the palladium complex with L², a dinuclear structure ([Pd2(L²2Cl4 ] has been proposed on the basis of NMR and IR spectroscopy.

  15. Gold and Nickel Extended Thiophenic-TTF Bisdithiolene Complexes

    Directory of Open Access Journals (Sweden)

    Rafaela A. L. Silva


    Full Text Available Gold and nickel bisdithiolene complexes with methyl and tert-butyl substituted thiophenetetrathiafulavalenedithiolate ligands (α-mtdt and α-tbtdt were prepared and characterized. These complexes were obtained, under anaerobic conditions, as tetrabutylammonium salts. The diamagnetic gold monoanion (n-Bu4N[Au(α-mtdt2] (3 and nickel dianionic species (n-Bu4Nx[Ni(α-mtdt2] (x = 1,2 (4 were similar to the related non-substituted extended thiophenic-TTF (TTF = tetrathiafulvalene bisdithiolenes. However the introduction of the large, bulky substituent tert-butyl, led to the formation of a Au (I dinuclear complex, (n-Bu4N2[Au2(α-tbtdt2] (5. The neutral methyl substituted gold and nickel complexes were easily obtained through air or iodine exposure as polycrystalline or amorphous fine powder. [Au(α-mtdt2] (6 and [Ni(α-mtdt2] (7 polycrystalline samples display properties of a metallic system with a room temperature electrical conductivity of 0.32 S/cm and ≈4 S/cm and a thermoelectric power of ≈5 µV/K and ≈32 µV/K, respectively. While [Au(α-mtdt2] (6 presented a Pauli-like magnetic susceptibility typical of conducting systems, in [Ni(α-mtdt2] (7 large magnetic susceptibilities indicative of high spin states were observed. Both electric transport properties and magnetic properties for gold and nickel [M(α-mtdt2] are indicative that these compounds are single component molecular conductors.

  16. Synthesis, characterization, and crystal structures of diruthenium complexes containing bridging salicylato ligands

    Energy Technology Data Exchange (ETDEWEB)

    Jiang, Mingxuan; Yau, Chun Huan; Hu, Yuxin; Tan, Yong Leng Kelvin [Hwa Chong Institution (Singapore); Li, Yingzhou; Ganguly, Rakesh; Leong, Weng Kee [Division of Chemistry and Biological Chemistry, School of Physical and Mathematical Sciences, Nanyang Technological University (Singapore)


    The thermal reaction of Ru{sub 3}(CO){sub 12} (1) with salicylic acid, in the presence of triphenylphosphine, pyridine, or dimethylsulfoxide, afforded the dinuclear complexes Ru{sub 2}(CO){sub 4}(μ-O{sub 2}CC{sub 6}H{sub 4}OH){sub 2}L{sub 2} (2) [L = PPh{sub 3} (2a). C{sub 5}H{sub 5}N (2b); (CH{sub 3}){sub 2}SO (2c)]. Complex 2b was further reacted with the aromatic dimmines 2,2'-dipyridine or 1,10-phenanthroline to give the cationic diruthenium complexes [Ru{sub 2}(CO){sub 2}(μ-CO){sub 2}(μ-O{sub 2}CC{sub 6}H{sub 4}OH)(N intersection N){sub 2}]{sup +} (3) [(N intersection N) = 2,2'-dipyridine (3a); 1,10-phenanthroline (3b)], which were isolated as their tetraphenylborate salts. All five novel complexes were characterized spectroscopically and analytically. For 2a-2b and 3a-3b, single-crystal X-ray diffraction studies were also carried out. (copyright 2017 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

  17. Complex Narratives

    NARCIS (Netherlands)

    Simons, J.; Buckland, W.


    In the opening chapter, "Complex Narratives," Jan Simons brings together narratology, game theory, and complexity theory to untangle the intricate nature of complex narratives in contemporary cinema. He presents an overview of the different concepts - forking path narratives, mind-game films,

  18. phenanthroline complex

    Indian Academy of Sciences (India)



    Feb 28, 2018 ... complex in a unique binding motif and provide additional stability to the compound in the solid state. This iron(II) complex is able to catalyze the cleavage of aromatic C-C linkage of 2,5-dihydroxybenzoic acid (Gentisic acid,. GA) in oxygen environment. The iron(II) complex in the presence of two equivalent ...

  19. (II) complexes

    African Journals Online (AJOL)

    activities of Schiff base tin (II) complexes. Neelofar1 ... Conclusion: All synthesized Schiff bases and their Tin (II) complexes showed high antimicrobial and ...... Singh HL. Synthesis and characterization of tin (II) complexes of fluorinated Schiff bases derived from amino acids. Spectrochim Acta Part A: Molec Biomolec.

  20. Nuclear inelastic scattering and density-functional-theory calculations on the understanding of the vibronic properties of polynuclear iron complexes

    International Nuclear Information System (INIS)

    Faus, Isabelle


    Transition metal complexes of 3d elements with an electronic configuration of d 4 to d 8 can show a temperature dependent spin transition. This process is called spin crossover (SCO) effect and describes the transition between two states, the low spin (LS) state and the high spin (HS) state. In the LS state the spin is as low as possible, caused by none or a minimal number of unpaired electrons. In the HS state the spin is as high as possible with a maximal number of unpaired electrons. Because of this bistability, SCO materials are promising candidates for innovative molecular storage devices. Directly related to the SCO effect is the cooperativity, which specifies the interaction of metal centers between molecules (intermolecular cooperativity) or in a molecule (intramolecular cooperativity). Cooperativity is of vital importance for the switching behavior of SCO complexes with broad hysteresis. Therefore, three dinuclear SCO complexes which show a varying degree of cooperativity due to different geometries of their bridging ligands were investigated. By means of nuclear inelastic scattering (NIS), it could be clarified whether it is possible to find intramolecular cooperative effects in the vibrational patterns of these complexes. With corresponding density functional theory (DFT) calculations, it was possible for all of the dinuclear complexes to correlate the experimental NIS bands to the corresponding molecular vibrational modes. In the LS-LS or HS-HS state of the three complexes two modes exist lying energetically close together, which show a similar movement of the whole complex, with only a difference in the movement of the iron atoms. Thereby, the irons are moving either in the same or in the opposite direction. For complexes with a high degree of cooperativity there are nearly exclusively small energy shifts between this kind of nearly twofold energetically degenerated modes (ΔE <7 cm -1 ), for the complex with a low degree of cooperativity there are

  1. Half-sandwich d6 metal complexes with bis(pyridine carboxamide)benzene ligand: Synthesis and spectral analysis (United States)

    Aradhyula, Basava Punna Rao; Kaminsky, Werner; Kollipara, Mohan Rao


    The reactions of [(arene)MCl2]2 dimers with the 1,4-bis(2-pyridine carboxamido)benzene (H2L) have been reported here with the formulations as [(arene)MCl(HL)] {where, arene = p-cymene, M = Ru (1), arene = Cp*, M = Rh (2) and Ir (3)}and [{(arene)MCl}2L] {where, arene = p-cymene, M = Ru (4), arene = Cp*, M = Rh (5) and Ir (6)}, which resulted in a series of mono- and di-nuclear neutral complexes. These complexes have been characterized by various spectral analyses. Complexes 2-6 are additionally described by the single crystal X-ray diffraction studies. Single crystal X-ray analyses of complexes showed that they are neutral in nature and vicinity around the metal is distorted octahedral. The chloride atoms and Cp* moieties are in cis orientation with respect to the ligand in the case of complex 6. Complexes 2, 3 and 5 are crystallized with the solvent dichloromethane molecule.

  2. Single crystal EPR study of the dinuclear Cu(II) complex [Cu(tda)(phen)](2)·H(2)tda (tda = thiodiacetate, phen = phenanthroline): influence of weak interdimeric magnetic interactions. (United States)

    Neuman, Nicolás I; Perec, Mireille; González, Pablo J; Passeggi, Mario C G; Rizzi, Alberto C; Brondino, Carlos D


    We report powder and single crystal EPR measurements of [Cu(tda)(phen)](2)·H(2)tda (tda = thiodiacetate, phen = phenanthroline) at 9.7 GHz. This compound consists of centrosymmetric copper(II) ion dimers, weakly ferromagnetically exchange-coupled (J = +3.2 cm(-1)), in which the dimeric units are linked by hydrophobic chemical paths involving the phen molecules. EPR revealed that the triplet spectra are collapsed by interdimeric exchange interactions mediated by that chemical path. Analysis and simulation of the single crystal EPR spectra were performed using Anderson's exchange narrowing model, together with statistical arguments. This approach allowed us to interpret the spectra modulated by the interdimeric interactions in situations of weak, intermediate, and strong exchange. We evaluated an interdimeric exchange constant J' = 0.0070(3) cm(-1), indicating that hydrophobic paths can transmit weak exchange interactions between centers at relatively long distances of the order of ∼10 Å.

  3. Mechanistic Insight into Reversible Core Structural Changes of Dinuclear μ-Hydroxoruthenium(II) Complexes with a 2,8-Di-2-pyridyl-1,9,10-anthyridine Backbone Prior to Water Oxidation Catalysis. (United States)

    Hirahara, Masanari; Nagai, Sho; Takahashi, Kosuke; Watabe, Shunsuke; Sato, Taisei; Saito, Kenji; Yui, Tatsuto; Umemura, Yasushi; Yagi, Masayuki


    proximal,proximal-(p,p)-[Ru II 2 (tpy) 2 LXY] n+ (tpy = 2,2';6',2″-terpyridine, L = 5-phenyl-2,8-di-2-pyridyl-1,9,10-anthyridine, and X and Y = other coordination sites) yields the structurally and functionally unusual Ru II (μ-OH)Ru II core, which is capable of catalyzing water oxidation with key water insertion to the core (Inorg. Chem. 2015, 54, 7627). Herein, we studied a sequence of bridging-ligand substitution among p,p-[Ru 2 (tpy) 2 L(μ-Cl)] 3+ (Ru 2 (μ-Cl)), p,p-[Ru 2 (tpy) 2 L(μ-OH)] 3+ (Ru 2 (μ-OH)), p,p-[Ru 2 (tpy) 2 L(OH)(OH 2 )] 3+ (Ru 2 (OH)(OH 2 )), and p,p-[Ru 2 (tpy) 2 L(OH) 2 ] 2+ (Ru 2 (OH) 2 ) in aqueous solution. Ru 2 (μ-Cl) converted slowly (10 -4 s -1 ) to Ru 2 (μ-OH), and further Ru 2 (μ-OH) converted very slowly (10 -6 s -1 ) to Ru 2 (OH)(OH 2 ) by the insertion of water to reach equilibrium at pH 8.5-12.3. On the basis of density functional theory (DFT) calculations, Ru 2 (OH)(OH 2 ) was predicted to be thermodynamically stable by 13.3 kJ mol -1 in water compared to Ru 2 (μ-OH) because of the specially stabilized core structure by multiple hydrogen-bonding interactions involving aquo, hydroxo, and L backbone ligands. The observed rate from Ru 2 (μ-OH) to Ru 2 (OH) 2 by the insertion of an OH - ion increased linearly with an increase in the OH - concentration from 10 to 100 mM. The water insertion to the core is very slow (∼10 -6 s -1 ) in aqueous solution at pH 8.5-12.3, whereas the insertion of OH - ions is accelerated (10 -5 -10 -4 s -1 ) above pH 13.4 by 2 orders of magnitude. The kinetic data including activation parameters suggest that the associative mechanism for the insertion of water to the Ru II (μ-OH)Ru II core of Ru 2 (μ-OH) at pH 8.5-12.3 alters the interchange mechanism for the insertion of an OH - ion to the core above pH 13.4 because of relatively stronger nucleophilic attack of OH - ions. The hypothesized p,p-[Ru 2 (tpy) 2 L(μ-OH 2 )] 4+ and p,p-[Ru 2 (tpy) 2 L(OH 2 ) 2 ] 4+ formed by protonation from Ru 2 (μ-OH) and Ru 2 (OH)(OH 2 ) were predicted to be unstable by 71.3 and 112.4 kJ mol -1 compared to Ru 2 (μ-OH) and Ru 2 (OH)(OH 2 ), respectively. The reverse reactions of Ru 2 (μ-OH), Ru 2 (OH)(OH 2 ), and Ru 2 (OH) 2 to Ru 2 (μ-Cl) below pH 5 could be caused by lowering the core charge by protonation of the μ-OH - or OH - ligand.

  4. Pseudo-base formation in the attempted synthesis of a conjugatively coupled bis(nitrosylruthenium) complex and spectroelectrochemistry of bipyrimidine-bridged dinuclear Ru(terpy)X precursor compounds (X = Cl, NO2)

    Czech Academy of Sciences Publication Activity Database

    Singh, P.; Sieger, M.; Fiedler, Jan; Su, Ch. Y.; Kaim, W.

    -, č. 7 (2008), s. 868-873 ISSN 1477-9226 R&D Projects: GA MŠk LC510; GA AV ČR IAA400400505 Institutional research plan: CEZ:AV0Z40400503 Keywords : Creutz-Taube ion * electron transfer * redox system * center-dot Subject RIV: CG - Electrochemistry Impact factor: 3.580, year: 2008

  5. Dysprosium complexes with mono-/di-carboxylate ligands—From simple dimers to 2D and 3D frameworks

    Energy Technology Data Exchange (ETDEWEB)

    Zhang, Yingjie, E-mail: [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); Scales, Nicholas; 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); Lu, Kim; Lumpkin, Gregory R. [Australian Nuclear Science and Technology Organization, Locked Bag 2001, Kirrawee DC, NSW 2232 (Australia)


    Four dysprosium (Dy) single carboxylates, a formate, a propionate, a butyrate and an oxalate have been synthesized and structurally characterized. The structure of Dy(HCO{sub 2}){sub 3} (1) contains nine-fold coordinated Dy polyhedra in perfect tricapped trigonal prisms. They are linked through trigonal O atoms forming 1D pillars which are further linked together through tricapped O atoms into a 3D pillared metal organic framework. The network structure is stable up to 360 °C. The structure of [Dy{sub 2}(C{sub 2}O{sub 4}){sub 3}(H{sub 2}O){sub 6}]·2.5H{sub 2}O (2) contains nine-fold coordinated Dy polyhedra linking together through μ{sub 2}-bridging oxalate anions into a 2D hexagonal layered structure. Both [Dy{sub 2}(Pr){sub 6}(H{sub 2}O){sub 4}]·(HPr){sub 0.5} (3) [Pr=(C{sub 2}H{sub 5}CO{sub 2}){sup −1}] and [Dy{sub 2}(Bu){sub 6}(H{sub 2}O){sub 4}] (4) [Bu=(C{sub 3}H{sub 7}CO{sub 2}){sup −1}] have similar di-nuclear structures. The Raman vibration modes of the complexes have been investigated. - Graphical abstract: Four dysprosium (Dy) complexes with formate, propionate, butyrate and oxalate ligands have been synthesized and characterized. The Dy formato complex has a 3D pillared metal organic framework and the structure is stable up to 360 °C whilst the complexes with longer alkyl chained mono-carboxylates possess similar di-nuclear structures. The Dy oxalato complex has a 2D hexagonal (honeycomb-type) structure. Their Raman vibration modes have been investigated. - Highlights: • New Dysprosium complexes with formate, propionate, butyrate and oxalate ligands. • Crystal structures range from dimers to two and three dimensional frameworks. • Vibrational modes have been investigated and correlated to the structures. • The complexes are thermal robust and stable to over 300 °C.

  6. Synthesis of nickel complexes with bidentate N,O-type ligands and application in the catalytic oligomerization of ethylene. (United States)

    Kermagoret, Anthony; Braunstein, Pierre


    The dinuclear complexes [Ni(micro-Cl){(4,5-dihydro-4,4-dimethyloxazol-2-yl)methanol}](2)Cl(2) and [Ni(micro-Cl){(pyridin-2-yl)methanol}](2)Cl(2) 16 have been synthesized in high yields by reaction of NiCl(2) with 2 mol. equiv. of the ligands 4,5-dihydro-4,4-dimethyloxazol-2-yl)methanol 13 or (pyridin-2-yl)methanol 15, respectively. The reaction of NiCl(2) with 3 mol. equiv. of 15 afforded in high yield the mononuclear, octahedral mer-[Ni{(pyridin-2-yl)methanol}(3)Cl(2)] complex 18. The reaction of 16 with NaH led to the deprotonation of one of the pyridine alcohol ligands to form [Ni{(pyridin-2-yl)methanol}{(pyridin-2-yl)methanolate}Cl] 21 in which the metal is coordinated by one pyridine alcohol and one pyridine alcoholate ligand. The crystal structures of the dinuclear, chloride-bridged octahedral complexes in 14.C(6)H(12) and in 16.3CH(2)Cl(2) and of the mononuclear, octahedral complex 18 in 18.CH(2)Cl(2) have been determined by X-ray diffraction. In the latter case, intermolecular OH...Cl bonding interactions generate a centrosymmetric pseudo-dimer. Complexes 14, 16, and 21 have been tested in ethylene oligomerization with AlEtCl(2) (Al/Ni ratios of 2, 4 or 6) or MAO (50, 100 or 200 equiv.) as co-catalysts under 10 bar of ethylene and yielded mostly dimers and trimers. Complex 16 in the presence of 6 equiv. of AlEtCl(2) proved to be the most active system with a turnover frequency (TOF) up to 187 500 C(2)H(4) (mol Ni h)(-1). Complex 16 with 200 equiv. of MAO was also the most active, with TOF up to 104 300 C(2)H(4) (mol Ni h)(-1) under 30 bar of ethylene.

  7. Complexity Plots

    KAUST Repository

    Thiyagalingam, Jeyarajan


    In this paper, we present a novel visualization technique for assisting the observation and analysis of algorithmic complexity. In comparison with conventional line graphs, this new technique is not sensitive to the units of measurement, allowing multivariate data series of different physical qualities (e.g., time, space and energy) to be juxtaposed together conveniently and consistently. It supports multivariate visualization as well as uncertainty visualization. It enables users to focus on algorithm categorization by complexity classes, while reducing visual impact caused by constants and algorithmic components that are insignificant to complexity analysis. It provides an effective means for observing the algorithmic complexity of programs with a mixture of algorithms and black-box software through visualization. Through two case studies, we demonstrate the effectiveness of complexity plots in complexity analysis in research, education and application. © 2013 The Author(s) Computer Graphics Forum © 2013 The Eurographics Association and Blackwell Publishing Ltd.

  8. Synthesis, Characterization, Luminescence and Biological Activity of Two Lanthanide Complexes Involving Mixed Ligands

    Energy Technology Data Exchange (ETDEWEB)

    Ma, Deyun; Guo, Haifu; Qin, Liang [Zhaoqing Univ., Zhaoqing (China); Xu, Jun [Jinan Univ., Guangzhou (China)


    Two new isostructural dinuclear complexes, Ln{sub 2}(4-cpa){sub 6}(bpy){sub 2} (Ln = Eu (1); Tb (2), 4-cpa = 4-chlorophenyl-acetate, bpy = 2,2'-bipyridine), have been hydrothermally synthesized and characterized by IR spectroscopy, elemental analysis, thermogravimetric analysis (TGA), powder X-ray diffraction and single-crystal X-ray diffraction. The lanthanide ions are bridged by two bidentate and two terdentate carboxylate groups to give centrosymmetric dimers with Ln···Ln separations of 3.967(2) and 3.956(3) A, respectively. Each metal atom is nine-coordinate and exhibits a distorted tricapped trigonal prismatic geometry. Three-dimensional fluorescence spectra show that both 1 and 2 emit bright red and green luminescence at room temperature, with long lifetimes of up to 0.369 ms (at 614 nm) and 0.432 ms (at 543 nm), respectively. Moreover, poor luminescence efficiency has been noted for complex 2. The 4-Hcpa ligand and complexes 1-2 have been screened for their phytogrowth-inhibitory activities against Brassica napus L. and Echinochloa crusgalli L., and the results are compared with the activity of quizalofop-P-ethyl.

  9. Synthesis and X-ray structure analysis of a new binuclear Schiff base Co(II) complex with the ligand N,N'-bis(3-methoxysalicylidene)-1,4-butanediamine

    Energy Technology Data Exchange (ETDEWEB)

    Nasr-Esfahani, M., E-mail: [Islamic Azad University, Najafabad Branch, Department of Materials Science and Engineering (Iran, Islamic Republic of)


    The title binuclear complex, tris[N,N-bis(3-methoxysalicylidene)-1,4-diaminobutane] dicobalt(II), C{sub 60}H{sub 70}Co{sub 2}N{sub 6}O{sub 15}, was prepared by the reaction of the tetradentate Schiff base ligand bis(3-methoxysalicylidene)-1,4-diaminobutane and Co(CH{sub 3}COO){sub 2} . 4H{sub 2}O in a ethanol solution and structurally characterized by single-crystal X-ray diffraction. This complex has a dinuclear structure where two Co(II) ions are bridged by one N{sup 0},N'-bis(3-methoxysalicylidene)-1,4-diaminobutane. The two Co(II) ions, have two distorted octahedral coordination involving two O and two N atoms.

  10. Complex odontoma. (United States)

    Preetha, A; Balikai, Bharati S; Sujatha, D; Pai, Anuradha; Ganapathy, K S


    Odontomas are hamartomatous lesions or malformations composed of mature enamel, dentin, and pulp. They may be compound or complex, depending on the extent of morphodifferentiation or their resemblance to normal teeth. The etiology of odontoma is unknown, although several theories have been proposed. This article describes a case of a large infected complex odontoma in the residual mandibular ridge, resulting in considerable mandibular expansion.

  11. Complex narratives

    NARCIS (Netherlands)

    Simons, J.


    This paper brings together narratology, game theory, and complexity theory to untangle the intricate nature of complex narratives in contemporary cinema. It interrogates the different terms - forking-path narratives, mind-game films, modular narratives, multiple-draft films, database narratives,

  12. Complexity Theory (United States)

    Lee, William H K.


    A complex system consists of many interacting parts, generates new collective behavior through self organization, and adaptively evolves through time. Many theories have been developed to study complex systems, including chaos, fractals, cellular automata, self organization, stochastic processes, turbulence, and genetic algorithms.

  13. Bis-ZnIIsalphen complexes bearing pyridyl functionalized ligands for efficient organic light-emitting diodes (OLEDs). (United States)

    Zhao, Jiang; Dang, Feifan; Liu, Boao; Wu, Yong; Yang, Xiaolong; Zhou, Guijiang; Wu, Zhaoxin; Wong, Wai-Yeung


    Inspired by the emissive features of Zn II complexes based on bis-Schiff base ligands, bis-Zn II salphen complexes bearing pyridyl functionalized ligands have been successfully synthesized. Their photophysical features, electrochemical behavior and electroluminescent (EL) properties have been investigated in detail. The functionalized bis-Zn II salphen complexes can exhibit high thermal stability up to 417 °C, and their photoluminescence (PL) spectra show a maximal emission wavelength peak at ca. 565 nm both in solution and PMMA doped films. The PL investigation of the neat films for these functionalized bis-Zn II salphen complexes indicated that the pyridyl functionalized ligands can effectively reduce the degree of molecular aggregation to enhance their emission intensity. Taking advantage of the charge carrier injection/transporting ability of the pyridyl functionalized ligands and their dendritic design, the optimized EL devices fabricated by a simple solution-processing method can achieve a peak luminance (L max ) of 3589 cd m -2 , a maximal external quantum efficiency (η ext ) of 1.46%, a maximal current efficiency (η L ) of 4.1 cd A -1 and a maximal power efficiency (η p ) of 3.8 lm W -1 . These results should afford important instructions for exploiting high performance fluorescent emitters based on dinuclear Zn II complexes.

  14. Complex variables

    CERN Document Server

    Fisher, Stephen D


    The most important topics in the theory and application of complex variables receive a thorough, coherent treatment in this introductory text. Intended for undergraduates or graduate students in science, mathematics, and engineering, this volume features hundreds of solved examples, exercises, and applications designed to foster a complete understanding of complex variables as well as an appreciation of their mathematical beauty and elegance. Prerequisites are minimal; a three-semester course in calculus will suffice to prepare students for discussions of these topics: the complex plane, basic

  15. Managing Complexity

    DEFF Research Database (Denmark)

    Maylath, Bruce; Vandepitte, Sonia; Minacori, Patricia


    This article discusses the largest and most complex international learning-by-doing project to date- a project involving translation from Danish and Dutch into English and editing into American English alongside a project involving writing, usability testing, and translation from English into Dutch...... and into French. The complexity of the undertaking proved to be a central element in the students' learning, as the collaboration closely resembles the complexity of international documentation workplaces of language service providers. © Association of Teachers of Technical Writing....

  16. Synthesis and characterization of novel M(II (M = Mn(II, Ni(II, Cu(II or Zn(II complexes with tridentate N2,O-donor ligand (E-2-amino-N’-[1-(pyridin-2-yl- ethylidene]benzohydrazide

    Directory of Open Access Journals (Sweden)

    C. H. Kane


    Full Text Available The coordination chemistry towards the M(II metal centre (M = Mn, Ni, Cu or Zn of the hydrazone ligand (E-2-amino-N’-[1-(pyridin-2-ylethylidene]benzohydrazide (H3L has been explored and complexes having formulae [Mn(H2L2] (1, {[Ni(H2L2].DMF.0.4H2O} (2, {[Cu2(H2L2(µ-Cl2].DMF} (3 and [Zn(H2L2] (4 have been isolated and characterized by IR, UV-Visible spectroscopy, elemental analysis and X-ray crystal diffraction. Structural studies reveal that the mononuclear complexes (1, (2 and (4 adopt highly distorted octahedral geometries while the dinuclear complex (3 adopts a square pyramidal geometry around each copper(II ion. DOI:

  17. Complex Covariance

    Directory of Open Access Journals (Sweden)

    Frieder Kleefeld


    Full Text Available According to some generalized correspondence principle the classical limit of a non-Hermitian quantum theory describing quantum degrees of freedom is expected to be the well known classical mechanics of classical degrees of freedom in the complex phase space, i.e., some phase space spanned by complex-valued space and momentum coordinates. As special relativity was developed by Einstein merely for real-valued space-time and four-momentum, we will try to understand how special relativity and covariance can be extended to complex-valued space-time and four-momentum. Our considerations will lead us not only to some unconventional derivation of Lorentz transformations for complex-valued velocities, but also to the non-Hermitian Klein-Gordon and Dirac equations, which are to lay the foundations of a non-Hermitian quantum theory.

  18. Communication Complexity

    Indian Academy of Sciences (India)

    Jaikumar Radhakrishnan

    Alice and Bob are randomized agents. They exchange messages in order to compute a function f(x, y). We allow a small probability of error. Goal: minimize the total number of bits transmitted. Jaikumar Radhakrishnan. Communication Complexity ...

  19. Synthesis, crystallographic and spectral studies of homochiral cobalt(II) and nickel(II) complexes of a new terpyridylaminoacid ligand (United States)

    Wang, Xing; Gao, Chang-Qing; Gao, Zhi-Yang; Wu, Ben-Lai; Niu, Yun-Yin


    Based on a chiral terpyridylaminoacid ligand, a series of homochiral Co(II) and Ni(II) complexes, namely, [Co(H2L)(HL)]·Cl·(PF6)2·2H2O (1), [Ni(H2L)(HL)]·Cl·(PF6)2 (2), [Co2(L)2(CH3OH)(H2O)]·(PF6)2·CH3OH (3), [Ni2(L)2(CH3OH)2]·(PF6)2·2CH3OH (4), [Co2(L)2(N3)2]·3H2O (5), and [Ni2(L)2(SCN)2]·4H2O (6) have been successfully synthesized and characterized by elemental analysis, TGA, spectroscopic methods (IR, CD and electronic absorption spectra) and single-crystal X-ray diffraction structural analysis (HL = (S)-2-((4-([2,2':6‧,2″-terpyridin]-4‧-yl)benzyl)amino)-4-methylpentanoic acid). In the acidic reaction conditions, one protonated (H2L)+ and one zwitterionic HL only used their terpyridyl groups to chelate one metal ion Co(II) or Ni(II), forming chiral mononuclear cationic complexes 1 or 2. But in the basic and hydro(solvo)thermal reaction conditions, deprotonated ligands (L)‒ acting as bridges used their terpyridyl and amino acid groups to link with two Co(II) or Ni(II) ions, fabricating chiral dinuclear metallocyclic complexes 3-6. Those chiral mononuclear and dinuclear complexes whose chirality originates in the homochiral ligand HL further self-assemble into higher-dimensional homochiral supramolecular frameworks through intermolecular hydrogen-bonding and π···π interactions. Notably, the coordination mode, hydrogen-bonding site, and existence form of HL ligand can be controlled by the protonation of its amino group, and the architectural diversity of those supramolecular frameworks is adjusted by pH and counter anions. Very interestingly, the 3D porous supramolecular frameworks built up from the huge chiral mononuclear cationic complexes 1 and 2 have novel helical layers only formed through every right-handed helical chain intertwining with two adjacent same helical chains, and the 2D supramolecular helicate 5 consists of two types of left-handed helical chains.

  20. X-ray and vibrational spectroscopy of manganese complexes relevant to the oxygen-evolving complex of photosynthesis

    Energy Technology Data Exchange (ETDEWEB)

    Visser, Hendrik [Univ. of California, Berkeley, CA (United States)


    Manganese model complexes, relevant to the oxygen-evolving complex (OEC) in photosynthesis, were studied with Mn K-edge X-ray absorption near-edge spectroscopy (XANES), Mn Kb X-ray emission spectroscopy (XES), and vibrational spectroscopy. A more detailed understanding was obtained of the influence of nuclearity, overall structure, oxidation state, and ligand environment of the Mn atoms on the spectra from these methods. This refined understanding is necessary for improving the interpretation of spectra of the OEC. Mn XANES and Kb XES were used to study a di-(mu)-oxo and a mono-(mu)-oxo di-nuclear Mn compound in the (III,III), (III,IV), and (IV,IV) oxidation states. XANES spectra show energy shifts of 0.8 - 2.2 eV for 1-electron oxidation-state changes and 0.4 - 1.8 eV for ligand-environment changes. The shifts observed for Mn XES spectra were approximately 0.21 eV for oxidation state-changes and only approximately 0.04 eV for ligand-environment changes. This indicates that Mn Kb XES i s more sensitive to the oxidation state and less sensitive to the ligand environment of the Mn atoms than XANES. These complimentary methods provide information about the oxidation state and the ligand environment of Mn atoms in model compounds and biological systems. A versatile spectroelectrochemical apparatus was designed to aid the interpretation of IR spectra of Mn compounds in different oxidation states. The design, based on an attenuated total reflection device, permits the study of a wide spectral range: 16,700 (600 nm) - 225

  1. Synthesis and evaluation of new polynuclear organometallic Ru(II), Rh(III) and Ir(III) pyridyl ester complexes as in vitro antiparasitic and antitumor agents. (United States)

    Chellan, Prinessa; Land, Kirkwood M; Shokar, Ajit; Au, Aaron; An, Seung Hwan; Taylor, Dale; Smith, Peter J; Riedel, Tina; Dyson, Paul J; Chibale, Kelly; Smith, Gregory S


    New polynuclear organometallic Platinum Group Metal (PGM) complexes containing di- and tripyridyl ester ligands have been synthesised and characterised using analytical and spectroscopic techniques including (1)H, (13)C NMR and infrared spectroscopy. Reaction of these polypyridyl ester ligands with either [Ru(p-cymene)Cl2]2, [Rh(C5Me5)Cl2]2 or [Ir(C5Me5)Cl2]2 dimers yielded the corresponding di- or trinuclear organometallic complexes. The polyaromatic ester ligands act as monodentate donors to each metal centre and this coordination mode was confirmed upon elucidation of the molecular structures for two of the dinuclear complexes. The di- and trinuclear PGM complexes synthesized were evaluated for inhibitory effects on the human protozoal parasites Plasmodium falciparum strain NF54 (chloroquine sensitive), Trichomonas vaginalis strain G3 and the human ovarian cancer cell lines, A2780 (cisplatin-sensitive) and A2780cisR (cisplatin-resistant) cell lines. All of the complexes were observed to have moderate to high antiplasmodial activities and the compounds with the best activities were evaluated for their ability to inhibit formation of synthetic hemozoin in a cell free medium. The in vitro antitumor evaluation of these complexes revealed that the trinuclear pyridyl ester complexes demonstrated moderate activities against the two tumor cell lines and were also less toxic to model non-tumorous cells.

  2. The preparation and use of metal salen complexes derived from cyclobutane diamine (United States)

    Patil, Smita

    The helix is an important chiral motif in nature, there is increasing development in field of helical transition metal complexes and related supramolecular structures. Hence, the goals of this work are to apply the principles of helicity in order to produce metal complexes with predictable molecular shapes and to study their properties as asymmetric catalysts. Computational studies suggest that the (1R,2 R)-cyclobutyldiamine unit can produce highly twisted salen complexes with a large energy barrier between the M and P helical forms. To test this prediction, the tartrate salt of (1R,2R)-cyclobutyldiamine was synthesized and condensed with a series of saliclaldehydes to produce novel salen ligands. The salicylaldehydes chosen have extended phenanthryl or benz[a]anthryl sidearms to encourage formation of helical coordination complexes. These ligands were metallated with zinc, iron and manganese salts to produce salen metal complexes which were characterized by NMR analysis, high-resolution mass spectrometry, and IR spectroscopy. A second ligand type, neutral bis(pyridine-imine) has also been synthesized from (1R,2R)-cyclobutyldiamine and quinolylaldehydes. The synthesis of bis(pyridine-imine) ligands was conducted using greener method, solvent assisted grinding. These ligands, in-situ with nickel metal salts, showed good catalytic activity for asymmetric Diels-Alder reactions. The third ligand type studied was chiral acid-functionalized Schiff-base ligands. These were synthesized by the condensation of 3-formyl-5-methyl salicylic acid and (1R,2R)-cyclobutyldiamine. With this type of ligand, there is possibility of producing both mono and dinuclear metal complexes. In our studies, we were only able to synthesize mononuclear complexs. These were tested as catalysts for asymmetric direct Mannich-type reaction, but were found to be ineffective.

  3. Broken Symmetry DFT Calculations/Analysis for Oxidized and Reduced Dinuclear Center in Cytochrome c Oxidase: Relating Structures, Protonation States, Energies, and Mössbauer Properties in ba3 Thermus thermophilus. (United States)

    Han Du, Wen-Ge; Noodleman, Louis


    The Fea3(3+)···CuB(2+) dinuclear center (DNC) structure of the as-isolated oxidized ba3 cytochrome c oxidase (CcO) from Thermus thermophilus (Tt) is still not fully understood. When the proteins are initially crystallized in the oxidized state, they typically become radiolyticly reduced through X-ray irradiation. Several X-ray crystal structures of reduced ba3 CcO from Tt are available. However, depending on whether the crystals were prepared in a lipidic cubic phase environment or in detergent micelles, and whether the CcO's were chemically or radiolyticly reduced, the X-ray diffraction analysis of the crystals showed different Fea3(2+)···CuB(+) DNC structures. On the other hand, Mössbauer spectroscopic experiments on reduced and oxidized ba3 CcOs from Tt (Zimmermann et al., Proc. Natl. Acad. Sci. USA 1988, 85, 5779-5783) revealed multiple (57)Fea3(2+) and (57)Fea3(3+) components. Moreover, one of the (57)Fea3(3+) components observed at 4.2 K transformed from a proposed "low-spin" state to a different high-spin species when the temperature was increased above 190 K, whereas the other high-spin (57)Fea3(3+) component remained unchanged. In the current Article, in order to understand the heterogeneities of the DNC in both Mössbauer spectra and X-ray crystal structures, the spin crossover of one of the (57)Fea3(3+) components, and how the coordination and spin states of the Fea3(3+/2+) and Cu(2+/1+) sites relate to the heterogeneity of the DNC structures, we have applied density functional OLYP calculations to the DNC clusters established based on the different X-ray crystal structures of ba3 CcO from Tt. As a result, specific oxidized and reduced DNC structures related to the observed Mössbauer spectra and to spectral changes with temperature have been proposed. Our calculations also show that, in certain intermediate states, the His233 and His283 ligand side chains may dissociate from the CuB(+) site, and they may become potential proton loading sites

  4. Synthesis, crystal structure and magnetic properties of a novel copper(II) complex with sulfoisophthalic acid (United States)

    Kurc, Teresa; Videnova-Adrabinska, Veneta; Turowska-Tyrk, Ilona; Duczmal, Marek; Jerzykiewicz, Maria


    A new Cu(II) complex, [Cu2(μ2-OH2)2(HSIP)2(H2O)6] (H3SIP = 5-sulfoisophthalic acid), has been synthesized and characterized by single crystal X-ray diffraction, EPR spectroscopy (X- (9.5 GHz) and Q-band (35 GHz)) and magnetic measurements. The solid state structure of the complex consists of coordination dimers [Cu2(μ2-OH2)2(HSIP)2(H2O)6] which are hydrogen bonded into 3D network. The neighbouring metal ions form a rare example of centrosymetric dinuclear core [Cu2(μ2-OH2)2] with equatorial - axial positions of the bridging ligands. The coordination dimers are organized into inorganic monolayers via water-sulfonate hydrogen bond intractions, and further linked in 3D structure via carboxylic-carboxylic hydrogen bond intractions. The magnetic properties and EPR spectra are discussed in terms of crystal structure features. The X- and Q-band EPR spectra exhibit fine structure signals due to S = 1 and the simulated parameters indicate small zero field splitting parameter Dexp (-0.035 cm-1) dominated by Ddip (-0.031 cm-1). A usually forbidden ΔMs = 2 line of lower intensity is observed in the half field region at about 150 mT. The susceptibility data have been analyzed using a spin-ladder model with both ferromagnetic (rungs) and antiferromagnetic (legs) coupling.

  5. Single-molecule magnet behavior in 2,2’-bipyrimidine-bridged dilanthanide complexes

    Directory of Open Access Journals (Sweden)

    Wen Yu


    Full Text Available A series of 2,2’-bipyrimidine-bridged dinuclear lanthanide complexes with the general formula [Ln(tmhd3]2bpm (tmhd = 2,2,6,6-tetramethyl-3,5-heptanedionate, bpm = 2,2’-bipyrimidine, Ln = Gd(III, 1; Tb(III, 2; Dy(III, 3; Ho(III, 4 and Er(III, 5 has been synthesized and characterized. Sublimation of [Tb(tmhd3]2bpm onto a Au(111 surface leads to the formation of a homogeneous film with hexagonal pattern, which was studied by scanning tunneling microscopy (STM. The bulk magnetic properties of all complexes have been studied comprehensively. The dynamic magnetic behavior of the Dy(III and Er(III compounds clearly exhibits single molecule magnet (SMM characteristics with an energy barrier of 97 and 25 K, respectively. Moreover, micro-SQUID measurements on single crystals confirm their SMM behavior with the presence of hysteresis loops.

  6. Complex analysis

    CERN Document Server

    Freitag, Eberhard


    The guiding principle of this presentation of ``Classical Complex Analysis'' is to proceed as quickly as possible to the central results while using a small number of notions and concepts from other fields. Thus the prerequisites for understanding this book are minimal; only elementary facts of calculus and algebra are required. The first four chapters cover the essential core of complex analysis: - differentiation in C (including elementary facts about conformal mappings) - integration in C (including complex line integrals, Cauchy's Integral Theorem, and the Integral Formulas) - sequences and series of analytic functions, (isolated) singularities, Laurent series, calculus of residues - construction of analytic functions: the gamma function, Weierstrass' Factorization Theorem, Mittag-Leffler Partial Fraction Decomposition, and -as a particular highlight- the Riemann Mapping Theorem, which characterizes the simply connected domains in C. Further topics included are: - the theory of elliptic functions based on...

  7. Complex Analysis

    CERN Document Server

    Stein, Elias M


    With this second volume, we enter the intriguing world of complex analysis. From the first theorems on, the elegance and sweep of the results is evident. The starting point is the simple idea of extending a function initially given for real values of the argument to one that is defined when the argument is complex. From there, one proceeds to the main properties of holomorphic functions, whose proofs are generally short and quite illuminating: the Cauchy theorems, residues, analytic continuation, the argument principle.With this background, the reader is ready to learn a wealth of additional m

  8. Complex manifolds

    CERN Document Server

    Morrow, James


    This book, a revision and organization of lectures given by Kodaira at Stanford University in 1965-66, is an excellent, well-written introduction to the study of abstract complex (analytic) manifolds-a subject that began in the late 1940's and early 1950's. It is largely self-contained, except for some standard results about elliptic partial differential equations, for which complete references are given. -D. C. Spencer, MathSciNet The book under review is the faithful reprint of the original edition of one of the most influential textbooks in modern complex analysis and geometry. The classic

  9. Halide/pseudohalide complexes of cadmium(II) with benzimidazole: Synthesis, crystal structures and fluorescence properties (United States)

    Zhao, Hai-Yan; Yang, Fu-Li; Li, Na; Wang, Xiao-Jing


    Two new dinuclear Cd(II) complexes, [CdL1Cl2]2·H2O (1) and [CdL1(N3)2]2·CH3OH (2) and one dicyanamide bridged one-dimensional polynuclear network [CdL1(μ1,5-dca)dca]n (3) of the potentially tridentate NNN-donor Schiff base 2-((1H-benzimidazol-2-yl-ethylimino)-methyl)pyridine (L1) and another dinucler Cd(II) complex [CdL2Cl(dca)]2 (4) of a similar NNN-donor Schiff base ligand 2-((1H-benzimidazol-2-yl-propylimino)-methyl)pyridine (L2), have been synthesized and characterized by elemental analyses, IR and single crystal X-ray crystallography. The ligands L1 and L2 are [1 + 1] condensation products of pyridine-2-carbaldehyde with 2-aminoethyl-1H-benzimidazole and 2-aminopropyl-1H-benzimidazole, respectively. In the complexes 1 and 4 the two Cd(II) centers are held together by the bridged chloride ligands, while in 2 the two Cd(II) centers are bridged by μ1,1-azide ions. Complex 3 has a one-dimensional infinite chain structure in which Cd(II) ions are bridged by single dicyanamide groups in end-to-end fashion. All the metal centers have a distorted octahedral geometry and H-bonding or π⋯π interactions are operative to bind the complex units in the solid state. Furthermore, these complexes have been investigated by thermogravimetric analyses and fluorescence spectra.

  10. Hexa- and heptacoordinated manganese(II) dicyanamide complexes containing a tetradentate N-donor Schiff base: Syntheses, composition tailored architectures and magnetic properties (United States)

    Bhar, Kishalay; Sutradhar, Dipu; Choubey, Somnath; Ghosh, Rajarshi; Lin, Chia-Her; Ribas, Joan; Ghosh, Barindra Kumar


    Two 1D coordination polymers [Mn(L)(μ1,5-dca)(MeOH)]n(ClO4)n (1) and [Mn(L)(μ1,5-dca)]n(PF6)n (2) and a dinuclear compound [Mn2(L)2(μ1,5-dca)2(dca)2]ṡH2O (3) [L = N,N'-(bis-(pyridin-2-yl)benzylidene)-ethane-1,2-diamine; dca = dicyanamide] have been isolated using one-pot synthesis of the building components in appropriate molar ratios and characterized. X-ray structural studies reveal that 1 forms a zigzag 1D chain through single Mn-(NCNCN)-Mn units in which each heptacoordinated manganese(II) center adopts a distorted pentagonal bipyramidal geometry with an MnN6O chromophore occupied with four N atoms of L, two nitrile N atoms of monobridged μ1,5-dca and one O atom of MeOH. In 2, each hexacoordinated metal(II) center has a distorted octahedral coordination environment with an MnN6 chromophore bound by four N atoms of L and two nitrile N atoms of two different single bridged μ1,5-dca units; the latter connects other neighboring metal centers in a non-ending fashion affording a linear 1D chain. Complex 3 is dinuclear where two [Mn(L)]2+ units are connected by double μ1,5-dca bridges with a distorted pentagonal bipyramidal environment. Variable-temperature magnetic susceptibility measurements of 1-3 show weak antiferromagnetic interactions among the metal centers through μ1,5-dca bridges.

  11. Communication Complexity

    Indian Academy of Sciences (India)

    Jaikumar Radhakrishnan

    Communication complexity. Motivation . . . An abstract model to study the communicaiton required for computation. A tool for showing lower bounds in several computational models. The study often requires deep understanding of computation using tools from combinatorics, coding theory, algebra, analysis, etc. Jaikumar ...

  12. Lecithin Complex

    African Journals Online (AJOL)

    1Department of Food Science and Engineering, Xinyang College of Agriculture and Forestry, Xinyang 464000, 2Henan. Economy and Trade ... Methanol of HPLC grade was purchased from Tedia (USA). Other chemicals used were of analytical grade. Preparation of polydatin-lecithin complex. Polydatin (200 mg) and ...

  13. Complex Networks

    CERN Document Server

    Evsukoff, Alexandre; González, Marta


    In the last decade we have seen the emergence of a new inter-disciplinary field focusing on the understanding of networks which are dynamic, large, open, and have a structure sometimes called random-biased. The field of Complex Networks is helping us better understand many complex phenomena such as the spread of  deseases, protein interactions, social relationships, to name but a few. Studies in Complex Networks are gaining attention due to some major scientific breakthroughs proposed by network scientists helping us understand and model interactions contained in large datasets. In fact, if we could point to one event leading to the widespread use of complex network analysis is the availability of online databases. Theories of Random Graphs from Erdös and Rényi from the late 1950s led us to believe that most networks had random characteristics. The work on large online datasets told us otherwise. Starting with the work of Barabási and Albert as well as Watts and Strogatz in the late 1990s, we now know th...

  14. Complex chemistry with complex compounds

    Directory of Open Access Journals (Sweden)

    Eichler Robert


    Full Text Available In recent years gas-phase chemical studies assisted by physical pre-separation allowed for the investigation of fragile single molecular species by gas-phase chromatography. The latest success with the heaviest group 6 transactinide seaborgium is highlighted. The formation of a very volatile hexacarbonyl compound Sg(CO6 was observed similarly to its lighter homologues molybdenum and tungsten. The interactions of these gaseous carbonyl complex compounds with quartz surfaces were investigated by thermochromatography. Second-generation experiments are under way to investigate the intramolecular bond between the central metal atom of the complexes and the ligands addressing the influence of relativistic effects in the heaviest compounds. Our contribution comprises some aspects of the ongoing challenging experiments as well as an outlook towards other interesting compounds related to volatile complex compounds in the gas phase.

  15. New complexes of Cu(II) with dipicolinate and pyridyl-based ligands: An experimental and DFT approach. (United States)

    Luzardo, Florencia; Álvarez, Natalia; Kremer, Carlos; de Camargo, Andrea S S; Gancheff, Jorge S


    The three novel mononuclear copper(II) complexes with dipicolinate and pyridyl-based ligands [Cu(dipic)(L)(OH 2 )] (L=4-picoline, vinylpyridine, 4-styrylpyridine; dipic 2- =dipicolinate) were afforded and structurally characterized. X-ray diffraction studies accounted for slight distorted square-pyramidal structures in which the dianion dipic 2- acts as a tridentate ligand in a mer-fashion, the N-donor species occupy an in-plane position, and a water molecule was detected apically coordinated. To assess the effect of the nature of the pyridyl-substituent (para position) on electronic properties, other complexes were also synthesized: [Cu(dipic)(py)(OH 2 )], [{Cu(dipic)(OH 2 )} 2 (μ-pyz)] and [{Cu(dipic)(OH 2 )}(μ-pypy){Cu(dipic)}] (py=pyridine, pyz=pyrazine, pypy=(E)-1,2-bis(pyridine-4-yl)ethane). Absorptive behavior in the UV-VIS region was studied in solution and in the solid state (reflectance measurements). Additionally, geometry and population analyses were conducted by means of DFT calculations. Electronic UV-VIS spectra were simulated for both dinuclear complexes in the framework of the TD-DFT methodology to assign the origin of the absorption bands. Copyright © 2017 Elsevier B.V. All rights reserved.

  16. Synthesis and structural study of platinum group metal complexes ...

    Indian Academy of Sciences (India)

    als by a number of ways yielding mono and dinu- clear compounds. It can also coordinate through pyri- dine and pyrazolyl nitrogens or nitrogens of pyrimidine and pyrazolyl group to form mono and dinuclear com- plexes. However, in the ..... This downfield chemical shift of phosphorus nucleus indicates the formation of ...

  17. Managing Complexity

    Energy Technology Data Exchange (ETDEWEB)

    Chassin, David P.; Posse, Christian; Malard, Joel M.


    Physical analogs have shown considerable promise for understanding the behavior of complex adaptive systems, including macroeconomics, biological systems, social networks, and electric power markets. Many of today’s most challenging technical and policy questions can be reduced to a distributed economic control problem. Indeed, economically-based control of large-scale systems is founded on the conjecture that the price-based regulation (e.g., auctions, markets) results in an optimal allocation of resources and emergent optimal system control. This paper explores the state of the art in the use physical analogs for understanding the behavior of some econophysical systems and to deriving stable and robust control strategies for them. In particular we review and discussion applications of some analytic methods based on the thermodynamic metaphor according to which the interplay between system entropy and conservation laws gives rise to intuitive and governing global properties of complex systems that cannot be otherwise understood.

  18. Time complexity and gate complexity

    International Nuclear Information System (INIS)

    Koike, Tatsuhiko; Okudaira, Yosuke


    We formulate and investigate the simplest version of time-optimal quantum computation theory (TO-QCT), where the computation time is defined by the physical one and the Hamiltonian contains only one- and two-qubit interactions. This version of TO-QCT is also considered as optimality by sub-Riemannian geodesic length. The work has two aims: One is to develop a TO-QCT itself based on a physically natural concept of time, and the other is to pursue the possibility of using TO-QCT as a tool to estimate the complexity in conventional gate-optimal quantum computation theory (GO-QCT). In particular, we investigate to what extent is true the following statement: Time complexity is polynomial in the number of qubits if and only if gate complexity is also. In the analysis, we relate TO-QCT and optimal control theory (OCT) through fidelity-optimal computation theory (FO-QCT); FO-QCT is equivalent to TO-QCT in the limit of unit optimal fidelity, while it is formally similar to OCT. We then develop an efficient numerical scheme for FO-QCT by modifying Krotov's method in OCT, which has a monotonic convergence property. We implemented the scheme and obtained solutions of FO-QCT and of TO-QCT for the quantum Fourier transform and a unitary operator that does not have an apparent symmetry. The former has a polynomial gate complexity and the latter is expected to have an exponential one which is based on the fact that a series of generic unitary operators has an exponential gate complexity. The time complexity for the former is found to be linear in the number of qubits, which is understood naturally by the existence of an upper bound. The time complexity for the latter is exponential in the number of qubits. Thus, both the targets seem to be examples satisfyng the preceding statement. The typical characteristics of the optimal Hamiltonians are symmetry under time reversal and constancy of one-qubit operation, which are mathematically shown to hold in fairly general situations.

  19. Welding complex

    Energy Technology Data Exchange (ETDEWEB)

    Lebedev, V.K.; Kuchuk-Yatsenko, S.I.; Sakharnov, V.A.; Galyan, B.A.; Krivenko, V.G.; Asoyants, G.B.


    A welding complex for construction of a continuous underwater pipeline is adapted to be installed aboard a ship. The complex includes a welding machine positionable at a joint of the pipeline with a pipe section to be welded, burr-removing trimmers positionable coaxially with the pipeline for displacement relative to the pipeline in the joint area, and a support device for the end part of the pipeline. A rotatably mounted holding device for setting, holding, and retaining the pipe section to be welded, the welding machine, and the trimmers is axially aligned with the end part of the pipeline. An accumulator is provided for storing and delivering successive pipe sections at a loading position laterally offset from the common axis of the pipeline and of the pipe section to be welded to it. The holding device includes a platform movable along the common axis of the pipeline and of the pipe section to be welded to it by a resistance butt welding machine, and a plate with a means for carrying the pipe section to be welded which is mounted on a pivot carried by the platform for rotation between the loading position and the aligning position. The welding complex of the invention provides for implementing resistance butt welding in construction of continuous underwater pipelines and ensures the accuracy of alignment and permanence of the gap between the edges being welded. The welding complex's structure allows handling of longer pipe sections, thus reducing the overall number of joints to be welded. 7 figs.

  20. Synthesis, structure and electrochemistry of cationic diruthenium complexes of the type [(N∩N)2Ru2 (CO)2 (μ-CO)2(μ-OOCFc)]+ containing a ferrocenecarboxylato bridge and two chelating aromatic diimine ligands


    Auzias, Mathieu; Therrien, Bruno; Süss-Fink, Georg; Štěpnička, Petr; Ludvík, Jiří


    The dinuclear bis(ferrocenecarboxylato) complex Ru2 (CO)4 (μ-OOCFc)2 (py)2 (Fc = ferrocenyl, py = pyridine) was found to react with aromatic diimines (2,2′-dipyridyl, 4,4′-dimethyl-2,2′-dipyridyl, 1,10-phenanthroline, 5-nitro-1,10-phenanthroline, and 5-amino-1,10-phenanthroline) in methanol to give the cationic diruthenium complexes [(N∩N)2Ru2 (CO)2 (μ-CO)2(μ-OOCFc)]+ (1: N∩N = 2,2′-dipyridyl, 2: N∩N = 4,4′-dimethyl-2,2′-dipyridyl, 3: N∩N = 1,10-phenanthroline, 4: N∩N = 5-nitro-1,10-phenanthr...

  1. Electrochemical Water Oxidation and Stereoselective Oxygen Atom Transfer Mediated by a Copper Complex. (United States)

    Kafentzi, Maria-Chrysanthi; Papadakis, Raffaello; Gennarini, Federica; Kochem, Amélie; Iranzo, Olga; Le Mest, Yves; Le Poul, Nicolas; Tron, Thierry; Faure, Bruno; Simaan, A Jalila; Réglier, Marius


    Water oxidation by copper-based complexes to form dioxygen has attracted attention in recent years, with the aim of developing efficient and cheap catalysts for chemical energy storage. In addition, high-valent metal-oxo species produced by the oxidation of metal complexes in the presence of water can be used to achieve substrate oxygenation with the use of H 2 O as an oxygen source. To date, this strategy has not been reported for copper complexes. Herein, a copper(II) complex, [(RPY2)Cu(OTf) 2 ] (RPY2=N-substituted bis[2-pyridyl(ethylamine)] ligands; R=indane; OTf=triflate), is used. This complex, which contains an oxidizable substrate moiety (indane), is used as a tool to monitor an intramolecular oxygen atom transfer reaction. Electrochemical properties were investigated and, upon electrolysis at 1.30 V versus a normal hydrogen electrode (NHE), both dioxygen production and oxygenation of the indane moiety were observed. The ligand was oxidized in a highly diastereoselective manner, which indicated that the observed reactivity was mediated by metal-centered reactive species. The pH dependence of the reactivity was monitored and correlated with speciation deduced from different techniques, ranging from potentiometric titrations to spectroscopic studies and DFT calculations. Water oxidation for dioxygen production occurs at neutral pH and is probably mediated by the oxidation of a mononuclear copper(II) precursor. It is achieved with a rather low overpotential (280 mV at pH 7), although with limited efficiency. On the other hand, oxygenation is maximum at pH 8-8.5 and is probably mediated by the electrochemical oxidation of an antiferromagnetically coupled dinuclear bis(μ-hydroxo) copper(II) precursor. This constitutes the first example of copper-centered oxidative water activation for a selective oxygenation reaction. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  2. Polymer-Supported Optically Active fac(S)-Tris(thiotato)rhodium(III) Complex for Sulfur-Bridging Reaction With Precious Metal Ions. (United States)

    Aizawa, Sen-Ichi; Tsubosaka, Soshi


    The optically active mixed-ligand fac(S)-tris(thiolato)rhodium(III) complexes, ΔL -fac(S)-[Rh(aet)2 (L-cys-N,S)](-) (aet = 2-aminoethanethiolate, L-cys = L-cysteinate) () and ΔLL -fac(S)-[Rh(aet)(L-cys-N,S)2 ](2-) were newly prepared by the equatorial preference of the carboxyl group in the coordinated L-cys ligand. The amide formation reaction of with 1,10-diaminodecane and polyallylamine gave the diamine-bridged dinuclear Rh(III) complex and the single-chain polymer-supported Rh(III) complex with retention of the ΔL configuration of , respectively. These Rh(III) complexes reacted with Co(III) or Co(II) to give the linear-type trinuclear structure with the S-bridged Co(III) center and the two Δ-Rh(III) terminal moieties. The polymer-supported Rh(III) complex was applied not only to the CD spectropolarimetric detection and determination of a trace of precious metal ions such as Au(III), Pt(II), and Pd(II) but also to concentration and extraction of these metal ions into the solid polymer phase. Chirality 28:85-91, 2016. © 2015 Wiley Periodicals, Inc. © 2015 Wiley Periodicals, Inc.

  3. Synthesis, Characterization and Antibacterial Activity of Novel 1,3-Diethyl-1,3-bis(4-nitrophenylurea and Its Metal(II Complexes

    Directory of Open Access Journals (Sweden)

    Hoda Pasdar


    Full Text Available A bioactive ligand and its dinuclear metal(II complexes were synthesized and characterized by Fourier-transform infrared spectroscopy (FT-IR, ultraviolet-visible (UV-Visible, nuclear magnetic resonance (1H-NMR, mass spectroscopy and molar conductance measurements. The ligand has been crystalized in the monoclinic system with a P21/c space group. The biological activities of metal complexes were evaluated using disc diffusion and broth dilution methods. In vitro antibacterial activities of the ligand and their metal complexes were examined against two Gram-positive bacteria (Bacillus subtilis and Staphylococcus aureus and two Gram-negative bacteria (Escherichia coli and Serratia marcescens and compared to the standard drugs. It was found that metal complexes displayed much higher antibacterial activities and better inhibitory effects than that of the ligand and standard drugs. Among these complexes, the compound having Zn-metal showed greater antibacterial activity against all four tested bacteria and was more effective against Serratia marcescens with the zone inhibition diameter of 26 mm and MIC value of 31.25 µg/mL.

  4. Achieving High-Performance Solution-Processed Orange OLEDs with the Phosphorescent Cyclometalated Trinuclear Pt(II) Complex. (United States)

    Yang, Xiaolong; Jiao, Bo; Dang, Jing-Shuang; Sun, Yuanhui; Wu, Yong; Zhou, Guijiang; Wong, Wai-Yeung


    Cyclometalated Pt(II) complexes can show intense phosphorescence at room temperature. Their emission properties are determined by both the organic ligand and the metal center. Whereas most of the related studies focus on tuning the properties by designing different types of organic ligands, only several reports investigate the key role played by the metal center. To address this issue, phosphorescent Pt(II) complexes with one, two, and three Pt(II) centers are designed and synthesized. With more Pt(II) centers, the cyclometalated multinuclear Pt(II) complexes display red-shifted emissions with increased photoluminescence quantum yields. Most importantly, solution-processed organic light-emitting diodes (OLEDs) with the conventional device structure using the multinuclear Pt(II) complexes as emitters show excellent performance. The controlled device based on the conventional mononuclear Pt(II) complex shows a peak external quantum efficiency, current efficiency, and power efficiency of 6.4%, 14.4 cd A -1 , and 12.1 lm W -1 , respectively. The efficiencies are dramatically improved to 10.5%, 21.4 cd A -1 , and 12.9 lm W -1 for the OLED based on the dinuclear Pt(II) complex and to 17.0%, 35.4 cd A -1 , and 27.2 lm W -1 for the OLED based on the trinuclear Pt(II) complex, respectively. To the best of our knowledge, these efficiencies are among the highest ever reported for the multinuclear Pt(II) complex-based OLEDs.

  5. Complex variables

    CERN Document Server

    Flanigan, Francis J


    A caution to mathematics professors: Complex Variables does not follow conventional outlines of course material. One reviewer noting its originality wrote: ""A standard text is often preferred [to a superior text like this] because the professor knows the order of topics and the problems, and doesn't really have to pay attention to the text. He can go to class without preparation."" Not so here-Dr. Flanigan treats this most important field of contemporary mathematics in a most unusual way. While all the material for an advanced undergraduate or first-year graduate course is covered, discussion

  6. Magneto-structural correlations in trinuclear Cu(II) complexes: a density functional study

    CERN Document Server

    Rodríguez-Forteá, A; Alvarez, S; Centre-De Recera-En-Quimica-Teorica; Alemany, P A; Centre-De Recera-En-Quimica-Teorica


    Density functional theoretical methods have been used to study magneto-structural correlations for linear trinuclear hydroxo-bridged copper(II) complexes. The nearest-neighbor exchange coupling constant shows very similar trends to those found earlier for dinuclear compounds for which the Cu-O-Cu angle and the out of plane displacement of the hydrogen atoms at the bridge are the two key structural factors that determine the nature of their magnetic behavior. Changes in these two parameters can induce variations of over 1000 cm sup - sup 1 in the value of the nearest-neighbor coupling constant. On the contrary, coupling between next-nearest neighbors is found to be practically independent of structural changes with a value for the coupling constant of about -60 cm sup - sup 1. The magnitude calculated for this coupling constant indicates that considering its value to be negligible, as usually done in experimental studies, can lead to considerable errors, especially for compounds in which the nearest-neighbor c...

  7. Humidity-controlled rectification switching in ruthenium-complex molecular junctions (United States)

    Atesci, Huseyin; Kaliginedi, Veerabhadrarao; Celis Gil, Jose A.; Ozawa, Hiroaki; Thijssen, Joseph M.; Broekmann, Peter; Haga, Masa-aki; van der Molen, Sense Jan


    Although molecular rectifiers were proposed over four decades ago1,2, until recently reported rectification ratios (RR) were rather moderate2-11 (RR 101). This ceiling was convincingly broken using a eutectic GaIn top contact12 to probe molecular monolayers of coupled ferrocene groups (RR 105), as well as using scanning tunnelling microscopy-break junctions13-16 and mechanically controlled break junctions17 to probe single molecules (RR 102-103). Here, we demonstrate a device based on a molecular monolayer in which the RR can be switched by more than three orders of magnitude (between RR 100 and RR ≥ 103) in response to humidity. As the relative humidity is toggled between 5% and 60%, the current-voltage (I-V) characteristics of a monolayer of di-nuclear Ru-complex molecules reversibly change from symmetric to strongly asymmetric (diode-like). Key to this behaviour is the presence of two localized molecular orbitals in series, which are nearly degenerate in dry circumstances but become misaligned under high humidity conditions, due to the displacement of counter ions (PF6-). This asymmetric gating of the two relevant localized molecular orbital levels results in humidity-controlled diode-like behaviour.

  8. Complex dynamics

    CERN Document Server

    Carleson, Lennart


    Complex dynamics is today very much a focus of interest. Though several fine expository articles were available, by P. Blanchard and by M. Yu. Lyubich in particular, until recently there was no single source where students could find the material with proofs. For anyone in our position, gathering and organizing the material required a great deal of work going through preprints and papers and in some cases even finding a proof. We hope that the results of our efforts will be of help to others who plan to learn about complex dynamics and perhaps even lecture. Meanwhile books in the field a. re beginning to appear. The Stony Brook course notes of J. Milnor were particularly welcome and useful. Still we hope that our special emphasis on the analytic side will satisfy a need. This book is a revised and expanded version of notes based on lectures of the first author at UCLA over several \\Vinter Quarters, particularly 1986 and 1990. We owe Chris Bishop a great deal of gratitude for supervising the production of cour...

  9. Complex Systems

    Directory of Open Access Journals (Sweden)

    Yi Zhao


    Full Text Available Quantum instanton (QI approximation is recently proposed for the evaluations of the chemical reaction rate constants with use of full dimensional potential energy surfaces. Its strategy is to use the instanton mechanism and to approximate time-dependent quantum dynamics to the imaginary time propagation of the quantities of partition function. It thus incorporates the properties of the instanton idea and the quantum effect of partition function and can be applied to chemical reactions of complex systems. In this paper, we present the QI approach and its applications to several complex systems mainly done by us. The concrete systems include, (1 the reaction of H+CH4→H2+CH3, (2 the reaction of H+SiH4→H2+SiH3, (3 H diffusion on Ni(100 surface; and (4 surface-subsurface transport and interior migration for H/Ni. Available experimental and other theoretical data are also presented for the purpose of comparison.

  10. Cosmic Complexity (United States)

    Mather, John C.


    What explains the extraordinary complexity of the observed universe, on all scales from quarks to the accelerating universe? My favorite explanation (which I certainty did not invent) ls that the fundamental laws of physics produce natural instability, energy flows, and chaos. Some call the result the Life Force, some note that the Earth is a living system itself (Gaia, a "tough bitch" according to Margulis), and some conclude that the observed complexity requires a supernatural explanation (of which we have many). But my dad was a statistician (of dairy cows) and he told me about cells and genes and evolution and chance when I was very small. So a scientist must look for me explanation of how nature's laws and statistics brought us into conscious existence. And how is that seemll"!gly Improbable events are actually happening a!1 the time? Well, the physicists have countless examples of natural instability, in which energy is released to power change from simplicity to complexity. One of the most common to see is that cooling water vapor below the freezing point produces snowflakes, no two alike, and all complex and beautiful. We see it often so we are not amazed. But physlc!sts have observed so many kinds of these changes from one structure to another (we call them phase transitions) that the Nobel Prize in 1992 could be awarded for understanding the mathematics of their common features. Now for a few examples of how the laws of nature produce the instabilities that lead to our own existence. First, the Big Bang (what an insufficient name!) apparently came from an instability, in which the "false vacuum" eventually decayed into the ordinary vacuum we have today, plus the most fundamental particles we know, the quarks and leptons. So the universe as a whole started with an instability. Then, a great expansion and cooling happened, and the loose quarks, finding themselves unstable too, bound themselves together into today's less elementary particles like protons and

  11. Synthesis and ferromagnetically coupled heterodinuclear oxamido-bridged copper(II)-oxovanadium(IV) complexes

    International Nuclear Information System (INIS)

    Li Yantuan; Yan Cuiwei; Wu Zhiyong; Zhu Chunyuan


    Three novel copper(II)-oxovanadium(IV) heterodinuclear complexes bridged by dianions of N,N'-oxamidobis(propionato)cuprate, [Cu(obp)], and endcapped with 2,9-dimethyl-1,10-phenanthroline (Me 2 phen), 4,7-diphenyl-1,10-phenanthroline (Ph 2 phen) or 5-methyl-1,10-phenanthroline (Mephen), respectively, have been synthesized and identified as [Cu(obp)VO(Me 2 phen)] (1), [Cu(obp)VO(Ph 2 phen)] (2) and [Cu(obp)VO(Mephen)] (3). The three dinuclear complexes have not yet been isolated in crystalline form suitable for X-ray structure analysis, but based on elemental analyses, IR and electronic spectra studies, magnetic moments at room temperature and molar conductivity measurements, these complexes are proposed to have an extended oxamido-bridged structure consisting of planar copper(II) and square-pyramidal oxovanadium(IV) ions. The three heterodinuclear complexes were further characterized by variable-temperature magnetic susceptibility (4.2-300K) measurements and the magnetic data have been used to deduce the indicated heterodinuclear structure. The results derived from least-squares fit of the experimental data have confirmed that the operation of a ferromagnetic interaction between the adjacent copper(II) and oxovanadium(IV) ions through the oxamido bridge within each molecule takes place. Based on spin Hamiltonian, H at=-2JS at 1 .S at 2 , the exchange integral (J) was evaluated as J=+21.9cm -1 for (1), J=+18.8cm -1 for (2) and +26.5cm -1 for (3). The influence of the symmetry of the magnetic orbitals and different terminal ligands on the nature and magnitude of the magnetic interaction between the paramagnetic centers is also discussed

  12. Multiple Bistability in Quinonoid-Bridged Diiron(II) Complexes: Influence of Bridge Symmetry on Bistable Properties. (United States)

    van der Meer, Margarethe; Rechkemmer, Yvonne; Breitgoff, Frauke D; Marx, Raphael; Neugebauer, Petr; Frank, Uta; van Slageren, Joris; Sarkar, Biprajit


    Quinonoid bridges are well-suited for generating dinuclear assemblies that might display various bistable properties. In this contribution we present two diiron(II) complexes where the iron(II) centers are either bridged by the doubly deprotonated form of a symmetrically substituted quinonoid bridge, 2,5-bis[4-(isopropyl)anilino]-1,4-benzoquinone (H 2 L2') with a [O,N,O,N] donor set, or with the doubly deprotonated form of an unsymmetrically substituted quinonoid bridge, 2-[4-(isopropyl)anilino]-5-hydroxy-1,4-benzoquinone (H 2 L5') with a [O,O,O,N] donor set. Both complexes display temperature-induced spin crossover (SCO). The nature of the SCO is strongly dependent on the bridging ligand, with only the complex with the [O,O,O,N] donor set displaying a prominent hysteresis loop of about 55 K. Importantly, only the latter complex also shows a pronounced light-induced spin state change. Furthermore, both complexes can be oxidized to the mixed-valent iron(II)-iron(III) form, and the nature of the bridge determines the Robin and Day classification of these forms. Both complexes have been probed by a battery of electrochemical, spectroscopic, and magnetic methods, and this combined approach is used to shed light on the electronic structures of the complexes and on bistability. The results presented here thus show the potential of using the relatively new class of unsymmetrically substituted bridging quinonoid ligands for generating intriguing bistable properties and for performing site-specific magnetic switching.

  13. Synthesis, structure, terahertz spectroscopy and luminescent properties of copper (I) complexes with bis(diphenylphosphino)methane and N-donor ligands (United States)

    Fan, Wei-Wei; Li, Zhong-Feng; Li, Jiao-Bao; Yang, Yu-Ping; Yuan, Yuan; Tang, Han-Qin; Gao, Ling-Xiao; Jin, Qiong-Hua; Zhang, Zhen-Wei; Zhang, Cun-Lin


    The reactions of copper(I) salts CuX [X = Cl, OTf (OTf = CF3SO3) and ClO4] and bis(diphenylphosphino)methane (dppm) with 4,4-bipyridine (4,4-bipy), 2,2-bipyridine (2,2-bipy), isoquinoline (i-C9H7N) and 1,10-phenanthroline (phen) lead to five new copper(I) complexes: [CuCl(dppm)(i-C9H7N)]2 (1), {[CuCl(dppm)(phen)]2•5H2O}n (2), [Cu2Cl2(dppm)2(4,4-bipy)]•4CH3CN (3), [Cu(dppm)(2,2-bipy)]2(OTf)2 (4), {[Cu2Cl(dppm)2(4,4-bipy)](ClO4)}n (5). Complexes 1, 3 and 4 are of dinuclear structure with eight-membered Cu2P4C2 rings. The structure of compound 2 can be simplified as three-dimensional topology. Complex 5 is of infinite chain structure linked by 4,4-bipy. All these complexes are characterized by IR, elemental analyses, single-crystal X-ray diffraction analysis, luminescence, NMR and terahertz time-domain spectroscopy.

  14. A computational study of structural and magnetic properties of bi- and trinuclear Cu(II) complexes with extremely long Cu-Cu distances (United States)

    Baryshnikov, Gleb V.; Minaev, Boris F.; Baryshnikova, Alina T.; Ågren, Hans


    Three recently synthesized copper(II) complexes with aroylhydrazones of trifluoroacetic and benzenecarboxylic acids (Dalton Trans., 2013, 42, 16878) have been computationally investigated by density functional theory within the broken symmetry approximation accounting for empirical dispersion corrections. A topological analysis of electron density distributions has been carried out using Bader's ;quantum theory of atoms in molecules; formalism. The calculated values of spin-spin exchange for the studied dinuclear complexes indicate a very weak ferromagnetic coupling of the unpaired electrons in good agreement with experimental data. At the same time, the trinuclear copper(II) complex possesses a low-spin doublet ground state with one ferromagnetic and two antiferromagnetic spin projections between the triangular-positioned Cu2+ ions. The estimated values of the coupling constants for the spin-spin exchange in this trinuclear complex are in a good agreement with experimental observations. The calculations support a mechanism of exchange coupling through the aromatic links in these strongly spin-separated systems.

  15. Different emissive properties in dithiolate gold(i) complexes as a function of the presence of phenylene spacers. (United States)

    Monzittu, Francesco M; Fernández-Moreira, Vanesa; Lippolis, Vito; Arca, Massimiliano; Laguna, Antonio; Gimeno, M Concepción


    A family of dinuclear neutral thiolate gold complexes of the type RPh2PAuS(C6H4)nSAuPPh2R (n = 2, 3), RPh2PAuS(C6H4)S(C6H4)SAuPPh2R, RPh2PAuSCH2(C6H4)2CH2SAuPPh2R where R represents a pyridine or a phenylene ring, has been prepared and fully characterized. X-ray crystallographic studies showed the presence of aurophilic interactions for those species bearing two phenylene spacers between the gold metal centers, leading to infinite chains. The complexes are emissive in the solid state. Theoretical calculations together with the photophysical analysis seem to indicate that the main excitations involved in the emissive processes are due to a mixture of ILCT transition involving the thiolate and the conjugated phenylene rings, and LL'CT transitions comprising the thiolate and the pyridine or phenyl from the phosphine fragment which contrast with the typical gold thiolate emission, LMCT from the thiolate fragment to the metal center.

  16. Lanthanide complexes with 2,3-dimethoxybenzoic acid and terpyridine. Crystal structures, thermal properties, and antibacterial activities

    Energy Technology Data Exchange (ETDEWEB)

    Shen, Pan-Pan; Wu, Xiao-Hui; Zhang, Jian-Jun [Testing and Analysis Center, Hebei Normal University, Shijiazhuang (China); College of Chemistry and Material Science, Hebei Normal University, Shijiazhuang (China); Ren, Ning [College of Chemical Engineering and Material, Handane College (China); Wang, Shu-Ping [College of Chemistry and Material Science, Hebei Normal University, Shijiazhuang (China)


    The lanthanide coordination complexes Er(2,3-DMOBA){sub 3}(terpy)(H{sub 2}O) (1) and [Nd(2,3-DMOBA){sub 3}(terpy)(H{sub 2}O)]{sub 2} (2) (2,3-DMOBA = 2,3-dimethoxybenzoate; terpy = 2,2':6',2{sup ''}-terpyridine) were synthesized and characterized by IR spectroscopy, powder X-ray diffraction (XRD), single-crystal X-ray diffraction, and thermogravimetric analysis. Complex 1 crystallizes in the triclinic system, space group P1, and the mononuclear subunits form a 1D chain structure along the a axis by hydrogen bonds. Complex 2 crystallizes in the monoclinic system, space group P2{sub 1}/c, and the dinuclear subunits are further linked via the offset face-to-face π..π weak stacking interactions to form a supramolecular 2D layered structure. Thermal analysis showed that the complexes have three decomposition steps. The first step is the loss of coordination water molecules. The neutral terpy ligands and partial 2,3-DMOBA ligands are lost in the second step. The remaining 2,3-DMOBA ligands are lost in the third step. The 3D stacked plots for the FT-IR spectra of the evolved gases are recorded and the gaseous products are identified by the typical IR spectra obtained at different temperatures from the 3D stacked plots. Meanwhile, the results of the antibacterial action tests show that 1 and 2 have better antibacterial activities to Candida albicans than to Escherichia coli or Staphylococcus aureus. In addition, complex 2 has better antibacterial action to Candida albicans than complex 1. (copyright 2017 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

  17. Synthesis and physicochemical characterization of two lead(II) complexes with O-, N-donor ligands. Lone pair functionality and crystal structure (United States)

    Masternak, Joanna; Barszcz, Barbara; Hodorowicz, Maciej; Khavryuchenko, Oleksiy V.; Majka, Alina


    A dinuclear [Pb2(4-CHO-5-MeIm)6(NO3)2](NO3)2 (1) and a polynuclear [Pb(2-pzc)2(H2O)]n (2) complexes (where 5(4)-carbaldehyde-4(5)-methylimidazole (5(4)-CHO-4(5)-MeIm) and pyrazine-2-carboxylic acid (2-pzcH)) have been synthesized and characterized by elemental analysis, IR spectroscopy and X-ray crystallography. Structural determination for complex 1 reveals a cationic species [Pb(4-CHO-5-MeIm)3]2+ connected through bridging nitrate(V) ions. There are also an uncoordinated nitrate ions as counterions. Complex 2 is a three-dimensional architecture consisting of Pb6O12 building units. The pyrazine-2-carboxylato ligand behaves as a chelating agent and a bi-connective bridge. The coordination polyhedra around lead(II) ion could be described as a distorted docecahedron (1) or monocapped trigonal prism (2). The luminescent properties of 1 and 2 investigated in the solid state at room temperature indicate structure-dependent photoluminescent properties. The DFT calculations and the X-ray structural data point on rather hemidirected type of coordination around Pb(II) ions of 1 and 2.

  18. Spacer-Controlled Supramolecular Assemblies of Cu(II with Bis(2-Hydroxyphenylimine Ligands. from Monoligand Complexes to Double-Stranded Helicates and Metallomacrocycles

    Directory of Open Access Journals (Sweden)

    Norman Kelly


    Full Text Available Reaction of Cu(NO32·3H2O or Cu(CH3COO2·H2O with the bis(2-hydroxyphenylimine ligands H2L1-H2L4 gave four Cu(II complexes of composition [Cu2(L1(NO32(H2O]·MeOH, [Cu2(L22], [Cu2(L32] and [Cu2(L42]·2MeOH. Depending on the spacer unit, the structures are characterized by a dinuclear arrangement of Cu(II within one ligand (H2L1, by a double-stranded [2+2] helical binding mode (H2L2 and H2L3 and a [2 + 2] metallomacrocycle formation (H2L4. In these complexes, the Cu(II coordination geometries are quite different, varying between common square planar or square pyramidal arrangements, and rather rare pentagonal bipyramidal and tetrahedral geometries. In addition, solution studies of the complex formation using UV/Vis and ESI-MS as well as solvent extraction are reported.

  19. The preparation and characterization of Cu(II complexes with N,N’,N”,N’”-tetrakis(2-pyridylmethyl-1,4,8,11-tetraazacyclotetradecane and 2,6-diacetylpyridine bis(semi/thiosemicarbazones

    Directory of Open Access Journals (Sweden)



    Full Text Available Two new Cu(II mixed-ligand complexes with octadentate N,N’,N”,N’”-tetrakis(2-pyridylmethyl-1,4,8,11-tetraazacyclotetradecane (tpmc and potentially pentadentate ligands 2,6-diacetylpyridine bis(semicarbazone (DAPsc2 or 2,6-diacetylpyridine bis(thiosemicarbazone (DAPtsc2 were prepared. The general formulas: [Cu4 DAPsc2(tpmc2]ClO48·5CH3COCH3·H2O and [Cu2 DAPtsc2(tpmc](ClO44·7C2H5OH were proposed on the basis of elemental analyses and conductometric measurements. The complexes were characterized by magnetic measurement, electronic absorption and IR spectroscopy. For the dinuclear complex, an exo coordination of Cu(II with four nitrogens from tpmc and m-bonded DAPtsc2 through sulfurs and possibly terminal hydrazinic (azomethine nitrogens is assumed. For the tetranuclear complex, it is supposed that one DAPsc2 bridges two [Cu2 tpmc]4+ units using oxygens and terminal hydrazinic nitrogens as ligators. Finally, some antibacterial activity of the complexes was found.

  20. A phosphino-oxazoline ligand as a P,N-bridge in palladium/cobalt or P,N-chelate in nickel complexes: catalytic ethylene oligomerization. (United States)

    Zhang, Shuanming; Pattacini, Roberto; Jie, Suyun; Braunstein, Pierre


    The Pd(II) complex [PdCl(2)(1)] [1 = ({oxazolin-2-yl}methyl)diphenylphosphine] was obtained by the 1:1 reaction of 1 with [PdCl(2)(NCPh)(2)]. Although this neutral complex is stable in the solid-state and in solution, it reacts with the dinuclear complex [CoCl(2)(μ-1)](2) to afford the heterometallic zwitterionic complex [{PdCl(1)}(+)(μ-1)(CoCl(3))(-)] (2). Under inert atmosphere, two equivalents of 1 reacted with [NiCl(2)(dme)] to give trans-[NiCl(2)(1)(2)] (3) in CH(2)Cl(2) but cis-[NiCl(2)(1)(2)] (4) in CHCl(3). When the latter reaction was performed in air, trans-[NiCl(2)(5)(2)] (6) [5 = ({oxazolin-2-yl}methyl)diphenylphosphine oxide] was obtained. All metal complexes, 2, 3, 4 and 6, have been structurally characterized by X-ray diffraction. Complexes 3, 4 and 6 have been evaluated as precatalysts for ethylene oligomerisation in the presence of AlEtCl(2) as cocatalyst. Complexes 3 and 6 yielded a turnover frequency (TOF) of 60,700 and 62,600 mol of C(2)H(4)/((mol of Ni)·h), respectively, in the presence of 10 equiv. of AlEtCl(2). In the presence of only 6 equiv. of cocatalyst, these Ni complexes yielded TOF values of 41,500 and 58,000 mol of C(2)H(4)/((mol of Ni)·h), respectively.

  1. Synthesis, structures, nuclease activity, cytotoxicity, DFT and molecular docking studies of two nitrato bridged homodinuclear (Cu-Cu, Zn-Zn) complexes containing 2,2'-bipyridine and a chalcone derivative. (United States)

    Gaur, Ruchi; Choubey, Diksha Kumari; Usman, Mohammad; Ward, Benzamin D; Roy, Jagat Kumar; Mishra, Lallan


    Nitrato briged dinuclear complexes of type [Cu 2 (L) 2 (bpy) 2 (NO 3 )](NO 3 )·4H 2 O, 1 and [Zn 2 (L) 2 (bpy) 2 (NO 3 )](NO 3 )·4H 2 O, 2 (L=deprotonated form of free ligand LH, [1-(2-hydroxyphenyl)-3-(9-anthracenyl) propenone; bpy=2,2'bipyridine] are synthesized and characterized using a battery of physicochemical techniques and X-ray crystallography. A distorted square pyramidal geometry is assigned to them with N 2 O 3 coordination core around the metal ion. The co-ligand L binds the metal ions through its O,O' atoms in anti-syn mode. The metal centers in complexes 1 and 2 are separated via bridging nitrato group at a distance of 6.073Å and 5.635Å respectively. Their structures and absorption spectra are supported by the computational studies using density functional theory (DFT) and TD-DFT. Both complexes exhibit nuclease activity and cleave supercoiled (form I) DNA. The complex 1 preferentially binds major groove of DNA and follows an oxidative pathway whereas complex 2 binds with minor groove of DNA via hydrolytic pathway. Both complexes inhibit topoisomerase I relaxation activity with IC 50 values of 7 and 35μM. Molecular docking studies support the groove binding and topoisomerase I binding of the complexes. The complex 1 showed a significant cytotoxicity against HeLa cell lines (a cervical cancer cell lines) in vitro with IC 50 value calculated as 2.9±0.021μM as compared to 28.2±0. 044μΜ for complex 2. Complex 2 induces the cell apoptosis at a later-stage as compared to complex 1. The cell apoptosis and topoisomerase inhibition by complexes enable them to be potential candidates as future anticancer drugs. Copyright © 2017 Elsevier B.V. All rights reserved.

  2. Synthesis, characterization and reactivity of group 4 metallocene bis(diphenylphosphino)acetylene complexes-a reactivity and bonding study. (United States)

    Haehnel, Martin; Hansen, Sven; Schubert, Kathleen; Arndt, Perdita; Spannenberg, Anke; Jiao, Haijun; Rosenthal, Uwe


    A study of the coordination chemistry of bis(diphenylphosphino)acetylene, Ph2P-C≡C-PPh2, with selected group 4 metallocenes is presented. By substitution of the alkyne in complexes of the type Cp'2M(L)(η(2)-Me3SiC2SiMe3) (M = Ti, no L; M = Zr, L = pyridine; Cp' = substituted or unsubstituted bridged or unbridged η(5)-cyclopentadienyl), the expected mononuclear complexes Cp*2Ti(η(2)-Ph2PC2PPh2) (4Ti), (rac-ebthi)Ti(η(2)-Ph2PC2PPh2) (5Ti), and (rac-ebthi)Zr(η(2)-Ph2PC2PPh2) (5Zr) [ebthi = ethylenebis(tetrahydroindenyl)] were obtained. When [Cp2Zr] was used in the reaction of Cp2Zr(py)(η(2)-Me3SiC2SiMe3) with Ph2P-C≡C-PPh2, the dinuclear complex [Cp2Zr(η(2)-Ph2PC2PPh2)]2 (6) was formed and isolated in the solid state. In solution, this complex is in equilibrium with the very spectacular structure of complex 7b as the first example of such a highly strained four-membered heterometallacycle of a group 4 metal, involving the rare R2PCCR' fragment in the cyclic unit. Both the stability and reactivity of heterodisubstituted alkynes X-C≡C-X (X = NR2, PR2, SR, SiR3, etc.) themselves and also of their complexes are of general interest. Complex 6 did not react with a second [Cp2Zr] fragment to form a homobimetallic complex. In contrast, for (rac-ebthi)Zr(η(2)-Ph2PC2PPh2) (5Zr) this reaction occurs. In the reaction of complex 4Ti with the Ni(0) complex (Cy3P)2Ni(η(2)-C2H4) (Cy = cyclohexyl), C-P bond cleavage of the alkyne ligand resulted in the formation of the isolated complex [(Cy3P)Ni(μ-PPh2)]2 (11). The structure and bonding of the complexes were investigated by DFT analysis to compare the different possible coordination modes of the R2P-C≡C-PR2 ligand. For compound 7b, a flip-flop coordination of the phosphorus atoms was proposed. Complexes 4Ti, 5Ti, 5Zr, 6, and 11 were characterized by X-ray crystallography.

  3. Synthesis, Crystal Structure, Spectroscopic Properties and Potential Biological Activities of Salicylate‒Neocuproine Ternary Copper(II Complexes

    Directory of Open Access Journals (Sweden)

    Lenka Kucková


    Full Text Available Mixed ligand copper(II complexes containing derivatives of salicylic acid and heterocyclic ligands with nitrogen donor atoms have been the subject of various studies and reviews. In this paper, synthesis and characterization of the ternary copper(II complexes of neocuproine (2,9-dimethyl-1,10-phenanthroline, Neo and salicylate ligands (Sal are reported. In addition, the crystal structures of ([Cu(H2O(5-Cl-Sal(Neo] (1, [Cu(μ-Sal(Neo]2 (2, Cu2(μ-5-Cl-Sal(5-Cl-HSal2(Neo2]·EtOH (3 were determined. In order to compare structural and biological properties of the prepared complexes, spectroscopic and biological studies were performed. Results of X-ray diffraction show that prepared complexes form three types of crystal structures in a given system: monomeric, dimeric and dinuclear complex. The preliminary study on the DNA cleavage activity has shown that the complexes under study behave as the chemical nucleases in the presence of added hydrogen peroxide with slight differences in the activity (1 > 2 > 3. The complexes 1 and 2 exhibited nuclease activity itself indicating the interaction of complexes with the DNA. It has been proposed that the enhanced destructive effect of the complexes 1 and 2 on the DNA is a result of two possible mechanisms of action: (i the conversion of closed circular DNA (form I to the nicked DNA (form II caused by the copper complex itself and (ii damage of DNA by Reactive Oxygen Species (ROS—products of the interaction of copper with hydrogen peroxide by means of Fenton reaction (hydroxyl radicals. Thus the biological activity of the prepared Cu(II complexes containing derivatives of salicylic acid and phenanthroline molecules is substantiated by two independent mechanisms. While derivatives of salicylic acids in the coordination sphere of copper complexes are responsible for radical-scavenging activity (predominantly towards superoxide radical anion, the presence of chelating ligand 2,9-dimethyl-1,10-phenanthroline

  4. Structure and Reactivity of Half-Sandwich Rh(+3) and Ir(+3) Carbene Complexes. Catalytic Metathesis of Azobenzene Derivatives. (United States)

    Tindall, Daniel J; Werlé, Christophe; Goddard, Richard; Philipps, Petra; Farès, Christophe; Fürstner, Alois


    Traditional rhodium carbene chemistry relies on the controlled decomposition of diazo derivatives with [Rh 2 (OAc) 4 ] or related dinuclear Rh(+2) complexes, whereas the use of other rhodium sources is much less developed. It is now shown that half-sandwich carbene species derived from [Cp*MX 2 ] 2 (M = Rh, Ir; X = Cl, Br, I, Cp* = pentamethylcyclopentadienyl) also exhibit favorable application profiles. Interestingly, the anionic ligand X proved to be a critical determinant of reactivity in the case of cyclopropanation, epoxide formation and the previously unknown catalytic metathesis of azobenzene derivatives, whereas the nature of X does not play any significant role in -OH insertion reactions. This perplexing disparity can be explained on the basis of spectral and crystallographic data of a representative set of carbene complexes of this type, which could be isolated despite their pronounced electrophilicity. Specifically, the donor/acceptor carbene 10a derived from ArC(═N 2 )COOMe and [Cp*RhCl 2 ] 2 undergoes spontaneous 1,2-migratory insertion of the emerging carbene unit into the Rh-Cl bond with formation of the C-metalated rhodium enolate 11. In contrast, the analogous complexes 10b,c derived from [Cp*RhX 2 ] 2 (X = Br, I) as well as the iridium species 13 and 14 derived from [Cp*IrCl 2 ] 2 are sufficiently stable and allow true carbene reactivity to be harnessed. These complexes are competent intermediates for the catalytic metathesis of azobenzene derivatives, which provides access to α-imino esters that would be difficult to make otherwise. Rather than involving metal nitrenes, the reaction proceeds via aza-ylides that evolve into diaziridines; a metastable compound of this type has been fully characterized.

  5. A chemical preformulation study of a host-guest complex of cucurbit[7]uril and a multinuclear platinum agent for enhanced anticancer drug delivery. (United States)

    Kennedy, Alan R; Florence, Alastair J; McInnes, Fiona J; Wheate, Nial J


    Single crystal and powder X-ray diffraction have been used to examine the host-guest complex of cucurbit[7]uril (CB[7]) and the model dinuclear platinum anticancer complex trans-[{PtCl(NH(3))(2)}(2)mu-dpzm](2+) (di-Pt, dpzm= 4,4'-dipyrazolylmethane). The single crystal structure shows that the host-guest complex forms with the di-Pt dpzm ligand within the CB[7] cavity and with the platinum groups just beyond the macrocycle portals. Binding is stabilised through hydrophobic interactions and six hydrogen bonds between the platinum ammine ligands and the dpzm pyrazole amine to the CB[7] carbonyls. Each host-guest complex crystallises with two chloride counterions and 5.5 water molecules. The unit cell comprises four asymmetric units, each of which contains three crystallographically independent CB[7]-di-Pt moieties. X-Ray powder diffraction demonstrated structural consistency of the bulk crystals with a single polycrystalline phase that is identical with the single crystal structure. Finally, the effect of CB[7] encapsulation of the thermal stability of di-Pt was examined by thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC). From the TGA experiments it was found that free CB[7] and the CB[7]-di-Pt complex lose 11 and 3.5% of their mass respectively, through the loss of water molecules, upon heating to 160 degrees C. The DSC results showed that the free dpzm ligand melts between 186 and 199 degrees C, with a standard enthalpy of fusion of 27.92 kJ mol(-1). As a 2+ inorganic salt the metal complex does not melt but undergoes several decomposition events between 140 and 290 degrees C. Encapsulation by CB[7] completely stabilises di-Pt with no decomposition of either the macrocycle or metal complex at temperatures up to 290 degrees C.

  6. Molecular Oxygen and Sulfur Reactivity of a Cyclotriveratrylene (CTV) Derived Trinuclear Copper(I) Complex (United States)

    Maiti, Debabrata; Woertink, Julia S.; Ghiladi, Reza A.; Solomon, Edward I.; Karlin, Kenneth D.


    Our continuing efforts into developing copper coordination chemistry relevant to dioxygen-processing copper proteins has led us to design and synthesize a cyclotriveratrylene (CTV)-based trinucleating ligand, CTV-TMPA, which employs tetradentate tris(2-pyridylmethyl)-amine chelates (TMPA) for their copper ion binding sites. Binding of three copper ions per CTV-TMPA unit was established by various chemical and spectroscopic methods such as UV-vis and resonance Raman (rR) spectroscopies. The following complexes were observed: A tricopper(I) complex [(CTV-TMPA)CuI3]3+ (1), a CO adduct [(CTV-TMPA)CuI3(CO)3]3+ (1-CO; ν(C=O) = 2094 cm−1), a triphenylphosphine adduct [(CTV-TMPA)CuI3(PPh3)3]3+ (1-PPh3), a tricopper(II) complex [(CTV-TMPA)CuII3]3+ (1-Ox) and its tris-monochloride or tris-monobromide adducts. Also, introduction of dioxygen to the −80 °C solutions of 1 leads to O2-adducts, the first example of a synthetic copper complex which can stabilize a mononuclear CuII-superoxo and dinuclear peroxo species simultaneously within one complex {[Cu] = 1.53 mM in THF: (μ-1,2-peroxo complex, λmax = 543 (ε 9650) nm): ν(O-O) = 825 ((Δ18O2) = −47) cm−1; ν(Cu-O) = 506 ((Δ18O2) = −26) cm−1: (superoxo complex, λmax = 427 (ε 3150) nm): ν(O-O) = 1129 ((Δ18O2) = −60) cm−1; ν(Cu-O) = 463 ((Δ18O2) =−27) cm−1}. Elemental sulfur reacts reversibly with 1 leading to a (proposed) hexanuclear species [{(CTV-TMPA)CuII3}2(μ-1,2-S22−)3]6+ (1-S) {λmax = 544 (ε 7270 nm }, possessing one dicopper(II)-disulfide structural type: {THF solvent) ν(S-S) = 489 ((Δ34S) = −10) cm−1; ν(Cu-S) = 506 ((Δ34S) = −5) cm−1}. Derivation of spectroscopic, structural and chemical conclusions were aided by the study of a close mononuclear analogue with one pyridyl group of the TMPA parent possessing a 6-CH2OCH3 substituent, this being part of the CTV-TMPA architecture. PMID:19663454

  7. Catalysis design for ring-opening polymerization of cyclic esters: 1. Group 1 metal and thallium(I) trispyrazolylborate complexes with hemilabile ligands. (United States)

    Chisholm, Malcolm H; Gallucci, Judith C; Yaman, Gülsah


    The synthesis of 3-(2-methoxy-1,1-dimethylethyl)pyrazole, pz*H is described together with its reactions with the borohydrides MBH(4), where M = Li, Na, and K, under melt conditions. At 180 degrees C, this procedure leads to a mixture of products for M = Li, and at higher temperatures, a derivative LiTp'pz*H, 1, is isolated, wherein a B-H bond and a methyl group have been eliminated and a B-O bond has been formed. For M = Na, the reaction proceeds to give the tris-pyrazolylborate derivative NaTp*, 2, but at higher temperatures the tetra-pyrazolylborate complex NaB(pz*)(4), 3, is obtained. The reactions involving KBH4 and pz*H yield the dinuclear complex K(2)(Tp*)(2)pz*H, 4. The reaction between NaTp* and TlOAc in CH(2)Cl(2) at room temperature leads to the formation of TlTp*, 5, along with NaOAc. Thallium 5 reacts with methyllithium in diethylether to give LiTp*, 6, and thallium metal, and, similarly, 5 and KH react in tetrahydrofuran to give KTp*, 7 and Tl(0). 1-7 have been characterized by elemental analysis, NMR spectroscopy, and by single-crystal X-ray studies, the latter of which reveal the versatile modes of binding for this new ligand bearing hemilabile ether appendages.

  8. DNA binding, cytotoxicity and apoptosis induction activity of a mixed-ligand copper(II) complex with taurine Schiff base and imidazole (United States)

    Li, Mei; kong, Lin Lin; Gou, Yi; Yang, Feng; Liang, Hong


    A novel binuclear copper(II) complex (complex 1) with taurine Schiff base and imidazole has been synthesized and structurally characterized by single crystal X-ray diffraction, elemental analysis, ESI-MS spectrometry, UV-vis and IR spectroscopy. Single-crystal analysis revealed that 1 displays the sulfonate-bridged dinuclear copper(II) centers. Both copper atoms are five-coordinated and exhibit slightly distorted square pyramidal geometries. Each of copper atom is surrounded by three oxygen atoms and one nitrogen atom from different taurine Schiff base ligands, and one nitrogen atom from one imidazole ligand. The interaction between 1 and calf thymus DNA (CT-DNA) was investigated by UV-vis, fluorescence, circular dichroism (CD) spectra and agarose gel electrophoresis. The experimental results indicated that 1 could bind to CT-DNA via an intercalative mode and show efficient cleavage activity. In addition, 1 showed an antitumor effect on cell cycle and apoptosis. Flow cytometric analysis revealed that MGC-803 cells were arrested in the S phase after treatment with 1. Fluorescence microscopic observation indicated that 1 could induce apoptosis of MGC-803 cells.

  9. Influence of inductive effects and steric encumbrance on the catecholase activities of copper(II) complexes of reduced Schiff base ligands. (United States)

    Thio, Yude; Yang, Xiandong; Vittal, Jagadese J


    A series of copper(ii) complexes derived from reduced Schiff base ligands has been synthesized and characterized by single-crystal X-ray diffraction and spectroscopic analyses. With the exception of [Cu(Ala5NO2)(H2O)] (), which crystallized as a mononuclear repeating unit, [Cu2L2(H2O)x(DMSO)y]·solvent (L = Ala5H (), Ala5OMe (), Ala5Cl (), Ala5Br (), Gly5Br (), Val5Br () and Leu5Br (), x = 1 or 2, y = 0 or 1, solvent = MeOH or DMSO and H2O) crystallized as phenoxo-bridged dinuclear building units containing Cu2O2 cores. In , , , and , the axial positions are occupied by solvent ligands and carboxylate oxygen atoms from adjacent dimers, resulting in the formation of 1D helical coordination polymers. In , a 2D network is constructed by utilizing weak CuO interactions (∼2.7 Å) with carboxylate groups. All complexes have been investigated for their catecholase activities with 3,5-DTBC, and they show significant catalytic activities except for . The catalytic activities are also observed to increase with increasing +I effects, as well as increase with increasing steric bulkiness on the α-carbon of the carboxylate group.

  10. Design and reactivity of mono- and polymetallic complexes of low valent f-elements

    International Nuclear Information System (INIS)

    Camp, Clement


    Beyond its importance in nuclear industry the redox chemistry uranium is attracting increasing interest because complexes of low-valent uranium can promote unusual reductive chemistry through unusual reaction pathways, including attractive examples of CO, CO 2 , N 2 , arenes and azides activation in mild condition. Due to the unique coordination and bonding properties of uranium, its compounds could provide an attractive alternative to transition metals for the catalytic transformation of small molecules. However, metal-based multi-electron processes remain uncommon in uranium chemistry especially in comparison with the d-block metals, the chemistry of low-valent uranium being dominated by single-electron transfers. In this context, the first aim of this project was to investigate the association of low-valent uranium to a non-innocent ligand acting as an independent electron reservoir at a same molecule. Accordingly, we interrogated the use of highly p-delocalized Schiff bases ligands for supporting low-valent uranium chemistry. This led to the isolation of electron-rich complexes which are stabilized by storing electrons on the ligands through the formation of C-C bonds. Interestingly, these C-C bonds can be cleaved by oxidizing agents and the electrons released to participate in multi-electron redox reactions. This process was observed within different Schiff-base ligand scaffolds, allowing a tuning of the properties of the compounds. The second part of this work was dedicated to the synthesis of novel trivalent uranium complexes supported by siloxy ligands and the study of their redox reactivity and coordination properties. Novel dinuclear highly-reactive low-valent uranium assemblies were developed. The study of their limited stability revealed that these compounds are spontaneously decomposing through the cleavage of tBu groups from the supporting ligands resulting in the formation of U(IV) species. In parallel, a mononuclear trivalent uranium complex was

  11. Bis(diphenylphosphino)methane-phosphonate ligands and their Pd(II), Ni(II) and Cu(I) complexes. Catalytic oligomerization of ethylene. (United States)

    Hamada, Adel; Braunstein, Pierre


    The bis(diphenylphosphino)methane-phosphonate-based (dppm-phosphonate) ligands (Ph(2)P)(2)CHP(O)(OR)(2) (R = Me, L(1); R = Ph, L(2)) form metal complexes by selective coordination of the diphosphine moiety to Pd(II) and Ni(II) centers. The formation of complexes containing the chelating, deprotonated form of ligand L(1) or L(2) occurred when basic ligands were present in the precursor complex, such as Me or dmba (on Pd(II)) or acac (on Ni(II)). The Cu(I) complex [CuL(1)](2)(BF(4))(2) (9) was obtained that is suggested to be dinuclear, each Cu(I) being chelated by a phosphine and a P=O donor and further bound to the phosphine group of another ligand. The crystal structures of the mononuclear complexes [PdCl(2){(Ph(2)P)(2)CHP(O)(OMe)(2)-P,P}] (2a), [PdCl(2){(Ph(2)P)(2)CHP(O)(OPh)(2)-P,P}] (2b), [Pd{(Ph(2)P)(2)CP(O)(OMe)(2)-P,P}(2)] (6a) in 6a.2CH(2)Cl(2), [Pd{(Ph(2)P)(2)CP(O)(OPh)(2)-P,P}(2)] (6b), [Ni{(Ph(2)P)(2)CP(O)(OMe)(2)-P,P}(2)] (10a) in 10a.4CHCl(3), [Ni{(Ph(2)P)(2)CP(O)(OPh)(2)-P,P}(2)] (10b) in 10b.4CHCl(3), [NiCl(2){(Ph(2)P)(2)CHP(O)(OMe)(2)-P,P}] (11a) in 11a.CHCl(3) and of the dinuclear complexes [Pd(mu-Cl){(Ph(2)P)(2)CP(O)(OMe)(2)-P,P}](2) (7a) and [Pd(mu-Cl){(Ph(2)P)(2)CP(O)(OPh)(2)-P,P}](2) (7b) have been determined by X-ray diffraction. The complexes [Ni{(Ph(2)P)(2)CC(O)NPh(2)-P,P}(2)] (13) and [Ni{Ph(2)PC(Ph)P(O)(OEt)(2)-P,O}(2)] (15) were prepared by reaction of [Ni(acac)(2)] with the known, neutral ligands (Ph(2)P)(2)CHC(O)NPh(2) and Ph(2)PCH(Ph)P(O)(OEt)(2), respectively. The Ni(II) complexes were evaluated for the catalytic oligomerization of ethylene and afforded similar results when AlEtCl(2) was used as cocatalyst. Complexes 11a,b were the most active, with a turnover frequency (TOF) of 78 300 mol of C(2)H(4)/(mol of Ni)h) for complex 11b in the presence of 10 equiv of AlEtCl(2) and showed a high selectivity for C(4) and C(6) olefins with up to 93% C(4) for 10a in the presence of 6 equiv AlEtCl(2), whereas when only 3 equiv cocatalyst was

  12. Complex analysis and geometry

    CERN Document Server

    Silva, Alessandro


    The papers in this wide-ranging collection report on the results of investigations from a number of linked disciplines, including complex algebraic geometry, complex analytic geometry of manifolds and spaces, and complex differential geometry.

  13. Complex Systems: An Introduction

    Indian Academy of Sciences (India)

    Home; Journals; Resonance – Journal of Science Education; Volume 14; Issue 9. Complex Systems: An Introduction - Anthropic Principle, Terrestrial Complexity, Complex Materials. V K Wadhawan. General Article Volume 14 Issue 9 September 2009 pp 894-906 ...

  14. New Mn(II, Ni(II, Cd(II, Pb(II complexes with 2-methylbenzimidazole and other ligands. Synthesis, spectroscopic characterization, crystal structure, magnetic susceptibility and biological activity studies

    Directory of Open Access Journals (Sweden)

    Shayma A. Shaker


    Full Text Available Synthesis and characterization of Mn(II, Ni(II, Cd(II and Pb(II mixed ligand complexes of 2-methylbenzimidazole with other ligands have been reported. The structure of the ligands and their complexes was investigated using elemental analysis, IR, UV–Vis, (1H, 13C NMR spectroscopy, molar conductivity and magnetic susceptibility measurements. In all the studies of complexes, the 2-methylbenzimidazole behaves as a neutral monodentate ligand which is coordinated with the metal ions through the N atom. While benzotriazole behaves as a neutral bidentate ligand which is coordinated with the Ni(II ion through the two N atoms. Moreover, the N-acetylglycine behaves as a bidentate ligand which is coordinated with the Mn(II, Ni(II and Pb(II ions through the N atom and the terminal carboxyl oxygen atom. The magnetic and spectral data indicate the tetrahedral geometry for Mn(II complex, irregular tetrahedral geometry for Pb(II complex and octahedral geometry for Ni(II complex. The X-ray single crystal diffraction method was used to confirm a centrosymmetric dinuclear Cd(II complex as each two metal ions are linked by a pair of thiocyanate N = S bridge. Two 2-methylbenzimidazole N-atom donors and one terminal thiocyanate N atom complete a highly distorted square pyramid geometry around the Cd atom. Besides, different cell types were used to determine the inhibitory effect of Mn(II, Ni(II, Cd(II and Pb(II complexes on cell growth using MTT assay. Cd(II complex showed cytotoxic effect on various types of cancer cell lines with different EC50 values.

  15. Synthesis of molecular complexes for small molecule activation

    International Nuclear Information System (INIS)

    Andrez, Julie


    The redox chemistry of f-elements is drawing the attention of inorganic chemists due to their unusual reaction pathways. Notably low-valent f-element complexes have been shown to be able to activate small molecules such as CO 2 and N 2 in mild conditions. Compared to d-block metals, f-elements present a coordination chemistry dominated by electrostatic interactions and steric constraints. Molecular complexes of f-elements could thus provide new catalytic routes to transform small molecules into valuable chemicals. However the redox chemistry of low valent f-elements is dominated by single-electron transfers while the reductions of CO 2 and N 2 require multi-electronic processes. Accordingly the first approach of this PhD work was the use of redox active ligands as electron reservoir to support f-element centres increasing the electron number available for reduction events. The coordination of uranium with tridentate Schiff base ligand was investigated and led to isolation of a dinuclear electron-rich species able to undertake up to eight-electron reduction combining the redox activity of the ligands and the uranium centres. In order to obtain electron-rich compounds potentially able to polarize the C=O bond of CO 2 , the synthesis of hetero-bimetallic species supported by salophen Schiff base ligand was also studied. In a second approach we have used bulky ligands with strong donor-character to tune the reducing abilities of low valent f-elements. In this case a bimolecular electron-transfer process is often observed. The reactivity of the U(III) siloxid complex [U(OSi(OtBu) 3 ) 4 K] was further investigated. Notably, reaction with Ph 3 PS led to the formation of a terminal U(IV) sulfide complex with multiple U-S bond which was analysed by DFT studies to better understand the bonding nature. Preliminary studies on the role of the counter-cation (M) in the system [U(OSi(OtBu) 3 ) 4 M] on the outcome of the reactivity with CS 2 and CO 2 have also been performed. The

  16. Metalloradical complexes of manganese and chromium featuring an oxidatively rearranged ligand. (United States)

    Celenligil-Cetin, Remle; Paraskevopoulou, Patrina; Lalioti, Nikolia; Sanakis, Yiannis; Staples, Richard J; Rath, Nigam P; Stavropoulos, Pericles


    Redox events involving both metal and ligand sites are receiving increased attention since a number of biological processes direct redox equivalents toward functional residues. Metalloradical synthetic analogues remain scarce and require better definition of their mode of formation and subsequent operation. The trisamido-amine ligand [(RNC6H4)3N]3-, where R is the electron-rich 4-t-Bu Ph, is employed in this study to generate redox active residues in manganese and chromium complexes. Solutions of [(L1)Mn(II)-THF]- in THF are oxidized by dioxygen to afford [(L1re-1)Mn(III)-(O)2-Mn(III)(L1 re-1)]2-as the major product. The rare dinuclear manganese (III,III) core is stabilized by a rearranged ligand that has undergone an one-electron oxidative transformation, followed by retention of the oxidation equivalent as a pi radical in ano-diiminobenzosemiquinonate moiety. Magnetic studies indicate that the ligand-centered radical is stabilized by means of extended antiferromagnetic coupling between the S ) 1/2 radical and the adjacent S ) 2 Mn(III) site, as well as between the two Mn(III) centers via the dioxo bridge. Electrochemical and EPR data suggest that this system can store higher levels of oxidation potency. Entry to the corresponding Cr(III) chemistry is achieved by employing CrCl3 to access both[(L1)Cr(III)-THF] and [(L1re-1)Cr(III)-THF(Cl)], featuring the intact and the oxidatively rearranged ligands, respectively. The latter is generated by ligand-centered oxidation of the former compound. The rearranged ligand is perceived to be the product of an one-electron oxidation of the intact ligand to afford a metal-bound aminyl radical that subsequently mediates a radical 1,4-(N-to-N) aryl migration.

  17. Sulfonated Schiff base Sn(IV) complexes as potential anticancer agents. (United States)

    Hazra, Susanta; Paul, Anup; Sharma, Gunjan; Koch, Biplob; da Silva, M Fátima C Guedes; Pombeiro, Armando J L


    Syntheses, crystal structures and biological activities of the diphenoxo-bridged diorgano dinuclear Sn(IV) compounds [Sn(Et) 2 (HL)(H 2 O)] 2 (1) and [Sn(n-Bu) 2 (HL)(H 2 O)] 2 (2) derived from the Schiff base 2-[(2,3-dihydroxyphenyl)methylideneamino]benzenesulfonic acid trihydrate (H 3 L·3H 2 O) are described. The monoprotonated form (HL 2- ) of the Schiff base behaves as O,O'-bidentate ligand, chelating the metal by the two phenoxo oxygen atoms. The hexacoordinated metal centres in 1 and 2 are bridged by a phenoxo oxygen and the remaining coordination positions are fulfilled by the other phenoxo oxygen, two organic groups (ethyl for 1 and n-butyl for 2) and a water molecule. A two dimensional zigzag sheet in 1 and three dimensional polymeric networks in H 3 L·3H 2 O and 2 are stabilized by a number of non-covalent, H-bonding and π⋯π stacking interactions. The DNA binding activities of these complexes have been studied by UV-vis and fluorescence spectroscopies. Their antiproliferative efficacies have been evaluated on A-549, HeLa and MDA-MB-231 cancer cell lines by 3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyltetrazolium bromide (MTT) assay. IC 50 values (1.35±0.23, 2.43±0.54 and 1.74±0.04μM for 2) are indicative of a substantial cytotoxicity of 2, mainly towards the A-549 lung cancer cell line. The greater antiproliferative efficacy of 2has further been studied by fluorescence activated cell sorting (FACS) and nuclear morphology by Hoechst/propidium iodide (PI) double staining method. The possible mode of the apoptotic pathway for 2has been substantiated by the reactive oxygen species (ROS) generation studies. Copyright © 2016 Elsevier Inc. All rights reserved.

  18. New metal-organic complexes based on bis(tetrazole) ligands: Synthesis, structures and properties (United States)

    Du, Ceng-Ceng; Fan, Jian-Zhong; Wang, Xin-Fang; Zhou, Sheng-Bin; Wang, Duo-Zhi


    In this paper, a series of new complexes, [Zn2(HL1)2(H2O)4]·H2O (1), [Co2(HL1)2]·TEA (2), [Co3(HL1)2(H2L1)2(H2O)4]n (3), [Cu(HL1)(H2O)2]n (4), {[Cu5(HL2)2(OH)4(ClO4)2]·4H2O}n (5) and [Cu2(L3)]n (6) were successfully prepared by utilizing three bis(tetrazole) ligands [bis-(1H-tetrazol-5-ylmethyl)-amine (H3L1), bis-(1H-tetrazol-5-ylethyl)-amine (H3L2) and 1,5-bis(5-tetrazolo)-3-thiapentane (H2L3)], all of which have been characterized by elemental analyses, FT-IR spectroscopy, powder X-ray diffraction (PXRD), thermogravimetric analyses as well as single-crystal X-ray diffraction analyses showing different dimensionalities (0D, 1D and 3D). Complexes 1 and 2 are 0D structures, 1 shows a dinuclear structure, 2 displays two crystallographically different mononuclear structures, 1 and 2 are further assembled to form 3D supramolecular framework and 2D supramolecular network by hydrogen-bonding interactions, respectively. Complexes 3, 4 and 5 are 1D structures, 3 features a mononuclear unit and a 1D chain, which are arranged into 3D supramolecular architecture by hydrogen-bonding interactions, 4 presents a zigzag chain, 5 shows an infinite chain structure constructed from pentanuclear Cu(II) subunits and ClO4- anions. Complex 6 exhibits a 3D coordination framework based on cyclic [Cu4(L3)2] dimmer subunits as nodes possessing an 8-connected network topology with the point symbol {424·64}. Further, semiconductor behaviors, the solid-state luminescent properties of the complexes 1-3 and 6 were measured and studied seriously at room temperature.

  19. The Mitochondrial Complex(Ity of Cancer

    Directory of Open Access Journals (Sweden)

    Félix A. Urra


    Full Text Available Recent evidence highlights that the cancer cell energy requirements vary greatly from normal cells and that cancer cells exhibit different metabolic phenotypes with variable participation of both glycolysis and oxidative phosphorylation. NADH–ubiquinone oxidoreductase (Complex I is the largest complex of the mitochondrial electron transport chain and contributes about 40% of the proton motive force required for mitochondrial ATP synthesis. In addition, Complex I plays an essential role in biosynthesis and redox control during proliferation, resistance to cell death, and metastasis of cancer cells. Although knowledge about the structure and assembly of Complex I is increasing, information about the role of Complex I subunits in tumorigenesis is scarce and contradictory. Several small molecule inhibitors of Complex I have been described as selective anticancer agents; however, pharmacologic and genetic interventions on Complex I have also shown pro-tumorigenic actions, involving different cellular signaling. Here, we discuss the role of Complex I in tumorigenesis, focusing on the specific participation of Complex I subunits in proliferation and metastasis of cancer cells.


    African Journals Online (AJOL)

    Preferred Customer

    Cobalt is essential for the production of the red blood cells and cobalamin acts as the substrate for the final enzymatic reaction that yields the active coenzyme derivatives of cyanocobalamin and aquacobalamin. Nickel is found in enzymes, such as urease, which is a dinuclear Ni(II)-containing metalloenzyme [8-10].

  1. 2 : 2 Fe(III): ligand and "adamantane core" 4 : 2 Fe(III): ligand (hydr)oxo complexes of an acyclic ditopic ligand

    DEFF Research Database (Denmark)

    Ghiladi, Morten; Larsen, Frank B.; McKenzie, Christine J.


    crystalline platelets. The Fe4O6 core of 2 shows an adamantane-like structure: The six bridging oxygen atoms are provided by the two phenolato groups of the two bpbp(-) ligands, two bridging oxo groups and two bridging hydroxo groups. The hydroxo and oxo ligands could be distinguished on the basis of Fe - O......-ray structure of the dinuclear complex [{( Hbpbp) Fe(mu-OH)}(2)](ClO4)(4) center dot 2C(3)H(6)O ( 1 center dot 2C(3)H(6)O) shows that only one of the metal-binding cavities of each ligand is occupied by an iron( III) atom and two [Fe(Hbpbp)](3+) units are linked together by two hydroxo bridging groups to form...... a [ Fe(III) -(mu-OH)](2) rhomb structure with Fe center dot center dot center dot Fe = 3.109(1) angstrom. The non-coordinated tertiary amine of Hbpbp is protonated. Magnetic susceptibility measurements show a well-behaved weak antiferromagnetic coupling between the two Fe( III) atoms, J =- 8 cm(-1...

  2. Anion-controlled nuclearity in nickel complexes with potentially dinucleating, poly(oxime) amine ligands. (United States)

    Deters, Elizabeth A; Goldcamp, Michael J; Krause Bauer, Jeanette A; Baldwin, Michael J


    Two new ligands consisting of bis(oxime) amine units tethered by a bridge have been synthesized. Their nickel chloride and nickel nitrate complexes have also been synthesized and characterized by X-ray crystallography, FTIR, mass spectrometry, and elemental analysis. One of these ligands, L1 (N,N,N',N'-tetra(1-propan-2-onyl oxime)-diamino-m-xylene), is always dinucleating, while the other ligand, L2 (N,N,N',N'-tetra(1-propan-2-onyl-oxime)-1,3-diaminopropane), shows an unusual anion dependence on the nuclearity. When nickel chloride is used, the ligand acts in a dinucleating manner and coordinates two nickels; however, when nickel nitrate is used, the ligand acts in a monodentate fashion and coordinates only one nickel. Once the mononuclear complex is formed, it is not possible to add a second nickel if Ni(NO(3))(2) is used as the nickel source; it is possible, however, to add a second nickel if NiCl(2) is used as the nickel source. The dinuclear complex can be converted to the mononuclear one by either using silver nitrate to exchange the chloride anions for nitrates or by dissolving the complex in water. Ni(2)(L1)Cl(4)(DMF)(2).DMF: orthorhombic, P2(1)2(1)2(1), a = 12.2524(11) A, b = 16.6145(15) A, c = 20.1234(19) A, V = 4096.5(6) A(3), Z = 4. [Ni(2)(L2)Cl(4)(DMF)](2).2DMF: triclinic, P-1, a = 12.5347(5) A, b = 12.5403(5) A, c = 14.3504(6) A, alpha = 67.348(1) degrees , beta = 69.705(1) degrees , gamma = 81.549(1) degrees , V = 1952.25(14) A(3), Z = 1. Ni(L2).(NO(3))(2): monoclinic, P2(1)/n, a = 9.6738(3) A, b = 30.2229(9) A, c = 15.8238(5) A, beta = 97.995(1) degrees , V = 4581.4(2) A(3), Z = 8.

  3. Synthesis, DNA Cleavage Activity, Cytotoxicity, Acetylcholinesterase Inhibition, and Acute Murine Toxicity of Redox-Active Ruthenium(II) Polypyridyl Complexes. (United States)

    Alatrash, Nagham; Narh, Eugenia S; Yadav, Abhishek; Kim, Mahn-Jong; Janaratne, Thamara; Gabriel, James; MacDonnell, Frederick M


    Four mononuclear [(L-L) 2 Ru(tatpp)] 2+ and two dinuclear [(L-L) 2 Ru(tatpp)Ru(L-L) 2 ] 4+ ruthenium(II) polypyridyl complexes (RPCs) containing the 9,11,20,22-tetraazatetrapyrido[3,2-a:2',3'-c:3'',2''-l:2''',3'''-n]pentacene (tatpp) ligand were synthesized, in which L-L is a chelating diamine ligand such as 2,2'-bipyridine (bpy), 1,10-phenanthroline (phen), 3,4,7,8-tetramethyl-1,10-phenanthroline (Me 4 phen) or 4,7-diphenyl-1,10-phenanthroline (Ph 2 phen). These Ru-tatpp analogues all undergo reduction reactions with modest reducing agents, such as glutathione (GSH), at pH 7. These, plus several structurally related but non-redox-active RPCs, were screened for DNA cleavage activity, cytotoxicity, acetylcholinesterase (AChE) inhibition, and acute mouse toxicity, and their activities were examined with respect to redox activity and lipophilicity. All of the redox-active RPCs show single-strand DNA cleavage in the presence of GSH, whereas none of the non-redox-active RPCs do. Low-micromolar cytotoxicity (IC 50 ) against malignant H358, CCL228, and MCF7 cultured cell lines was mainly restricted to the redox-active RPCs; however, they were substantially less toxic toward nonmalignant MCF10 cells. The IC 50 values for AChE inhibition in cell-free assays and the acute toxicity of RPCs in mice revealed that whereas most RPCs show potent inhibitory action against AChE (IC 50 values complexes as a class are surprisingly well tolerated in animals relative to other RPCs. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  4. Complex differential geometry

    CERN Document Server

    Zheng, Fangyang


    The theory of complex manifolds overlaps with several branches of mathematics, including differential geometry, algebraic geometry, several complex variables, global analysis, topology, algebraic number theory, and mathematical physics. Complex manifolds provide a rich class of geometric objects, for example the (common) zero locus of any generic set of complex polynomials is always a complex manifold. Yet complex manifolds behave differently than generic smooth manifolds; they are more coherent and fragile. The rich yet restrictive character of complex manifolds makes them a special and interesting object of study. This book is a self-contained graduate textbook that discusses the differential geometric aspects of complex manifolds. The first part contains standard materials from general topology, differentiable manifolds, and basic Riemannian geometry. The second part discusses complex manifolds and analytic varieties, sheaves and holomorphic vector bundles, and gives a brief account of the surface classifi...

  5. Radioisotope trithiol complexes (United States)

    Jurisson, Silvia S.; Cutler, Cathy S.; Degraffenreid, Anthony J.


    The present invention is directed to a series of stable radioisotope trithiol complexes that provide a simplified route for the direct complexation of radioisotopes present in low concentrations. In certain embodiments, the complex contains a linking domain configured to conjugate the radioisotope trithiol complex to a targeting vector. The invention is also directed to a novel method of linking the radioisotope to a trithiol compound to form the radioisotope trithiol complex. The inventive radioisotope trithiol complexes may be utilized for a variety of applications, including diagnostics and/or treatment in nuclear medicine.

  6. Complex and symplectic geometry

    CERN Document Server

    Medori, Costantino; Tomassini, Adriano


    This book arises from the INdAM Meeting "Complex and Symplectic Geometry", which was held in Cortona in June 2016. Several leading specialists, including young researchers, in the field of complex and symplectic geometry, present the state of the art of their research on topics such as the cohomology of complex manifolds; analytic techniques in Kähler and non-Kähler geometry; almost-complex and symplectic structures; special structures on complex manifolds; and deformations of complex objects. The work is intended for researchers in these areas.

  7. Oligocyclopentadienyl transition metal complexes

    Energy Technology Data Exchange (ETDEWEB)

    de Azevedo, Cristina G.; Vollhardt, K. Peter C.


    Synthesis, characterization, and reactivity studies of oligocyclopentadienyl transition metal complexes, namely those of fulvalene, tercyclopentadienyl, quatercyclopentadienyl, and pentacyclopentadienyl(cyclopentadienyl) are the subject of this account. Thermal-, photo-, and redox chemistries of homo- and heteropolynuclear complexes are described.

  8. Mycobacterium Avium Complex (MAC) (United States)

    ... 30, 2014 Select a Language: Fact Sheet 514 Mycobacterium Avium Complex (MAC) WHAT IS MAC? HOW DO ... INTERACTION PROBLEMS THE BOTTOM LINE WHAT IS MAC? Mycobacterium Avium Complex (MAC) is a serious illness caused ...

  9. Complex sulfides and thiosalts

    International Nuclear Information System (INIS)

    Uehlls, A.


    Different types of the structures of complex sulfides, thiosalts of alkali, alkaline earth, rare earth, transition and actinide metals are considered in the review of the papers published before 1980 and devoted to the crystal structure of complex sulfides

  10. Holograms as complex media (United States)

    Caulfield, H. John


    Complex media can be grown, found in nature, or manufactured.. Holography is one way of fabricating such media. Here I review some examples of holographically manufactured complex media and speculate about some that could be made.

  11. The simple complex numbers


    Zalesny, Jaroslaw


    A new simple geometrical interpretation of complex numbers is presented. It differs from their usual interpretation as points in the complex plane. From the new point of view the complex numbers are rather operations on vectors than points. Moreover, in this approach the real, imaginary and complex numbers have similar interpretation. They are simply some operations on vectors. The presented interpretation is simpler, more natural, and better adjusted to possible applications in geometry and ...

  12. Tungsten phosphanylarylthiolato complexes [W{PhP(2-SC6H4)2-kappa3S,S',P} 2] and [W{P(2-SC6H4)3-kappa4S,S',S",P}2]: synthesis, structures and redox chemistry. (United States)

    Hildebrand, Alexandra; Lönnecke, Peter; Silaghi-Dumitrescu, Luminita; Hey-Hawkins, Evamarie


    PhP(2-SHC6H4)2 (PS2H2) reacts with WCl6 with reduction of tungsten to give the air-sensitive tungsten(IV) complex [W{PhP(2-SC6H4)2-kappa(3)S,S',P}2] (1). 1 is oxidised in air to [WO{PhPO(2-SC6H4)2-kappa(3)S,S',O}{PhP(2-SC6H4)2-kappa(3)S,S',P}] (2). The attempted synthesis of 2 by reaction of 1 with iodosobenzene as oxidising agent was unsuccessful. [W{P(2-SC6H4)3-kappa(4)S,S',S",P}2] (3) was formed in the reaction of P(2-SHC6H4)3 (PS3H3) with WCl6. The W(VI) complex 3 contains two PS3(3-) ligands, each coordinated in a tetradentate fashion resulting in a tungsten coordination number of eight. The reaction of 3 with AgBF4 yields the dinuclear tungsten complex [W2{P(2-SC6H4)3-kappa(4)S,S',S",P}3]BF4 (4). Complexes 1-4 were characterised by spectral methods and X-ray structure determination.

  13. The Visibility Complex

    NARCIS (Netherlands)

    Pocchiola, Michel; Vegter, Gert


    We introduce the visibility complex of a collection O of n pairwise disjoint convex objects in the plane. This 2–dimensional cell complex may be considered as a generalization of the tangent visibility graph of O. Its space complexity k is proportional to the size of the tangent visibility graph. We

  14. Complex fuzzy soft multisets (United States)

    Alkouri, Abd Ulazeez M.; Salleh, Abdul Razak


    In this paper we combine two definitions, namely fuzzy soft multiset and complex fuzzy set to construct the definition of a complex fuzzy soft multiset and study its properties. In other words, we study the extension of a fuzzy soft multiset from real numbers to complex numbers. We also introduce its basic operations, namely complement, union and intersection. Some examples are given.

  15. Complex variables I essentials

    CERN Document Server

    Solomon, Alan D


    REA's Essentials provide quick and easy access to critical information in a variety of different fields, ranging from the most basic to the most advanced. As its name implies, these concise, comprehensive study guides summarize the essentials of the field covered. Essentials are helpful when preparing for exams, doing homework and will remain a lasting reference source for students, teachers, and professionals. Complex Variables I includes functions of a complex variable, elementary complex functions, integrals of complex functions in the complex plane, sequences and series, and poles and r

  16. Nickel complexes with new bidentate P,N phosphinitooxazoline and -pyridine ligands: application for the catalytic oligomerization of ethylene. (United States)

    Speiser, Fredy; Braunstein, Pierre; Saussine, Lucien; Welter, Richard


    The phosphinitooxazoline 4,4-dimethyl-2-[1-oxy(diphenylphosphine)-1-methylethyl]-4,5-dihydrooxazole (9), the corresponding phosphinitopyridine ligands 2-ethyl-[1'-methyl-1'-oxy(diphenylphosphino)]pyridine (11) and 2-ethyl-6-methyl-[1'-methyl-1'-oxy(diphenylphosphino)]pyridine (12), which have a one-carbon spacer between the phosphinite oxygen and the heterocycle, and the homologous ligand 2-propyl-[2'-methyl-2'-oxy(diphenylphosphino)]pyridine (13), with a two-carbon spacer, were prepared in good yields. The corresponding mononuclear [NiCl(2)(P,N)] complexes 14 (P,N = 9), 15 (P,N = 11), and 16 (P,N = 12) and the dinuclear [NiCl(micro-Cl)(P,N)](2) 17 (P,N = 13) Ni(II) complex were evaluated in the catalytic oligomerization of ethylene. These four complexes were characterized by single-crystal X-ray diffraction in the solid state and in solution with the help of the Evans method, which indicated differences between the coordination spheres in the solution and the solid state. In the presence of methylalumoxane (MAO) or AlEt(3), only the decomposition of the Ni complexes was observed. However, complexes 14-17 provided activities up to 50000 mol C(2)H(4)/(mol Ni).h (16 and 17) in the presence of only 6 equiv of AlEtCl(2). The observed selectivities for ethylene dimers were higher than 91% (for 14 or 15 in the presence of only 1.3 equiv of AlEtCl(2)). The activities for 14-17 were superior to that of [NiCl(2)(PCy(3))(2)], a typical dimerization catalyst taken as a reference. The selectivities of the complexes 14-17 for ethylene dimers and alpha-olefins were the same order of magnitude. From the study of the phosphinite 9/AlEtCl(2) system, we concluded that in our case ligand transfer from the nickel atom to the aluminum cocatalyst is unlikely to represent an activation mechanism.

  17. A series of Cd(II) complexes with π-π stacking and hydrogen bonding interactions: Structural diversities by varying the ligands

    International Nuclear Information System (INIS)

    Wang Xiuli; Zhang Jinxia; Liu Guocheng; Lin Hongyan


    Seven new Cd(II) complexes consisting of different phenanthroline derivatives and organic acid ligands, formulated as [Cd(PIP) 2 (dnba) 2 ] (1), [Cd(PIP)(ox)].H 2 O (2), [Cd(PIP)(1,4-bdc)(H 2 O)].4H 2 O (3), [Cd(3-PIP) 2 (H 2 O) 2 ].4H 2 O (4), [Cd 2 (3-PIP) 4 (4,4'-bpdc)(H 2 O) 2 ].5H 2 O (5), [Cd(3-PIP)(nip)(H 2 O)].H 2 O (6), [Cd 2 (TIP) 4 (4,4'-bpdc)(H 2 O) 2 ].3H 2 O (7) (PIP=2-phenylimidazo[4,5-f]1,10-phenanthroline, 3-PIP=2-(3-pyridyl)imidazo[4,5-f]1,10-phenanthroline, TIP=2-(2-thienyl)imidazo[4,5-f]1,10-phenanthroline, Hdnba=3,5-dinitrobenzoic acid, H 2 ox=oxalic acid, 1,4-H 2 bdc=benzene-1,4-dicarboxylic acid, 4,4'-H 2 bpdc=biphenyl-4,4'-dicarboxylic acid, H 2 nip=5-nitroisophthalic acid) have been synthesized under hydrothermal conditions. Complexes 1 and 4 possess mononuclear structures; complexes 5 and 7 are isostructural and have dinuclear structures; complexes 2 and 3 feature 1D chain structures; complex 6 contains 1D double chain, which are further extended to a 3D supramolecular structure by π-π stacking and hydrogen bonding interactions. The N-donor ligands with extended π-system and organic acid ligands play a crucial role in the formation of the final supramolecular frameworks. Moreover, thermal properties and fluorescence of 1-7 are also investigated. -- Graphical abstract: Seven new supramolecular architectures have been successfully isolated under hydrothermal conditions by reactions of different phen derivatives and Cd(II) salts together with organic carboxylate anions auxiliary ligands. Display Omitted Research highlights: → Complexes 1-7 are 0D or 1D polymeric structure, the π-π stacking and H-bonding interactions extend the complexes into 3D supramolecular network. To our knowledge, systematic study on π-π stacking and H-bonding interactions in cadmium(II) complexes are still limited. → The structural differences among the title complexes indicate the importance of N-donor chelating ligands for the creation of molecular

  18. A bipyridine-ligated zinc(II) complex with bridging flavonolate ligation: synthesis, characterization, and visible-light-induced CO release reactivity. (United States)

    Sorenson, Shayne; Popova, Marina; Arif, Atta M; Berreau, Lisa M


    Metal-flavonolate compounds are of significant current interest as synthetic models for quercetinase enzymes and as bioactive compounds of importance to human health. Zinc-3-hydroxyflavonolate compounds, including those of quercetin, kampferol, and morin, generally exhibit bidentate coordination to a single Zn II center. The bipyridine-ligated zinc-flavonolate compound reported herein, namely bis(μ-4-oxo-2-phenyl-4H-chromen-3-olato)-κ 3 O 3 :O 3 ,O 4 ;κ 3 O 3 ,O 4 :O 3 -bis[(2,2'-bipyridine-κ 2 N,N')zinc(II)] bis(perchlorate), {[Zn 2 (C 15 H 9 O 3 ) 2 (C 10 H 8 N 2 ) 2 ](ClO 4 ) 2 } n , (1), provides an unusual example of bridging 3-hydroxyflavonolate ligation in a dinuclear metal complex. The symmetry-related Zn II centers of (1) exhibit a distorted octahedral geometry, with weak coordination of a perchlorate anion trans to the bridging deprotonated O atom of the flavonolate ligand. Variable-concentration conductivity measurements provide evidence that, when (1) is dissolved in CH 3 CN, the complex dissociates into monomers. 1 H NMR resonances for (1) dissolved in d 6 -DMSO were assigned via HMQC to the H atoms of the flavonolate and bipyridine ligands. In CH 3 CN, (1) undergoes quantitative visible-light-induced CO release with a quantum yield [0.004 (1)] similar to that exhibited by other mononuclear zinc-3-hydroxyflavonolate complexes. Mass spectroscopic identification of the [(bpy) 2 Zn(O-benzoylsalicylate)] + ion provides evidence of CO release from the flavonol and of ligand exchange at the Zn II center.

  19. Simplicial complexes of graphs

    CERN Document Server

    Jonsson, Jakob


    A graph complex is a finite family of graphs closed under deletion of edges. Graph complexes show up naturally in many different areas of mathematics, including commutative algebra, geometry, and knot theory. Identifying each graph with its edge set, one may view a graph complex as a simplicial complex and hence interpret it as a geometric object. This volume examines topological properties of graph complexes, focusing on homotopy type and homology. Many of the proofs are based on Robin Forman's discrete version of Morse theory. As a byproduct, this volume also provides a loosely defined toolbox for attacking problems in topological combinatorics via discrete Morse theory. In terms of simplicity and power, arguably the most efficient tool is Forman's divide and conquer approach via decision trees; it is successfully applied to a large number of graph and digraph complexes.

  20. Measuring static complexity

    Directory of Open Access Journals (Sweden)

    Ben Goertzel


    Full Text Available The concept of “pattern” is introduced, formally defined, and used to analyze various measures of the complexity of finite binary sequences and other objects. The standard Kolmogoroff-Chaitin-Solomonoff complexity measure is considered, along with Bennett's ‘logical depth’, Koppel's ‘sophistication'’, and Chaitin's analysis of the complexity of geometric objects. The pattern-theoretic point of view illuminates the shortcomings of these measures and leads to specific improvements, it gives rise to two novel mathematical concepts--“orders” of complexity and “levels” of pattern, and it yields a new measure of complexity, the “structural complexity”, which measures the total amount of structure an entity possesses.

  1. Avoiding Simplicity Is Complex (United States)

    Allender, Eric

    It is a trivial observation that every decidable set has strings of length n with Kolmogorov complexity logn + O(1) if it has any strings of length n at all. Things become much more interesting when one asks whether a similar property holds when one considers resource-bounded Kolmogorov complexity. This is the question considered here: Can a feasible set A avoid accepting strings of low resource-bounded Kolmogorov complexity, while still accepting some (or many) strings of length n?

  2. Complex Systems and Dependability

    CERN Document Server

    Zamojski, Wojciech; Sugier, Jaroslaw


    Typical contemporary complex system is a multifaceted amalgamation of technical, information, organization, software and human (users, administrators and management) resources. Complexity of such a system comes not only from its involved technical and organizational structure but mainly from complexity of information processes that must be implemented in the operational environment (data processing, monitoring, management, etc.). In such case traditional methods of reliability analysis focused mainly on technical level are usually insufficient in performance evaluation and more innovative meth

  3. Cobalt(III) complex

    Indian Academy of Sciences (India)


    e, 40 µM complex, 10 hrs after dissolution, f, 40 µM complex, after irradiation dose 15 Gy. and H-atoms result in reduction of Co(III) to Co. (II). 6. It is interesting to see in complex containing multiple ligands what is the fate of electron adduct species formed by electron addition. Reduction to. Co(II) and intramolecular transfer ...

  4. Conducting metal dithiolate complexes

    DEFF Research Database (Denmark)

    Underhill, A. E.; Ahmad, M. M.; Turner, D. J.


    Further work on the chemical composition of the one-dimensional metallic metal dithiolene complex Li-Pt(mnt) is reported. The electrical conduction and thermopower properties of the nickel and palladium complexes are reported and compared with those of the platinum compound......Further work on the chemical composition of the one-dimensional metallic metal dithiolene complex Li-Pt(mnt) is reported. The electrical conduction and thermopower properties of the nickel and palladium complexes are reported and compared with those of the platinum compound...

  5. Four-coordinate trispyrazolylboratomanganese and -iron complexes with a pyrazolato co-ligand: syntheses and properties as oxidation catalysts. (United States)

    Tietz, Thomas; Limberg, Christian; Stösser, Reinhard; Ziemer, Burkhard


    A series of complexes of the type [(Tp(R1,R2))M(X)] (Tp = trispyrazolylborato) with R(1)/R(2) combinations Me/tBu, Ph/Me, iPr/iPr, Me/Me and for M = Mn or Fe coordinating [Pz(Me,tBu)](-) (Pz = pyrazolato) or Cl(-) as co-ligand X has been synthesised. Although the chloride complexes were very unreactive and stable in air, the pyrazolato series was far more reactive in contact with oxidants like O(2) and tBuOOH. The [(Tp(R1,R2))M(Pz(Me,tBu))] complexes proved to be active pre-catalysts for the oxidation of cyclohexene with tBuOOH, reaching turnover frequencies (TOFs) ranging between moderate and good in comparison to other manganese catalysts. Cyclohexene-3-one and cyclohexene-3-ol were always found to represent the main products, with cyclohexene oxide occasionally formed as a side product. The ratios of the different oxidation products varied with the reaction conditions: in the case of a peroxide/alkene ratio of 4:1, considerably more ketone than alcohol was obtained and cyclohexene oxide formation was almost negligible, whereas a ratio of 1:10 led to a significant increase of the alcohol proportion and to the formation of at least small amounts of the epoxide. Pre-treatment of the dissolved [(Tp(R1,R2))M(Pz(Me,tBu))] pre-catalysts with O(2) led to product distributions and TOFs that were very similar to those found in the absence of O(2), so that it may be argued that tBuOOH and O(2) both lead to the same active species. The results of EPR spectroscopy and ESI-MS suggest that the initial product of the reaction of [(Tp(Me,Me))Mn(Pz(Me,tBu))] with O(2) contains a Mn(III)(O)(2)Mn(IV) core. Prolonged exposure to O(2) leads to a different dinuclear complex containing three O-bridges and resulting in different TOFs/product distributions. Analogous findings were made for other complexes and formation of these overoxidised products may explain the deviation of the catalytic performances if the reactions are carried out in an O(2) atmosphere. Copyright © 2011 WILEY

  6. Synthesis and Crystal Structures of Copper(II) Complexes with Schiff Base Ligands: [Cu2(acpy-mdtc)2(HBA)(ClO4)]·H2O and [Cu2(acpy-phtsc)2(HBA)]·ClO4

    International Nuclear Information System (INIS)

    Koo, Bon Kweon


    Two new Cu(II) complexes, [Cu 2 (acpy-mdtc) 2 (HBA)(ClO 4 )]·H 2 O (1) (acpy-mdtc - = 2-acetylpyridine S-methyldithiocarbamate and HBA - = benzilic acid anion) and [Cu 2 (acpy-phtsc) 2 (HBA)]·ClO 4 (2) (acpy-phtsc - = 2-acetylpyridine 4-phenyl-3-thiosemicarbazate) have been synthesized and characterized by elemental analysis, infrared spectroscopy, thermogravimetric analysis, and single crystal X-ray diffraction. The X-ray analysis reveals that the structures of 1 and 2 are dinuclear copper(II) complexes bridged by two thiolate sulfur atoms of Schiff base ligand and bidentate bridging HBA - anion. For 1, each of the two copper atoms has different coordination environments. Cu1 adopts a five-coordinate square-pyramidal with a N 2 OS 2 donor, while Cu 2 exhibits a distorted octahedral geometry in a N 2 O 2 S 2 manner. For 2, two Cu(II) ions all have a five-coordinate square-pyramidal with a N 2 OS 2 donor. In each complex, the Schiff base ligand is coordinated to copper ions as a tridentate thiol mode

  7. Structural, spectroscopic, and multiconfigurational quantum chemical investigations of the electron-rich metal-metal triple-bonded Tc(2)X(4)(PMe(3))(4) (X = Cl, Br) complexes. (United States)

    Poineau, Frederic; Forster, Paul M; Todorova, Tanya K; Gagliardi, Laura; Sattelberger, Alfred P; Czerwinski, Kenneth R


    The compounds Tc(2)Cl(4)(PMe(3))(4) and Tc(2)Br(4)(PMe(3))(4) were formed from the reaction between (n-Bu(4)N)(2)Tc(2)X(8) (X = Cl, Br) and trimethylphosphine. The Tc(II) dinuclear species were characterized by single-crystal XRD, UV-visible spectroscopy, and cyclic voltammetry techniques, and the results are compared to those obtained from density functional theory and multiconfigurational (CASSCF/CASPT2) quantum chemical studies. The compound Tc(2)Cl(4)(PMe(3))(4) crystallizes in the monoclinic space group C2/c [a = 17.9995(9) A, b = 9.1821(5) A, c = 17.0090(9) A, beta = 115.4530(10) degrees ] and is isostructural to M(2)Cl(4)(PMe(3))(4) (M = Re, Mo, W) and to Tc(2)Br(4)(PMe(3))(4). The metal-metal distance (2.1318(2) A) is similar to the one found in Tc(2)Br(4)(PMe(3))(4) (2.1316(5) A). The calculated molecular structures of the ground states are in excellent agreement with the structures determined experimentally. Calculations of effective bond orders for Tc(2)X(8)(2-) and Tc(2)X(4)(PMe(3))(4) (X = Cl, Br) indicate stronger pi bonds in the Tc(2)(4+) core than in Tc(2)(6+) core. The electronic spectra were recorded in benzene and show a series of low intensity bands in the range 10 000-26 000 cm(-1). Assignment of the bands as well as computing their excitation energies and intensities were performed at both TD-DFT and CASSCF/CASPT2 levels of theory. Calculations predict that the lowest energy band corresponds to the delta* --> sigma* transition, the difference between calculated and experimental values being 228 cm(-1) for X = Cl and 866 cm(-1) for X = Br. The next bands are attributed to delta* --> pi*, delta --> sigma*, and delta --> pi* transitions. The cyclic voltammograms exhibit two reversible waves and indicate that Tc(2)Br(4)(PMe(3))(4) exhibits more positive oxidation potentials than Tc(2)Cl(4)(PMe(3))(4.) This phenomenon is discussed and ascribed to stronger metal (d) to halide (d) back bonding in the bromo complex. Further analysis indicates that Tc

  8. Photoresponsive Molecular Memory Films Composed of Sequentially Assembled Heterolayers Containing Ruthenium Complexes. (United States)

    Nagashima, Takumi; Ozawa, Hiroaki; Suzuki, Takashi; Nakabayashi, Takuya; Kanaizuka, Katsuhiko; Haga, Masa-Aki


    Photoresponsive molecular memory films were fabricated by a layer-by-layer (LbL) assembling of two dinuclear Ru complexes with tetrapodal phosphonate anchors, containing either 2,3,5,6-tetra(2-pyridyl)pyrazine or 1,2,4,5-tetra(2-pyridyl)benzene as a bridging ligand (Ru-NP and Ru-CP, respectively), using zirconium phosphonate to link the layers. Various types of multilayer homo- and heterostructures were constructed. In the multilayer heterofilms such as ITO||(Ru-NP)m |(Ru-CP)n , the difference in redox potentials between Ru-NP and Ru-CP layers was approximately 0.7 V, which induced a potential gradient determined by the sequence of the layers. In the ITO||(Ru-NP)m |(Ru-CP)n multilayer heterofilms, the direct electron transfer (ET) from the outer Ru-CP layers to the ITO were observed to be blocked for m>2, and charge trapping in the outer Ru-CP layers became evident from the appearance of an intervalence charge transfer (IVCT) band at 1140 nm from the formation of the mixed-valent state of Ru-CP units, resulting from the reductive ET mediation of the inner Ru-NP layers. Therefore, the charging/discharging ("1"and "0") states in the outer Ru-CP layers could be addressed and interconverted by applying potential pulses between -0.5 and +0.7 V. The two states could be read out by the direction of the photocurrent (anodic or cathodic). The molecular heterolayer films thus represent a typical example of a photoresponsive memory device; that is, the writing process may be achieved by the applied potential (-0.5 or +0.7 V), while the readout process is achieved by measuring the direction of the photocurrent (anodic or cathodic). Sequence-sensitive multilayer heterofilms, using redox-active complexes as building blocks, thus demonstrate great potential for the design of molecular functional devices. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  9. The visibility complex

    NARCIS (Netherlands)

    Pocchiola, M; Vegter, G

    We introduce the visibility complex (rr 2-dimensional regular cell complex) of a collection of n pairwise disjoint convex obstacles in the plane. It can be considered as a subdivision of the set of free rays (i.e., rays whose origins lie in free space, the complement of the obstacles). Its cells

  10. complexes of pyrimidine derived

    Indian Academy of Sciences (India)


    HL3, HL4 and HL5) respectively. These ligands are already reported as good donors for Mo(VI) state. The μ-oxo Mo(V) complexes reported here bears a distorted octahedral geometry around each Mo atom with either N2O2Cl or N2O2Br chromophores. Fine variations in the spectroscopic behaviour of the complexes.

  11. Visual Complexity: A Review (United States)

    Donderi, Don C.


    The idea of visual complexity, the history of its measurement, and its implications for behavior are reviewed, starting with structuralism and Gestalt psychology at the beginning of the 20th century and ending with visual complexity theory, perceptual learning theory, and neural circuit theory at the beginning of the 21st. Evidence is drawn from…

  12. Complex Materials and Devices (United States)


    Disruptive Basic Research Areas” – Metamaterials and Plasmonics – Quantum Information Science – Cognitive Neuroscience – Nanoscience and...function Complex Electronics and Fundamental Quantum Processes Complex engineered materials and devices Devices based on quantum phenomena...fundamental quantum processes Quantum Electronic Solids (Weinstock) Photonics and Optoelectronics (Pomrenke) GHz-THz Electronics (Hwang) Natural

  13. Complexity in Picture Books (United States)

    Sierschynski, Jarek; Louie, Belinda; Pughe, Bronwyn


    One of the key requirements of Common Core State Standards (CCSS) in English Language Arts is that students are able to read and access complex texts across all grade levels. The CCSS authors emphasize both the limitations and lack of accuracy in the current CCSS model of text complexity, calling for the development of new frameworks. In response…

  14. Complex conductivity of soils

    NARCIS (Netherlands)

    Revil, A.; Coperey, A.; Shao, Z.; Florsch, N.; Fabricus, I.L.; Deng, Y.; Delsman, J.R.; Pauw, P.S.; Karaoulis, M.; Louw, P.G.B. de; Baaren, E.S. van; Dabekaussen, W.; Menkovic, A.; Gunnink, J.L.


    The complex conductivity of soils remains poorly known despite the growing importance of this method in hydrogeophysics. In order to fill this gap of knowledge, we investigate the complex conductivity of 71 soils samples (including four peat samples) and one clean sand in the frequency range 0.1 Hz

  15. Genetics of complex disorders. (United States)

    Kere, Juha


    The success stories of identifying genes in Mendelian disorders have stimulated research that aims at identifying the genetic determinants in complex disorders, in which both genetics, environment and chance affect the pathogenetic processes. This review summarizes the brief history and lessons learned from genetic analysis of complex disorders and outlines some landscapes ahead for medical research. 2010. Published by Elsevier Inc.

  16. Life Complexity and Diversity

    Indian Academy of Sciences (India)

    It is as if the stage is cleared from time to time to make for fresh beginnings, with major bouts of extinction. Humans are amongst the most complex products of evolution having in turn populated the world with ever growing numbers of complex artefacts. These artefacts are now threatening to overwhelm the diversity of life.

  17. Photocytotoxic lanthanide complexes

    Indian Academy of Sciences (India)

    The chemistry of photoactive lanthanide complexes showing biological applications is of recent origin. Photodynamic therapy (PDT) is a non-invasive treatment modality of cancer using a photosensitizer drug and light. This review primarily focuses on different aspects of the chemistry of lanthanide complexes showing ...

  18. complexes of pyrimidine derived

    Indian Academy of Sciences (India)


    complexes are not so common in literature. Because of a tendency of Mo(V) species to form oxo- ... enzymes such as DMSO reductase are common in microbial systems and are mononuclear in nature. 11 ..... ligands with centroid to centroid distances of 3⋅52 Å. 4. Conclusion. Ten new Mo(V) complexes are prepared which ...

  19. Complexity and behavioral economics. (United States)

    Rosser, J Barkley; Rosser, Marina V


    This paper will consider the relationship between complexity economics and behavioral economics. A crucial key to this is to understand that Herbert Simon was both the founder of explicitly modern behavioral economics as well as one of the early developers of complexity theory. Bounded rationality was essentially derived from Simon's view of the impossibility of full rationality on the part of economic agents. Modern complexity theory through such approaches as agent-based modeling offers an approach to understanding behavioral economics by allowing for specific behavioral responses to be assigned to agents who interact within this context, even without full rationality. Other parts of modern complexity theory are considered in terms of their relationships with behavioral economics. Fundamentally, complexity provides an ultimate foundation for bounded rationality and hence the need to use behavioral economics in a broader array of contexts than most economists have thought appropriate.

  20. Leading healthcare in complexity. (United States)

    Cohn, Jeffrey


    Healthcare institutions and providers are in complexity. Networks of interconnections from relationships and technology create conditions in which interdependencies and non-linear dynamics lead to surprising, unpredictable outcomes. Previous effective approaches to leadership, focusing on top-down bureaucratic methods, are no longer effective. Leading in complexity requires leaders to accept the complexity, create an adaptive space in which innovation and creativity can flourish and then integrate the successful practices that emerge into the formal organizational structure. Several methods for doing adaptive space work will be discussed. Readers will be able to contrast traditional leadership approaches with leading in complexity. They will learn new behaviours that are required of complexity leaders, along with challenges they will face, often from other leaders within the organization.

  1. Structural variety in solvated lanthanoid (III) halide complexes

    International Nuclear Information System (INIS)

    Deacon, G.B; Feng, T.; Scott, N.M.; Junk, P.C.; James Cook University, Townsville, QLD; Meyer, G.; Skelton, B.W.; White, A.H.


    Treatment of lanthanum metal with CH 2 Br 2 or CH 2 I 2 in tetrahydrofuran (thf) under ultrasound conditions yields the corresponding [LaX 3 (thf) 4 ] (X Br, I) complexes in good yield. Recrystallization of [LaBr 3 (thf) 4 ] from 1,2-dimethoxyethane (dme) or bis(2-methoxyethyl) ether (dig-lyme) generates [LaBr 2 (μ-Br)(dme) 2 ] 2 and [LaBr 2 (dig-lyme) 2 ][LaBr 4 (diglyme)]. Treatment of lanthanoid metals with hexachloroethane in dme yields [LnCl 3 (dme) 2 ] (Ln = La, Nd, Er or Yb) and in acetonitrile [YbCl 2 (MeCN) 5 ] 2 [YbCl 3 (MeCN)(-Cl) 2 YbCl 3 (MeCN)]. The reaction of Yb metal pieces with 1,2-dibromoethane in thf and dme gave single crystals of [YbBr 3 (thf) 3 ] and [YbBr 3 (dme) 2 ], respectively. The X-ray determined structure of [LaBr 3 (thf) 4 ] shows a seven-coordinate monomer with pentagonal-bipyramidal stereochemistry and apical bromide ligands. For [YbBr 3 (thf) 3 ], a monomeric structure with mer-octahedral stereochemistry is observed. In [LaBr 2 (μ-Br)(dme) 2 ] 2 , two eight-coordinate La centres are linked by two bridging bromides. The dme ligands have a trans relationship to each other, and cis terminal bromides are transoid to the bridging bromides with dodecahedral stereochemistry for La. By contrast, the 1: 1.5 diglyme adduct is found to be ionic [LaBr 2 (diglyme) 2 ][LaBr 4 (diglyme)], with an eight-coordinate bicapped trigonal-prismatic lanthanum cation and a seven-coordinate pentagonal-bipyramidal lanthanum anion. In the cation, the bromide ligands are cis to each other, and in the anion, two bromides are equatorial and two are axial. In [YbBr 3 (dme) 2 ], [YbCl 3 (dme) 2 ] and [ErCl 3 (dme) 2 ], a seven-coordinate pentagonal-bipyramidal arrangement exists with apical halogen ligands. Far-infrared data, and in particular the absence of absorptions attributable to I(La-Cl ter ), suggest that [LaCl 3 (dme)] is polymeric with six bridging chlorides per lanthanum. For [YbCl 2 (MeCN) 5 ] 2 [YbCl 3 (MeCN)(-Cl) 2 YbCl 3 -(MeCN)], a remarkable

  2. Quantum Entropy and Complexity (United States)

    Benatti, F.; Oskouei, S. Khabbazi; Abad, A. Shafiei Deh

    We study the relations between the recently proposed machine-independent quantum complexity of P. Gacs [1] and the entropy of classical and quantum systems. On one hand, by restricting Gacs complexity to ergodic classical dynamical systems, we retrieve the equality between the Kolmogorov complexity rate and the Shannon entropy rate derived by A. A. Brudno [2]. On the other hand, using the quantum Shannon-McMillan theorem [3], we show that such an equality holds densely in the case of ergodic quantum spin chains.

  3. Study of complex modes

    International Nuclear Information System (INIS)

    Pastrnak, J.W.


    This eighteen-month study has been successful in providing the designer and analyst with qualitative guidelines on the occurrence of complex modes in the dynamics of linear structures, and also in developing computer codes for determining quantitatively which vibration modes are complex and to what degree. The presence of complex modes in a test structure has been verified. Finite element analysis of a structure with non-proportional dumping has been performed. A partial differential equation has been formed to eliminate possible modeling errors

  4. Simulation in Complex Modelling

    DEFF Research Database (Denmark)

    Nicholas, Paul; Ramsgaard Thomsen, Mette; Tamke, Martin


    This paper will discuss the role of simulation in extended architectural design modelling. As a framing paper, the aim is to present and discuss the role of integrated design simulation and feedback between design and simulation in a series of projects under the Complex Modelling framework. Complex...... Restraint developed for the research exhibition Complex Modelling, Meldahls Smedie Gallery, Copenhagen in 2016. Where the direct project aims and outcomes have been reported elsewhere, the aim for this paper is to discuss overarching strategies for working with design integrated simulation....

  5. Complexity from the ordinary

    DEFF Research Database (Denmark)

    Ayres, Phil


    Herbert Simon proposed that complexity is an emergent property that can result from the interaction of a simple mechanism within a complex environment. The Kielder context exhibits continual variation across many time scales and offers a rich resource for exploring the notions of novelty, variety......, specificity and complexity. By considering the design process as a continual iterative cycle in which the digital and analogue are closely coupled, we might imagine a construct that continually redefines itself in relation to its context, attempting to become increasingly specific to location and purpose over...


    NARCIS (Netherlands)


    Thermolysis of Cp*Zr(COT)R (Cp* = eta5-C5Me5, COT = eta8-C8H8, R = CH2SiMe3, Me) proceeds via a double hydrogen abstraction from a cyclooctatetraene ligand to give RH and Cp*Zr(mu-eta8:eta2-C8H6)ZrCp*(eta4-C8H8) as the kinetic product. Cp*Zr(mu-eta8:eta2-C8H6) undergoes a thermally induced hydrogen

  7. Complex Flow Workshop Report

    Energy Technology Data Exchange (ETDEWEB)



    This report documents findings from a workshop on the impacts of complex wind flows in and out of wind turbine environments, the research needs, and the challenges of meteorological and engineering modeling at regional, wind plant, and wind turbine scales.

  8. Low complexity MIMO receivers

    CERN Document Server

    Bai, Lin; Yu, Quan


    Multiple-input multiple-output (MIMO) systems can increase the spectral efficiency in wireless communications. However, the interference becomes the major drawback that leads to high computational complexity at both transmitter and receiver. In particular, the complexity of MIMO receivers can be prohibitively high. As an efficient mathematical tool to devise low complexity approaches that mitigate the interference in MIMO systems, lattice reduction (LR) has been widely studied and employed over the last decade. The co-authors of this book are world's leading experts on MIMO receivers, and here they share the key findings of their research over years. They detail a range of key techniques for receiver design as multiple transmitted and received signals are available. The authors first introduce the principle of signal detection and the LR in mathematical aspects. They then move on to discuss the use of LR in low complexity MIMO receiver design with respect to different aspects, including uncoded MIMO detection...

  9. Physical Sciences Complex (United States)

    Federal Laboratory Consortium — This 88,000 square foot complex is used to investigate basic physical science in support of missile technology development. It incorporates office space, dedicated...

  10. Bitter Sweetness of Complexity (United States)

    Horst, A. K.; Wagener, C.

    Glycosylation of proteins, lipids and mucins has gained increasing complexity in the course of evolution. Metazoans and mammals exhibit extensively exploited pathways of N-glycan biosynthesis, with unique features that are not found in plants or protozoans.

  11. complexes of Ciprofloxacin

    African Journals Online (AJOL)



    2002). Magnesium, Calcium and Barium Percholate complexes of ciprofloxacin and Norfloxacin. Acta. Chim. Slov. 49: 457-466. Akanji MA, Olagoke OA, Oloyede OB (1993). Effects of chronic consumption of metabisulphite on ...

  12. Complex Strategic Choices

    DEFF Research Database (Denmark)

    Leleur, Steen

    . Complex Strategic Choices provides clear principles and methods which can guide and support strategic decision making to face the many current challenges. By considering ways in which planning practices can be renewed and exploring the possibilities for acquiring awareness and tools to add value...... and students in the field of planning and decision analysis as well as practitioners dealing with strategic analysis and decision making. More broadly, Complex Strategic Choices acts as guide for professionals and students involved in complex planning tasks across several fields such as business...... to strategic decision making, Complex Strategic Choices presents a methodology which is further illustrated by a number of case studies and example applications. Dr. Techn. Steen Leleur has adapted previously established research based on feedback and input from various conferences, journals and students...

  13. Indicators: Physical Habitat Complexity (United States)

    Physical habitat complexity measures the amount and variety of all types of cove at the water’s edge in lakes. In general, dense and varied shoreline habitat is able to support more diverse communities of aquatic life.

  14. Complex Networks IX

    CERN Document Server

    Coronges, Kate; Gonçalves, Bruno; Sinatra, Roberta; Vespignani, Alessandro; Proceedings of the 9th Conference on Complex Networks; CompleNet 2018


    This book aims to bring together researchers and practitioners working across domains and research disciplines to measure, model, and visualize complex networks. It collects the works presented at the 9th International Conference on Complex Networks (CompleNet) 2018 in Boston, MA in March, 2018. With roots in physical, information and social science, the study of complex networks provides a formal set of mathematical methods, computational tools and theories to describe prescribe and predict dynamics and behaviors of complex systems. Despite their diversity, whether the systems are made up of physical, technological, informational, or social networks, they share many common organizing principles and thus can be studied with similar approaches. This book provides a view of the state-of-the-art in this dynamic field and covers topics such as group decision-making, brain and cellular connectivity, network controllability and resiliency, online activism, recommendation systems, and cyber security.

  15. Reconstruction Using Witness Complexes (United States)

    Oudot, Steve Y.


    We present a novel reconstruction algorithm that, given an input point set sampled from an object S, builds a one-parameter family of complexes that approximate S at different scales. At a high level, our method is very similar in spirit to Chew’s surface meshing algorithm, with one notable difference though: the restricted Delaunay triangulation is replaced by the witness complex, which makes our algorithm applicable in any metric space. To prove its correctness on curves and surfaces, we highlight the relationship between the witness complex and the restricted Delaunay triangulation in 2d and in 3d. Specifically, we prove that both complexes are equal in 2d and closely related in 3d, under some mild sampling assumptions. PMID:21643440

  16. Complexity for Artificial Substrates (

    NARCIS (Netherlands)

    Loke, L.H.L.; Jachowski, N.R.; Bouma, T.J.; Ladle, R.J.; Todd, P.A.


    Physical habitat complexity regulates the structure and function of biological communities, although the mechanisms underlying this relationship remain unclear. Urbanisation, pollution, unsustainable resource exploitation and climate change have resulted in the widespread simplification (and loss)

  17. Thermodynamics of complexity

    DEFF Research Database (Denmark)

    Westerhoff, Hans V.; Jensen, Peter Ruhdal; Snoep, Jacky L.


    the thesis that the aforesaid holds a fortiori for the living cell: Much of the essence of the live state depends more on the manner in which the molecules are organised than on the properties of single molecules. This is due to the phenomenon of 'Complexity'. BioComplexity is defined here as the phenomenon...... understanding of this BioComplexity, modem thermodynamic concepts and methods (nonequilibrium thermodynamics, metabolic and hierarchical control analysis) will be needed. We shall propose to redefine nonequilibrium thermodynamics as: The science that aims at understanding the behaviour of nonequilibrium systems...... with metabolic control analysis. Subsequently, the complexity of the control of the energy metabolism of E. coli will be analysed in detail. New control theorems will be derived for newly defined control coefficients. It will become transparent that molecular genetic experimentation will allow one to penetrate...

  18. Complex variable HVPT

    Energy Technology Data Exchange (ETDEWEB)

    Killingbeck, John P [Mathematics Department, University of Hull, Hull HU6 7RX (United Kingdom); Grosjean, Alain [Laboratoire d' Astrophysique de l' Observatoire de Besancon (CNRS, UPRES-A 6091), 41 bis Avenue de l' Observatoire, BP 1615, 25010 Besancon Cedex (France); Jolicard, Georges [Laboratoire d' Astrophysique de l' Observatoire de Besancon (CNRS, UPRES-A 6091), 41 bis Avenue de l' Observatoire, BP 1615, 25010 Besancon Cedex (France)


    Complex variable hypervirial perturbation theory is applied to the case of oscillator and Coulomb potentials perturbed by a single term potential of the form Vx{sup n} or Vr{sup n}, respectively. The trial calculations reported show that this approach can produce accurate complex energies for resonant states via a simple and speedy calculation and can also be useful in studies of PT symmetry and tunnelling resonance effects. (addendum)

  19. An erupted complex odontoma. (United States)

    Tozoglu, Sinan; Yildirim, Umran; Buyukkurt, M Cemil


    Odontomas are benign tumors of odontogenic origin. The cause of the odontoma is unknown, but it is believed to be hereditary or due to a disturbance in tooth development triggered by trauma or infection. Odontomas may be either compound or complex. Although these tumors are seen frequently, erupted odontomas are rare. The purpose of this study is to present a rare case of complex odontoma that erupted into the oral cavity.

  20. Complexity and Safety (FAA) (United States)


    Carnegie Mellon University for the operation of the Software Engineering Institute, a federally funded research and development center sponsored by...their error propagation potentials are Enable use of complexity as an indicator of risk , to be tracked using standard techniques Future research...into “How much can we discount the complexity of a system given that X% has been used before?” can be framed as “ credit for precedence” and ties to

  1. Simulation with complex measures

    International Nuclear Information System (INIS)

    Kieu, T.D.; Griffin, C.J.


    The simulation of statistical and quantum systems suffers from the sign problem when the generating function measures are indefinite or are complex, such as lattice quantum chromodynamics with finite temperature and density and chiral gauge theory. A new approach is proposed which yields statistical errors smaller than the crude Monte Carlo using absolute values of the original measures. The one-dimensional complex-coupling Ising model is employed as an illustration. 2 refs., 1 tab., 1 fig

  2. Advances in network complexity

    CERN Document Server

    Dehmer, Matthias; Emmert-Streib, Frank


    A well-balanced overview of mathematical approaches to describe complex systems, ranging from chemical reactions to gene regulation networks, from ecological systems to examples from social sciences. Matthias Dehmer and Abbe Mowshowitz, a well-known pioneer in the field, co-edit this volume and are careful to include not only classical but also non-classical approaches so as to ensure topicality. Overall, a valuable addition to the literature and a must-have for anyone dealing with complex systems.

  3. Provability, complexity, grammars

    CERN Document Server

    Beklemishev, Lev; Vereshchagin, Nikolai


    The book contains English translations of three outstanding dissertations in mathematical logic and complexity theory. L. Beklemishev proves that all provability logics must belong to one of the four previously known classes. The dissertation of M. Pentus proves the Chomsky conjecture about the equivalence of two approaches to formal languages: the Chomsky hierarchy and the Lambek calculus. The dissertation of N. Vereshchagin describes a general framework for criteria of reversability in complexity theory.

  4. Conversation, coupling and complexity

    DEFF Research Database (Denmark)

    Fusaroli, Riccardo; Abney, Drew; Bahrami, Bahador

    We investigate the linguistic co-construction of interpersonal synergies. By applying a measure of coupling between complex systems to an experimentally elicited corpus of joint decision dialogues, we show that interlocutors’ linguistic behavior displays increasing signature of multi-scale coupling......, known as complexity matching, over the course of interaction. Furthermore, we show that stronger coupling corresponds with more effective interaction, as measured by collective task performance....

  5. Electrospun complexes - functionalised nanofibres

    Energy Technology Data Exchange (ETDEWEB)

    Meyer, T.; Wolf, M.; Dreyer, B.; Unruh, D.; Krüger, C.; Menze, M. [Leibniz University Hannover, Institute of Inorganic Chemistry (Germany); Sindelar, R. [University of Applied Science Hannover, Faculty II (Germany); Klingelhöfer, G. [Gutenberg-University, Institute of Inorganic and Analytic Chemistry (Germany); Renz, F., E-mail: [Leibniz University Hannover, Institute of Inorganic Chemistry (Germany)


    Here we present a new approach of using iron-complexes in electro-spun fibres. We modify poly(methyl methacrylate) (PMMA) by replacing the methoxy group with Diaminopropane or Ethylenediamine. The complex is bound covalently via an imine-bridge or an amide. The resulting polymer can be used in the electrospinning process without any further modifications in method either as pure reagent or mixed with small amounts of not functionalised polymer resulting in fibres of different qualities (Fig. 1).

  6. Organotin complexes with phosphines

    International Nuclear Information System (INIS)

    Passos, B. de F.T.; Jesus Filho, M.F. de; Filgueiras, C.A.L.; Abras, A.


    A series of organotin complexes was prepared involving phosphines bonded to the organotin moiety. The series include derivatives of SnCl x Ph 4-x (where x varied from zero to four with the phosphines Ph 3 P, (Ph 2 P)CH 2 , (Ph 2 P) 2 (CH 2 ) 2 , cis-(Ph 2 P)CH 2 , and CH 3 C(CH 2 PPh 2 ) 3 . A host of new complexes was obtained, showing different stoichiometries, bonding modes, and coordination numbers around the tin atom. These complexes were characterized by several different chemical and physical methods. The 119 Sn Moessbauer parameters varied differently. Whereas isomer shift values did not great variation for each group of complexs with the same organotin parent (SnCl x Ph 4-x ), reflecting a small change in s charge distribution on the Sn atom upon complexation, quadrupole splitting results varied widely, however, when the parent organotin compound was wholly symmetric (SnCl 4 and SnPPh 4 ), the complexes also tended to show quadrupole splitting values approaching zero. (author)


    Directory of Open Access Journals (Sweden)

    Marian STAN


    Full Text Available The actuality of the investigated theme. Nowadays, human evolution, including his intellectual development, proves the fact that especially the creation manpower and the employment was the solution of all life’s ambitions in society. So, the fact is that in reality, man is the most important capital of the society. Also, in an individual’s life, the practice of sport plays a significant role and that’s why the initiation, the launch and the management of sports complexes activity reveal the existence of specific management features that we will identify and explain in the current study. The aim of the research refers to the elaboration of a theoretical base of the management of the sport complexes, to the pointing of the factors that influence the efficient existence and function of a sport complex in our country and to the determination of the responsibilities that have a manager who directs successfully the activity of the sport complexes. The investigation is based on theoretical methods, such as: scientific documentation, analysis, synthesis, comparison and on empirical research methods, like: study of researched literature and observation. The results of the research indicate the fact that the profitability of a sport complex must assure a particular structure to avoid the bankruptcy risk and also, that the administration of the sport complexes activity must keep in view the reliable functions of the contemporaneous management.

  8. Unsymmetrical Chelation of N-Thioether-Functionalized Bis(diphenylphosphino)amine-Type Ligands and Substituent Effects on the Nuclearity of Iron(II) Complexes: Structures, Magnetism, and Bonding. (United States)

    Fliedel, Christophe; Rosa, Vitor; Falceto, Andrés; Rosa, Patrick; Alvarez, Santiago; Braunstein, Pierre


    Starting from the short-bite ligands N-thioether-functionalized bis(diphenylphosphino)amine-type (Ph2P)2N(CH2)3SMe (1) and (Ph2P)2N(p-C6H4)SMe (2), the Fe(II) complexes [FeCl2(1)]n (3), [FeCl2(2)]2 (4), [Fe(OAc)(1)2]PF6 (5), and [Fe(OAc)(2)2]PF6 (6) were synthesized and characterized by Fourier transform IR, mass spectrometry, elemental analysis, and also by X-ray diffraction for 3, 4, and 6. Complex 3 is a coordination polymer in which 1 acts as a P,P-pseudochelate and a (P,P),S-bridge, whereas 4 has a chlorido-bridged dinuclear structure in which 2 acts only as a P,P-pseudochelate. Since these complexes were obtained under strictly similar synthetic and crystallization conditions, these unexpected differences were ascribed to the different spacer between the nitrogen atom and the −SMe group. In both compounds, one Fe–P bond was found to be unusually long, and a theoretical analysis was performed to unravel the electronic or steric reasons for this difference. Density functional theory calculations were performed for a set of complexes of general formula [FeCl2(SR2){R21PN(R2)P′R23}] (R = H, Me; R1, R2, and R3 = H, Me, Ph), to understand the reasons for the significant deviation of the iron coordination sphere away from tetrahedral as well as from trigonal bipyramidal and the varying degree of unsymmetry of the two Fe–P bonds involving pseudochelating PN(R)P ligands. Electronic factors nicely explain the observed structures, and steric reasons were further ruled out by the structural analysis in the solid-state of the bis-chelated complex 6, which displays usual and equivalent Fe–P bond lengths. Magnetic susceptibility studies were performed to examine how the structural differences between 3 and 4 would affect the interactions between the iron centers, and it was concluded that 3 behaves as an isolated high-spin Fe(II) mononuclear complex, while significant intra- and intermolecular ferromagnetic interactions were evidenced for 4 at low temperatures

  9. The Orion complex

    International Nuclear Information System (INIS)

    Goudis, C.


    This work deals with some of the most typical complexes of interstellar matter and presents a holistic view of the well studied complexes in Orion, built on information derived from various branches of modern astrophysics. A wealth of published data is presented in the form of photographs, contour maps, diagrams and numerous heavily annotated tables. Chapter 1, which is concerned with the large scale view of the Orion region, outlines the morphology of the area and examines in particular the nature of Barnard's Loop and the associated filamentary structure in addition to the origin of the I Orion OB association. Chapter 2 focuses on the Great Orion Nebula (M42 or NGC 1976) and the small H II region to the north (M43 or NGC 1982). Chapter 3 examines the Orion Complex as a whole, i.e. the H II regions M42 and M43, the associated molecular clouds OMC 1 and OMC 2 and their interrelations. Chapter 4 contains a discussion of the empirical models introduced to attempt to explain certain aspects of this very complex region, and chapter 5 investigates the second prominent H II region and molecular cloud complex, NGC 2024 (Orion B, W12). (Auth.)

  10. Algorithmic Relative Complexity

    Directory of Open Access Journals (Sweden)

    Daniele Cerra


    Full Text Available Information content and compression are tightly related concepts that can be addressed through both classical and algorithmic information theories, on the basis of Shannon entropy and Kolmogorov complexity, respectively. The definition of several entities in Kolmogorov’s framework relies upon ideas from classical information theory, and these two approaches share many common traits. In this work, we expand the relations between these two frameworks by introducing algorithmic cross-complexity and relative complexity, counterparts of the cross-entropy and relative entropy (or Kullback-Leibler divergence found in Shannon’s framework. We define the cross-complexity of an object x with respect to another object y as the amount of computational resources needed to specify x in terms of y, and the complexity of x related to y as the compression power which is lost when adopting such a description for x, compared to the shortest representation of x. Properties of analogous quantities in classical information theory hold for these new concepts. As these notions are incomputable, a suitable approximation based upon data compression is derived to enable the application to real data, yielding a divergence measure applicable to any pair of strings. Example applications are outlined, involving authorship attribution and satellite image classification, as well as a comparison to similar established techniques.

  11. Complexes and imagination. (United States)

    Kast, Verena


    Fantasies as imaginative activities are seen by Jung as expressions of psychic energy. In the various descriptions of active imagination the observation of the inner image and the dialogue with inner figures, if possible, are important. The model of symbol formation, as Jung describes it, can be experienced in doing active imagination. There is a correspondence between Jung's understanding of complexes and our imaginations: complexes develop a fantasy life. Complex episodes are narratives of difficult dysfunctional relationship episodes that have occurred repeatedly and are internalized with episodic memory. This means that the whole complex episode (the image for the child and the image for the aggressor, connected with emotions) is internalized and can get constellated in everyday relationship. Therefore inner dialogues do not necessarily qualify as active imaginations, often they are the expression of complex-episodes, very similar to fruitless soliloquies. If imaginations of this kind are repeated, new symbols and new possibilities of behaviour are not found. On the contrary, old patterns of behaviour and fantasies are perpetuated and become cemented. Imaginations of this kind need an intervention by the analyst. In clinical examples different kinds of imaginations are discussed. © 2014, The Society of Analytical Psychology.

  12. Modeling Complex Systems

    CERN Document Server

    Boccara, Nino


    Modeling Complex Systems, 2nd Edition, explores the process of modeling complex systems, providing examples from such diverse fields as ecology, epidemiology, sociology, seismology, and economics. It illustrates how models of complex systems are built and provides indispensable mathematical tools for studying their dynamics. This vital introductory text is useful for advanced undergraduate students in various scientific disciplines, and serves as an important reference book for graduate students and young researchers. This enhanced second edition includes: . -recent research results and bibliographic references -extra footnotes which provide biographical information on cited scientists who have made significant contributions to the field -new and improved worked-out examples to aid a student’s comprehension of the content -exercises to challenge the reader and complement the material Nino Boccara is also the author of Essentials of Mathematica: With Applications to Mathematics and Physics (Springer, 2007).

  13. Complex Strategic Choices

    DEFF Research Database (Denmark)

    Leleur, Steen

    Effective decision making requires a clear methodology, particularly in a complex world of globalisation. Institutions and companies in all disciplines and sectors are faced with increasingly multi-faceted areas of uncertainty which cannot always be effectively handled by traditional strategies....... Complex Strategic Choices provides clear principles and methods which can guide and support strategic decision making to face the many current challenges. By considering ways in which planning practices can be renewed and exploring the possibilities for acquiring awareness and tools to add value...... to strategic decision making, Complex Strategic Choices presents a methodology which is further illustrated by a number of case studies and example applications. Dr. Techn. Steen Leleur has adapted previously established research based on feedback and input from various conferences, journals and students...

  14. Large erupted complex odontoma

    Directory of Open Access Journals (Sweden)

    Vijeev Vasudevan


    Full Text Available Odontomas are a heterogeneous group of jaw bone lesions, classified as odontogenic tumors which usually include well-diversified dental tissues. Odontoma is a term introduced to the literature by Broca in 1867. Trauma, infection and hereditary factors are the possible causes of forming this kind of lesions. Among odontogenic tumors, they constitute about 2/3 of cases. These lesions usually develop slowly and asymptomatically, and in most cases they do not cross the bone borders. Two types of odontoma are recognized: compound and complex. Complex odontomas are less common than the compound variety in the ratio 1:2.3. Eruption of an odontoma in the oral cavity is rare. We present a case of complex odontoma, in which apparent eruption has occurred in the area of the right maxillary second molar region.

  15. Alanine water complexes. (United States)

    Vaquero, Vanesa; Sanz, M Eugenia; Peña, Isabel; Mata, Santiago; Cabezas, Carlos; López, Juan C; Alonso, José L


    Two complexes of alanine with water, alanine-(H2O)n (n = 1,2), have been generated by laser ablation of the amino acid in a supersonic jet containing water vapor and characterized using Fourier transform microwave spectroscopy. In the observed complexes, water molecules bind to the carboxylic group of alanine acting as both proton donors and acceptors. In alanine-H2O, the water molecule establishes two intermolecular hydrogen bonds forming a six-membered cycle, while in alanine-(H2O)2 the two water molecules establish three hydrogen bonds forming an eight-membered ring. In both complexes, the amino acid moiety is in its neutral form and shows the conformation observed to be the most stable for the bare molecule. The microsolvation study of alanine-(H2O)n (n = 1,2) can be taken as a first step toward understanding bulk properties at a microscopic level.

  16. Can Complexity be Planned?

    Directory of Open Access Journals (Sweden)

    Ilona Koutny


    Full Text Available The long accepted complexity invariance of human languages has become controversial within the last decade. In investigations of the problem, both creole and planned languages have often been neglected. After a presentation of the scope of the invariance problem and the proposition of the natural to planned language continuum, this article will discuss the contribution of planned languages. It will analyze the complexity of Esperanto at the phonological, morphological, syntactic and semantic levels, using linguistic data bases. The role of the L2 speech community and development of the language will also be taken into account when discussing the endurance of the same level of simplicity of this planned international language. The author argues that complexity can be variable and to some extent planned and maintained.

  17. Complex Strategic Choices

    DEFF Research Database (Denmark)

    Leleur, Steen

    to strategic decision making, Complex Strategic Choices presents a methodology which is further illustrated by a number of case studies and example applications. Dr. Techn. Steen Leleur has adapted previously established research based on feedback and input from various conferences, journals and students......Effective decision making requires a clear methodology, particularly in a complex world of globalisation. Institutions and companies in all disciplines and sectors are faced with increasingly multi-faceted areas of uncertainty which cannot always be effectively handled by traditional strategies....... Complex Strategic Choices provides clear principles and methods which can guide and support strategic decision making to face the many current challenges. By considering ways in which planning practices can be renewed and exploring the possibilities for acquiring awareness and tools to add value...

  18. Philosophy of complex systems

    CERN Document Server


    The domain of nonlinear dynamical systems and its mathematical underpinnings has been developing exponentially for a century, the last 35 years seeing an outpouring of new ideas and applications and a concomitant confluence with ideas of complex systems and their applications from irreversible thermodynamics. A few examples are in meteorology, ecological dynamics, and social and economic dynamics. These new ideas have profound implications for our understanding and practice in domains involving complexity, predictability and determinism, equilibrium, control, planning, individuality, responsibility and so on. Our intention is to draw together in this volume, we believe for the first time, a comprehensive picture of the manifold philosophically interesting impacts of recent developments in understanding nonlinear systems and the unique aspects of their complexity. The book will focus specifically on the philosophical concepts, principles, judgments and problems distinctly raised by work in the domain of comple...

  19. Synchronization in complex networks

    Energy Technology Data Exchange (ETDEWEB)

    Arenas, A.; Diaz-Guilera, A.; Moreno, Y.; Zhou, C.; Kurths, J.


    Synchronization processes in populations of locally interacting elements are in the focus of intense research in physical, biological, chemical, technological and social systems. The many efforts devoted to understand synchronization phenomena in natural systems take now advantage of the recent theory of complex networks. In this review, we report the advances in the comprehension of synchronization phenomena when oscillating elements are constrained to interact in a complex network topology. We also overview the new emergent features coming out from the interplay between the structure and the function of the underlying pattern of connections. Extensive numerical work as well as analytical approaches to the problem are presented. Finally, we review several applications of synchronization in complex networks to different disciplines: biological systems and neuroscience, engineering and computer science, and economy and social sciences.

  20. Management of complex fisheries

    DEFF Research Database (Denmark)

    Frost, Hans Staby; Andersen, Peder; Hoff, Ayoe


    . This is defined as the management scheme which produces the highest net present value over a 25 year period. The assessed management schemes (scenarios) are composed by several measures as used in the Common Fisheries Policy of the European Union for the cod fishery in the Baltic Sea. The scenarios are total......The purpose of this paper is to demonstrate how fisheries economics management issues or problems can be analyzed by using a complex model based on conventional bioeconomic theory. Complex simulation models contain a number of details that make them suitable for practical management advice......, including taking into account the response of the fishermen to implemented management measures. To demonstrate the use of complex management models this paper assesses a number of second best management schemes against a first rank optimum (FRO), an ideal individual transferable quotas (ITQ) system...

  1. Introduction to Complex Plasmas

    CERN Document Server

    Bonitz, Michael; Ludwig, Patrick


    Complex plasmas differ from traditional plasmas in many ways: these are low-temperature high pressure systems containing nanometer to micrometer size particles which may be highly charged and strongly interacting. The particles may be chemically reacting or be in contact with solid surfaces, and the electrons may show quantum behaviour. These interesting properties have led to many applications of complex plasmas in technology, medicine and science. Yet complex plasmas are extremely complicated, both experimentally and theoretically, and require a variety of new approaches which go beyond standard plasma physics courses. This book fills this gap presenting an introduction to theory, experiment and computer simulation in this field. Based on tutorial lectures at a very successful recent Summer Institute, the presentation is ideally suited for graduate students, plasma physicists and experienced undergraduates.

  2. Modeling Complex Time Limits

    Directory of Open Access Journals (Sweden)

    Oleg Svatos


    Full Text Available In this paper we analyze complexity of time limits we can find especially in regulated processes of public administration. First we review the most popular process modeling languages. There is defined an example scenario based on the current Czech legislature which is then captured in discussed process modeling languages. Analysis shows that the contemporary process modeling languages support capturing of the time limit only partially. This causes troubles to analysts and unnecessary complexity of the models. Upon unsatisfying results of the contemporary process modeling languages we analyze the complexity of the time limits in greater detail and outline lifecycles of a time limit using the multiple dynamic generalizations pattern. As an alternative to the popular process modeling languages there is presented PSD process modeling language, which supports the defined lifecycles of a time limit natively and therefore allows keeping the models simple and easy to understand.

  3. Simulation in Complex Modelling

    DEFF Research Database (Denmark)

    Nicholas, Paul; Ramsgaard Thomsen, Mette; Tamke, Martin


    This paper will discuss the role of simulation in extended architectural design modelling. As a framing paper, the aim is to present and discuss the role of integrated design simulation and feedback between design and simulation in a series of projects under the Complex Modelling framework. Complex...... performance, engage with high degrees of interdependency and allow the emergence of design agency and feedback between the multiple scales of architectural construction. This paper presents examples for integrated design simulation from a series of projects including Lace Wall, A Bridge Too Far and Inflated...... Restraint developed for the research exhibition Complex Modelling, Meldahls Smedie Gallery, Copenhagen in 2016. Where the direct project aims and outcomes have been reported elsewhere, the aim for this paper is to discuss overarching strategies for working with design integrated simulation....

  4. Complex Polynomial Vector Fields

    DEFF Research Database (Denmark)

    vector fields. Since the class of complex polynomial vector fields in the plane is natural to consider, it is remarkable that its study has only begun very recently. There are numerous fundamental questions that are still open, both in the general classification of these vector fields, the decomposition...... of parameter spaces into structurally stable domains, and a description of the bifurcations. For this reason, the talk will focus on these questions for complex polynomial vector fields.......The two branches of dynamical systems, continuous and discrete, correspond to the study of differential equations (vector fields) and iteration of mappings respectively. In holomorphic dynamics, the systems studied are restricted to those described by holomorphic (complex analytic) functions...

  5. Entropy, Search, Complexity

    CERN Document Server

    Katona, Gyula O H; Tardos, Gábor


    The present volume is a collection of survey papers in the fields of entropy, search and complexity. They summarize the latest developments in their respective areas. More than half of the papers belong to search theory which lies on the borderline of mathematics and computer science, information theory and combinatorics, respectively. Search theory has variegated applications, among others in bioinformatics. Some of these papers also have links to linear statistics and communicational complexity. Further works survey the fundamentals of information theory and quantum source coding. The volume is recommended to experienced researchers as well as young scientists and students both in mathematics and computer science

  6. Complex HVPT and hyperasymptotics

    Energy Technology Data Exchange (ETDEWEB)

    Killingbeck, John P [Mathematics Department, University of Hull, Hull HU6 7RX (United Kingdom); Grosjean, Alain [Laboratoire d' Astrophysique de l' Observatoire de Besancon(CNRS, UMR 6091), 41 bis Avenue de l' Observatoire, BP 1615, 25010 Besancon Cedex (France); Jolicard, Georges [Laboratoire d' Astrophysique de l' Observatoire de Besancon(CNRS, UMR 6091), 41 bis Avenue de l' Observatoire, BP 1615, 25010 Besancon Cedex (France)


    Complex hypervirial perturbation theory (HVPT) is applied to the problem of a harmonic oscillator with a perturbation gx{sup 3}exp(i{psi}), for which the traditional Rayleigh-Schodinger perturbation theory has to be supplemented by hyperasymptotics for obtaining accurate resonance energies in the negative {psi} region. Complex HVPT gives accurate results for positive {psi} and for negative {psi} up to about vertical bar {phi} vertical bar = {pi}/24. The case of a quartic perturbed oscillator is also treated. (letter to the editor)

  7. Luminescent macrocyclic lanthanide complexes (United States)

    Raymond, Kenneth N; Corneillie, Todd M; Xu, Jide


    The present invention provides a novel class of macrocyclic compounds as well as complexes formed between a metal (e.g., lanthanide) ion and the compounds of the invention. Preferred complexes exhibit high stability as well as high quantum yields of lanthanide ion luminescence in aqueous media without the need for secondary activating agents. Preferred compounds incorporate hydroxy-isophthalamide moieties within their macrocyclic structure and are characterized by surprisingly low, non-specific binding to a variety of polypeptides such as antibodies and proteins as well as high kinetic stability. These characteristics distinguish them from known, open-structured ligands.

  8. Theories of computational complexity

    CERN Document Server

    Calude, C


    This volume presents four machine-independent theories of computational complexity, which have been chosen for their intrinsic importance and practical relevance. The book includes a wealth of results - classical, recent, and others which have not been published before.In developing the mathematics underlying the size, dynamic and structural complexity measures, various connections with mathematical logic, constructive topology, probability and programming theories are established. The facts are presented in detail. Extensive examples are provided, to help clarify notions and constructions. The lists of exercises and problems include routine exercises, interesting results, as well as some open problems.

  9. Complex function theory

    CERN Document Server

    Sarason, Donald


    Complex Function Theory is a concise and rigorous introduction to the theory of functions of a complex variable. Written in a classical style, it is in the spirit of the books by Ahlfors and by Saks and Zygmund. Being designed for a one-semester course, it is much shorter than many of the standard texts. Sarason covers the basic material through Cauchy's theorem and applications, plus the Riemann mapping theorem. It is suitable for either an introductory graduate course or an undergraduate course for students with adequate preparation. The first edition was published with the title Notes on Co

  10. Planning Complex Projects Automatically (United States)

    Henke, Andrea L.; Stottler, Richard H.; Maher, Timothy P.


    Automated Manifest Planner (AMP) computer program applies combination of artificial-intelligence techniques to assist both expert and novice planners, reducing planning time by orders of magnitude. Gives planners flexibility to modify plans and constraints easily, without need for programming expertise. Developed specifically for planning space shuttle missions 5 to 10 years ahead, with modifications, applicable in general to planning other complex projects requiring scheduling of activities depending on other activities and/or timely allocation of resources. Adaptable to variety of complex scheduling problems in manufacturing, transportation, business, architecture, and construction.

  11. Complex variables II essentials

    CERN Document Server

    Solomon, Alan D


    REA's Essentials provide quick and easy access to critical information in a variety of different fields, ranging from the most basic to the most advanced. As its name implies, these concise, comprehensive study guides summarize the essentials of the field covered. Essentials are helpful when preparing for exams, doing homework and will remain a lasting reference source for students, teachers, and professionals. Complex Variables II includes elementary mappings and Mobius transformation, mappings by general functions, conformal mappings and harmonic functions, applying complex functions to a

  12. Humic acid protein complexation (United States)

    Tan, W. F.; Koopal, L. K.; Weng, L. P.; van Riemsdijk, W. H.; Norde, W.


    Interactions of purified Aldrich humic acid (PAHA) with lysozyme (LSZ) are investigated. In solution LSZ is moderately positively and PAHA negatively charged at the investigated pH values. The proton binding of PAHA and of LSZ is determined by potentiometric proton titrations at various KCl concentrations. It is also measured for two mixtures of PAHA-LSZ and compared with theoretically calculated proton binding assuming no mutual interaction. The charge adaptation due to PAHA-LSZ interaction is relatively small and only significant at low and high pH. Next to the proton binding, the mass ratio PAHA/LSZ at the iso-electric point (IEP) of the complex at given solution conditions is measured together with the pH using the Mütek particle charge detector. From the pH changes the charge adaptation due to the interaction can be found. Also these measurements show that the net charge adaptation is weak for PAHA-LSZ complexes at their IEP. PAHA/LSZ mass ratios in the complexes at the IEP are measured at pH 5 and 7. At pH 5 and 50 mmol/L KCl the charge of the complex is compensated for 30-40% by K +; at pH 7, where LSZ has a rather low positive charge, this is 45-55%. At pH 5 and 5 mmol/L KCl the PAHA/LSZ mass ratio at the IEP of the complex depends on the order of addition. When LSZ is added to PAHA about 25% K + is included in the complex, but no K + is incorporated when PAHA is added to LSZ. The flocculation behavior of the complexes is also different. After LSZ addition to PAHA slow precipitation occurs (6-24 h) in the IEP, but after addition of PAHA to LSZ no precipitation can be seen after 12 h. Clearly, PAHA/LSZ complexation and the colloidal stability of PAHA-LSZ aggregates depend on the order of addition. Some implications of the observed behavior are discussed.

  13. Complex matrix model duality

    Energy Technology Data Exchange (ETDEWEB)

    Brown, T.W.


    The same complex matrix model calculates both tachyon scattering for the c=1 non-critical string at the self-dual radius and certain correlation functions of half-BPS operators in N=4 super- Yang-Mills. It is dual to another complex matrix model where the couplings of the first model are encoded in the Kontsevich-like variables of the second. The duality between the theories is mirrored by the duality of their Feynman diagrams. Analogously to the Hermitian Kontsevich- Penner model, the correlation functions of the second model can be written as sums over discrete points in subspaces of the moduli space of punctured Riemann surfaces. (orig.)

  14. Complex/Symplectic Mirrors

    Energy Technology Data Exchange (ETDEWEB)

    Chuang, Wu-yen; Kachru, Shamit; /Stanford U., ITP /SLAC; Tomasiello, Alessandro; /Stanford U., ITP


    We construct a class of symplectic non-Kaehler and complex non-Kaehler string theory vacua, extending and providing evidence for an earlier suggestion by Polchinski and Strominger. The class admits a mirror pairing by construction. Comparing hints from a variety of sources, including ten-dimensional supergravity and KK reduction on SU(3)-structure manifolds, suggests a picture in which string theory extends Reid's fantasy to connect classes of both complex non-Kaehler and symplectic non-Kaehler manifolds.

  15. Resilience and Complexity

    DEFF Research Database (Denmark)

    Dahlberg, Rasmus


    This paper explores two key concepts: resilience and complexity. The first is understood as an emergent property of the latter, and their inter-relatedness is discussed using a three tier approach. First, by exploring the discourse of each concept, next, by analyzing underlying relationships and...... robust. Robustness is a property of simple or complicated systems characterized by predictable behavior, enabling the system to bounce back to its normal state following a perturbation. Resilience, however, is an emergent property of complex adaptive systems. It is suggested that this distinction...

  16. Simulations with complex measure

    International Nuclear Information System (INIS)

    Markham, J.K.; Kieu, T.D.


    A method is proposed to handle the sign problem in the simulation of systems having indefinite or complex-valued measures. In general, this new approach, which is based on renormalisation blocking, is shown to yield statistical errors smaller that the crude Monte Carlo method using absolute values of the original measures. The improved method is applied to the 2D Ising model with temperature generalised to take on complex values. It is also adapted to implement Monte Carlo Renormalisation Group calculations of the magnetic and thermal critical exponents. 10 refs., 4 tabs., 7 figs


    Indian Academy of Sciences (India)


  18. μ-Phenoxo-μ-pseudohalide and μ-pseudohalide dinuclear ...

    Indian Academy of Sciences (India)

    7 621; (b) Zhang J-P and. Kitagawa S 2008 J. Am. Chem. Soc. 130 907. 9. Poulsen R D, Overgaard J, Schulman A, Østergaard C,. Murillo C A, Spackman M A and Iversen B B 2009. J. Am. Chem. Soc. 131 7580. 10. Ma L and Lin W 2008 J. Am. Chem. Soc. 130 13834. 11. (a) Feng P L, Stephenson C J, Amjad A, Ogawa G,.

  19. Two hybrids based on Keggin polyoxometalates and dinuclear ...

    Indian Academy of Sciences (India)

    By introducing mixed-ligands en and ox, Cu²⁺ and different polyoxotungstates as synthons, two new polyoxotungstate-based inorganic-organic hybrid compounds {[Cu₂ (en) ₂ (ox)][HPW₁₂O₄₀]} · (en) ₂ · 2H₂O (1) and {[Cu₂ (en) ₂ (ox)] [H₃BW₁₂O₄₀]} · (en) ₂ · 2H₂O (2) (en = ethylenediamine and ox ...

  20. Two 3D supramolecular frameworks assembled from the dinuclear ...

    Indian Academy of Sciences (India)

    : A crystallographic evidence of carboxylate(O)...π interaction. SUDIP MOHAPATRAa, SYAMANTAK ROYa, DEBAJYOTI GHOSHALb and TAPAS KUMAR MAJIa,∗. aMolecular Materials Laboratory, Chemistry and Physics of Materials Unit, ...

  1. Mononuclear and dinuclear manganese compounds stabilized by supramolecular interactions

    NARCIS (Netherlands)

    Viciano-Chumillas, M.; Giménez-Marqués, M.; Tanase, S.; Mutikainen, I.; Turpeinen, U.; Smits, J.M.M.; van Gelder, R.; de Jongh, L.J.; Reedijk, J.


    New manganese compounds [Mn(HphpzMe)2(H2phpzMe)(HCO2)] (1), [Mn2(phpzMe)2(HphpzMe)2(OCH3)]·2CH3OH (2), Na{[Mn(HphpzPh)(phpzPh)(MeOH)2]2}(HCO2) (3), [Mn(HphpzPh)2(EtOH)2]ClO4·2EtOH (4) and [Mn(HphpzPh)2N3] (5) were synthesized and characterized with various techniques. 1, 4 and 5 are mononuclear

  2. Estudio estructural de complejos dinucleares con doble puente de fosfinato


    Vázquez Sánchez, Trinidad


    El presente Proyecto Fin de Carrera se encuentra enmarcado en una de las líneas de investigación que desarrolla el Área de Química Inorgánica de la Universidad Poli-técnica de Cartagena en colaboración con el Departamento de Química Inorgánica de la Universidad de Murcia mediante la presentación de Comunicaciones a Congresos1,2,3 y la publicación de trabajos científicos4,5 que incluyen compuestos de níquel(II) con fosfa-tos, fosfonatos y fosfinatos. Escuela Técnica Superior de Ingeniería I...

  3. Estudio estructural de complejos dinucleares con doble puente de fosfato


    Barberá Rico, Jonathan


    El presente Proyecto Fin de Carrera se encuentra enmarcado en una de las líneas de investigación que desarrolla el Área de Química Inorgánica de la Universidad Poli-técnica de Cartagena en colaboración con el Departamento de Química Inorgánica de la Universidad de Murcia mediante la presentación de Comunicaciones a Congresos1,2,3 y la publicación de trabajos científicos4,5 que incluyen compuestos de níquel(II) con fosfa-tos, fosfonatos y fosfinatos. Escuela Técnica Superior de Ingeniería I...

  4. Silver(I) based dinuclear metallacycles with free thiophenyl ...

    Indian Academy of Sciences (India)

    and dipyrin14 derivatives. However, the design and syn- thesis of silver(I)-based metallacycles .... Another option is that the presence of con- formers that undergo a rapid equilibrium in solution on the NMR time .... plan to explore this aspect in our future work. Supplementary Information. Copies of NMR, mass spectra and ...

  5. Synthesis and crystal structure of a trihydrate of dinuclear ...

    African Journals Online (AJOL)

    A new compound, [Cd2(C7H6N2)3(C6H4O2N)4]·3H2O (1), has been prepared under mild hydrothermal conditions and structurally characterized by single crystal X-ray diffraction. The two cadmium(II) ions are bridged by a carboxyl group from one 2-pyridinecarboxylate ligand. The thermal gravimetry (TG) data indicate ...

  6. Syntheses, structures and properties of two dinuclear mercury(II ...

    Indian Academy of Sciences (India)

    27. Farrugia L J, ORTEP-3 1997 J. Appl. Crystallogr. 30. 565. 28. Geary W J 1971 Coord. Chem. Rev. 7 81. 29. Nakamoto K 2009 Infrared and Raman spectra of inor- ganic and coordination compounds, Part B, Hoboken,. New Jersey: John Wiley & Sons, sixth ed. 30. Lever A B P 1984 Inorganic electronic spectroscopy,.

  7. Well-defined iron complexes as efficient catalysts for "green" atom-transfer radical polymerization of styrene, methyl methacrylate, and butyl acrylate with low catalyst loadings and catalyst recycling. (United States)

    Nakanishi, So-Ichiro; Kawamura, Mitsunobu; Kai, Hidetomo; Jin, Ren-Hua; Sunada, Yusuke; Nagashima, Hideo


    Environmentally friendly iron(II) catalysts for atom-transfer radical polymerization (ATRP) were synthesized by careful selection of the nitrogen substituents of N,N,N-trialkylated-1,4,9-triazacyclononane (R3 TACN) ligands. Two types of structures were confirmed by crystallography: "[(R3 TACN)FeX2 ]" complexes with relatively small R groups have ionic and dinuclear structures including a [(R3 TACN)Fe(μ-X)3 Fe(R3 TACN)](+) moiety, whereas those with more bulky R groups are neutral and mononuclear. The twelve [(R3 TACN)FeX2 ]n complexes that were synthesized were subjected to bulk ATRP of styrene, methyl methacrylate (MMA), and butyl acrylate (BA). Among the iron complexes examined, [{(cyclopentyl)3 TACN}FeBr2 ] (4 b) was the best catalyst for the well-controlled ATRP of all three monomers. This species allowed easy catalyst separation and recycling, a lowering of the catalyst concentration needed for the reaction, and the absence of additional reducing reagents. The lowest catalyst loading was accomplished in the ATRP of MMA with 4 b (59 ppm of Fe based on the charged monomer). Catalyst recycling in ATRP with low catalyst loadings was also successful. The ATRP of styrene with 4 b (117 ppm Fe atom) was followed by precipitation from methanol to give polystyrene that contained residual iron below the calculated detection limit (0.28 ppm). Mechanisms that involve equilibria between the multinuclear and mononuclear species were also examined. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  8. Real and complex analysis

    CERN Document Server

    Apelian, Christopher; Taft, Earl; Nashed, Zuhair


    The Spaces R, Rk, and CThe Real Numbers RThe Real Spaces RkThe Complex Numbers CPoint-Set Topology Bounded SetsClassification of Points Open and Closed SetsNested Intervals and the Bolzano-Weierstrass Theorem Compactness and Connectedness Limits and Convergence Definitions and First Properties Convergence Results for SequencesTopological Results for Sequences Properties of Infinite SeriesManipulations of Series in RFunctions: Definitions and Limits DefinitionsFunctions as MappingsSome Elementary Complex FunctionsLimits of FunctionsFunctions: Continuity and Convergence Continuity Uniform Continuity Sequences and Series of FunctionsThe DerivativeThe Derivative for f: D1 → RThe Derivative for f: Dk → RThe Derivative for f: Dk → RpThe Derivative for f: D → CThe Inverse and Implicit Function TheoremsReal IntegrationThe Integral of f: [a, b] → RProperties of the Riemann Integral Further Development of Integration TheoryVector-Valued and Line IntegralsComplex IntegrationIntroduction to Complex Integrals Fu...

  9. Nitrido complexes of technetium

    International Nuclear Information System (INIS)

    Abram, U.; Abram, S.


    In this report synthesis, characterization and chemical behaviour of coordination compounds of the element technetium are reported containing a geminal nitrogen ligand. In addition, an evaluation of the in-vitro behaviour of the complexes is given as well as a list of all literature to this matter. (author)

  10. Complex Regional Pain Syndrome (United States)

    ... 40. It is uncommon in children and rare in the elderly. How is complex regional pain syndrome diagnosed? Your ... Mental Health Sex and Birth Control Sex and Sexuality Birth Control Family ... Men Seniors In The News Your Health Resources Healthcare Management End- ...

  11. Proteasomes: a complex story

    DEFF Research Database (Denmark)

    Hendil, Klavs B; Hartmann-Petersen, Rasmus


    Protein degradation in eukaryotic cells is important for regulation of metabolism, progression through the division cycle, in cell signalling pathways, and in mammals also for generation of antigen fragments for presentation on the major histocompatibility complex (MHC) class I. Most cell protein...

  12. Cobalt(III) complex

    Indian Academy of Sciences (India)


    CO. –. 2 radi- cals with [Co(III)(phendione)2Cl2]Cl (complex) have been studied by electron pulse radiolysis. Time resolved transient absorption spectra for all the four species show two peaks which match with those of phendione anion radical produced by the reaction of e. – aq with phendione. However, there are some ...

  13. Life Complexity and Diversity

    Indian Academy of Sciences (India)

    Home; Journals; Resonance – Journal of Science Education; Volume 1; Issue 12. Life Complexity and Diversity Whither Diversity. Madhav Gadgil. Series Article Volume 1 Issue 12 December 1996 pp 17-25. Fulltext. Click here to view fulltext PDF. Permanent link: ...

  14. Smoothed Complexity Theory

    NARCIS (Netherlands)

    Bläser, Markus; Manthey, Bodo

    Smoothed analysis is a new way of analyzing algorithms introduced by Spielman and Teng. Classical methods like worst-case or average-case analysis have accompanying complexity classes, such as P and Avg-P, respectively. Whereas worst-case or average-case analysis give us a means to talk about the

  15. Entropy and Kolmogorov complexity

    NARCIS (Netherlands)

    Moriakov, N.V.


    This thesis is dedicated to studying the theory of entropy and its relation to the Kolmogorov complexity. Originating in physics, the notion of entropy was introduced to mathematics by C. E. Shannon as a way of measuring the rate at which information is coming from a data source. There are, however,

  16. The CERN accelerator complex

    CERN Multimedia

    Christiane Lefèvre


    The LHC is the last ring (dark grey line) in a complex chain of particle accelerators. The smaller machines are used in a chain to help boost the particles to their final energies and provide beams to a whole set of smaller experiments, which also aim to uncover the mysteries of the Universe.

  17. The hamstring muscle complex

    NARCIS (Netherlands)

    van der Made, A. D.; Wieldraaijer, T.; Kerkhoffs, G. M.; Kleipool, R. P.; Engebretsen, L.; van Dijk, C. N.; Golanó, P.


    The anatomical appearance of the hamstring muscle complex was studied to provide hypotheses for the hamstring injury pattern and to provide reference values of origin dimensions, muscle length, tendon length, musculotendinous junction (MTJ) length as well as width and length of a tendinous

  18. Electromeric rhodium radical complexes

    NARCIS (Netherlands)

    Puschmann, F.F.; Harmer, J.; Stein, D.; Rüegger, H.; de Bruin, B.; Grützmacher, H.


    Radical changes: One single P-Rh-P angle determines whether the odd electron in the paramagnetic complex [Rh(trop2PPh)(PPh3)] is delocalized over the whole molecule (see picture, blue) or is localized on the P—Rh unit (red). The two energetically almost degenerate electromers exist in a fast

  19. Supporting complex search tasks

    DEFF Research Database (Denmark)

    Gäde, Maria; Hall, Mark; Huurdeman, Hugo


    introductory to specialized, and from authoritative to speculative or opinionated, when to show what sources of information? How does the information seeking process evolve and what are relevant differences between different stages? With complex task and search process management, blending searching, browsing...

  20. Complexity and formative experiences

    Directory of Open Access Journals (Sweden)

    Roque Strieder


    Full Text Available The contemporaneity is characterized by instability and diversity calling into question certainties and truths proposed in modernity. We recognize that the reality of things and phenomena become effective as a set of events, interactions, retroactions and chances. This different frame extends the need for revision of the epistemological foundations that sustain educational practices and give them sense. The complex thinking is an alternative option for acting as a counterpoint to classical science and its reductionist logic and knowledge compartmentalization, as well as to answer to contemporary epistemological and educational challenges. It aims to associate different areas and forms of knowledge, without, however merge them, distinguishing without separating the several disciplines and instances of the realities. This study, in theoretical references, highlights the relevance of complex approaches to support formative experiences because also able to produce complexities in reflections about educational issues. We conclude that formative possibilities from complexity potentialize the resignification of human’s conception and the understanding of its singularity in interdependence; The understanding that pedagogical and educational activities is a constant interrogation about the possibilities of knowing the knowledge and reframe learning, far beyond knowing its functions and utilitarian purposes; and, as a formative possibility, places us on the trail of responsibility, not as something eventual, but present and indicative of freedom to choose to stay or go beyond.

  1. The CERN accelerator complex

    CERN Multimedia

    Mobs, Esma Anais


    The LHC is the last ring (dark blue line) in a complex chain of particle accelerators. The smaller machines are used in a chain to help boost the particles to their final energies and provide beams to a whole set of smaller experiments, which also aim to uncover the mysteries of the Universe.

  2. Managing complex child law

    DEFF Research Database (Denmark)

    Svendsen, Idamarie Leth


    The article reports the findings of a qualitative study of Danish legal regulation of the public initial assessment of children and young persons and municipal practitioners’ decision-making under this regulation. The regulation mirrors new and complex relations between families and society and t...

  3. Complexity driven photonics

    KAUST Repository

    Fratalocchi, Andrea


    Disorder and chaos are ubiquitous phenomena that are mostly unwanted in applications. On the contrary, they can be exploited to create a new technology. In this talk I will summarize my research in this field, discussing chaotic energy harvesting, nonlinear stochastic resonance and complex nanolasers.

  4. The CERN accelerator complex

    CERN Multimedia

    Haffner, Julie


    The LHC is the last ring (dark grey line) in a complex chain of particle accelerators. The smaller machines are used in a chain to help boost the particles to their final energies and provide beams to a whole set of smaller experiments, which also aim to uncover the mysteries of the Universe.

  5. Complexity measures of music (United States)

    Pease, April; Mahmoodi, Korosh; West, Bruce J.


    We present a technique to search for the presence of crucial events in music, based on the analysis of the music volume. Earlier work on this issue was based on the assumption that crucial events correspond to the change of music notes, with the interesting result that the complexity index of the crucial events is mu ~ 2, which is the same inverse power-law index of the dynamics of the brain. The search technique analyzes music volume and confirms the results of the earlier work, thereby contributing to the explanation as to why the brain is sensitive to music, through the phenomenon of complexity matching. Complexity matching has recently been interpreted as the transfer of multifractality from one complex network to another. For this reason we also examine the mulifractality of music, with the observation that the multifractal spectrum of a computer performance is significantly narrower than the multifractal spectrum of a human performance of the same musical score. We conjecture that although crucial events are demonstrably important for information transmission, they alone are not suficient to define musicality, which is more adequately measured by the multifractality spectrum.

  6. Optical Complex Systems 2008 (United States)

    Brun, Guillaume

    The Optical Complex Systems are more and more in the heart of various systems that industrial applications bring to everyday life. From environment up to spatial applications, OCS is also relevant in monitoring, transportation, robotics, life sciences, sub-marine, and even for agricultural purposes.

  7. Complex adaptive systems ecology

    DEFF Research Database (Denmark)

    Sommerlund, Julie


    In the following, I will analyze two articles called Complex Adaptive Systems EcologyI & II (Molin & Molin, 1997 & 2000). The CASE-articles are some of the more quirkyarticles that have come out of the Molecular Microbial Ecology Group - a groupwhere I am currently making observational studies...

  8. Macroevolution of complex retroviruses

    DEFF Research Database (Denmark)

    Katzourakis, Aris; Gifford, Robert J; Tristem, Michael


    Retroviruses can leave a "fossil record" in their hosts' genomes in the form of endogenous retroviruses. Foamy viruses, complex retroviruses that infect mammals, have been notably absent from this record. We have found an endogenous foamy virus within the genomes of sloths and show that foamy vir...

  9. Energy momentum complex

    Energy Technology Data Exchange (ETDEWEB)

    Nashed, Gamal G.L. [Ain Shams University, Cairo (Egypt). Faculty of Science. Mathematics Dept.


    We show that the definition of the energy-momentum complex given by Moeller using Weitzenboeck spacetime in the calculations of gravitational energy gives results which are different from those obtained from other definitions given in the framework of general relativity. (author)

  10. unsymmetrical Schiff base complexes

    Indian Academy of Sciences (India)

    ecoline-RE 104 thermostat. FT- .... refluxed for 24 h under nitrogen atmosphere. The result- ing oil was grinded with n-hexane to extract impurities, ... diethyl ether into a solution of the metal complex in dimethylformamide (DMF) at room temperature ...

  11. Light in complex dielectrics

    NARCIS (Netherlands)

    Schuurmans, F.J.P.


    In this thesis the properties of light in complex dielectrics are described, with the two general topics of "modification of spontaneous emission" and "Anderson localization of light". The first part focuses on the spontaneous emission rate of an excited atom in a dielectric host with variable

  12. Prediction of Biomolecular Complexes

    KAUST Repository

    Vangone, Anna


    Almost all processes in living organisms occur through specific interactions between biomolecules. Any dysfunction of those interactions can lead to pathological events. Understanding such interactions is therefore a crucial step in the investigation of biological systems and a starting point for drug design. In recent years, experimental studies have been devoted to unravel the principles of biomolecular interactions; however, due to experimental difficulties in solving the three-dimensional (3D) structure of biomolecular complexes, the number of available, high-resolution experimental 3D structures does not fulfill the current needs. Therefore, complementary computational approaches to model such interactions are necessary to assist experimentalists since a full understanding of how biomolecules interact (and consequently how they perform their function) only comes from 3D structures which provide crucial atomic details about binding and recognition processes. In this chapter we review approaches to predict biomolecular complexesBiomolecular complexes, introducing the concept of molecular dockingDocking, a technique which uses a combination of geometric, steric and energetics considerations to predict the 3D structure of a biological complex starting from the individual structures of its constituent parts. We provide a mini-guide about docking concepts, its potential and challenges, along with post-docking analysis and a list of related software.

  13. Accessibility in complex networks (United States)

    Travençolo, B. A. N.; da F. Costa, L.


    This Letter describes a method for the quantification of the diversity of non-linear dynamics in complex networks as a consequence of self-avoiding random walks. The methodology is analyzed in the context of theoretical models and illustrated with respect to the characterization of the accessibility in urban streets.

  14. Complex Event Recognition Architecture (United States)

    Fitzgerald, William A.; Firby, R. James


    Complex Event Recognition Architecture (CERA) is the name of a computational architecture, and software that implements the architecture, for recognizing complex event patterns that may be spread across multiple streams of input data. One of the main components of CERA is an intuitive event pattern language that simplifies what would otherwise be the complex, difficult tasks of creating logical descriptions of combinations of temporal events and defining rules for combining information from different sources over time. In this language, recognition patterns are defined in simple, declarative statements that combine point events from given input streams with those from other streams, using conjunction, disjunction, and negation. Patterns can be built on one another recursively to describe very rich, temporally extended combinations of events. Thereafter, a run-time matching algorithm in CERA efficiently matches these patterns against input data and signals when patterns are recognized. CERA can be used to monitor complex systems and to signal operators or initiate corrective actions when anomalous conditions are recognized. CERA can be run as a stand-alone monitoring system, or it can be integrated into a larger system to automatically trigger responses to changing environments or problematic situations.

  15. Life: Complexity and Diversity

    Indian Academy of Sciences (India)

    Research, Bangalore. His fascination for the .... largest being an egg of the ostrich, largely loaded with stored food. So, to achieve larger sizes .... viruses and fungi. Packing Species. The diversity of living organisms has exploded, hand in hand with the evolving complexity of their interactions in communi- ties. In the dance ...

  16. pyridine-carboxamide complexes

    Indian Academy of Sciences (India)

    DOI 10.1007/s12039-016-1215-9. REGULAR ARTICLE. Synthesis, characterization, crystal structure and DNA-binding study of four cadmium(II) ...... be due to the presence of four non-planar ligand moi- eties in complexes (1), which probably play a key role to interact with DNA in electrostatic/covalent binding mode. 4.

  17. Query complexity in expectation

    NARCIS (Netherlands)

    Kaniewski, J.; Lee, T.; de Wolf, R.; Halldórsson, M.M.; Iwama, K.; Kobayashi, N.; Speckmann, B.


    We study the query complexity of computing a function f:{0,1}n→R+ in expectation. This requires the algorithm on input x to output a nonnegative random variable whose expectation equals f(x), using as few queries to the input x as possible. We exactly characterize both the randomized and the quantum

  18. Tevatron's complex collider cousins

    CERN Multimedia

    Fischer, W


    Letter referring to Schwarzschild's story "Disappointing performance and tight budgets confront Fermilab with tough decisions" and contesting that the Tevatron is not the most complex accelerator operating. They use the examples of CERN's SPS collider, HERA at DESY and the RHIC at Brookhaven (1/4 page)

  19. Typical Complexity Numbers

    Indian Academy of Sciences (India)

    First page Back Continue Last page Overview Graphics. Typical Complexity Numbers. Say. 1000 tones,; 100 Users,; Transmission every 10 msec. Full Crosstalk cancellation would require. Full cancellation requires a matrix multiplication of order 100*100 for all the tones. 1000*100*100*100 operations every second for the ...

  20. Life: Complexity and Diversity

    Indian Academy of Sciences (India)

    Home; Journals; Resonance – Journal of Science Education; Volume 1; Issue 4. Life : Complexity and Diversity Growing Larger. Madhav Gadgil. Series Article Volume 1 Issue 4 April 1996 pp 15-22. Fulltext. Click here to view fulltext PDF. Permanent link: ...

  1. Photocytotoxic lanthanide complexes

    Indian Academy of Sciences (India)

    Ln(III) complexes are also expected to be non-toxic in dark owing to the redox stability of the Ln(III) ions thus making them suitable for cellular applications in the presence of reducing cellular glutathione. The presence of heavy lanthanide metal is likely to facilitate the ISC due to heavy atom effect thereby contributing to the ...

  2. pyridine-carboxamide complexes

    Indian Academy of Sciences (India)

    In addition, a short ring interaction between thiophene S1 and pyri- dine N1 of a symmetry related complex (centroid-to- centroid distance = 3.707(4) Ε; dihedral angle between planes = 2.3(3) ..... Changes in the Histology of Kidneys in Common Carp,. Cyprinus carpio (Cyprinidae) Bull. Environ. Contam. Toxicol. 58 456. 10.

  3. Automatic Complexity Analysis

    DEFF Research Database (Denmark)

    Rosendahl, Mads


    One way to analyse programs is to to derive expressions for their computational behaviour. A time bound function (or worst-case complexity) gives an upper bound for the computation time as a function of the size of input. We describe a system to derive such time bounds automatically using abstrac...

  4. Crystal structure of a mixed-ligand silver(I complex of the non-steroidal anti-inflammatory drug diclofenac and pyrimidine

    Directory of Open Access Journals (Sweden)

    Sevim Hamamci Alisir


    Full Text Available In the title mixed-ligand silver(I coordination polymeric complex with the non-steroidal anti-inflammatory drug diclofenac (C14H11Cl2NO2 (diclH and pyrimidine (pym, namely poly[{μ2-2-[2-(2,6-dichloroanilinophenyl]acetato-κ2O:O′}(μ2-pyrimidine-κ2N1:N3silver(I], [Ag(C14H10Cl2NO2(C4H4N2]n or [Ag(μ-dicl(μ-pym]n, the very distorted tetrahedral AgN2O2 coordination centres comprise two N-atom donors from bridging pym ligands [Ag—N = 2.381 (3 and 2.412 (3 Å] and two carboxylate O-atom donors from dicl ligands [Ag—O = 2.279 (2 and 2.280 (2 Å], which bridge Ag atoms, giving a centrosymmetric dinuclear units with a short Ag...Ag separation [2.8931 (5 Å]. Within the units are short intraligand C—Cl...π(pym interactions [3.6409 (15 Å]. The units are linked through the bridging N atoms of the pym ligand into a two-dimensional sheet–polymer structure lying parallel to (100 and stabilized by inter-ring π–π interactions between the pym ligands [Cg...Cg = 3.4199 (17 Å]. Additional inter-unit C—H...O and C—H...Cg hydrogen-bonding interactions between the sheets give an overall three-dimensional structure.

  5. Interdisciplinary Symposium on Complex Systems

    CERN Document Server

    Rössler, Otto; Zelinka, Ivan


    The book you hold in your hands is the outcome of the “2014 Interdisciplinary Symposium on Complex Systems” held in the historical city of Florence. The book consists of 37 chapters from 4 areas of Physical Modeling of Complex Systems, Evolutionary Computations, Complex Biological Systems and Complex Networks. All 4 parts contain contributions that give interesting point of view on complexity in different areas in science and technology. The book starts with a comprehensive overview and classification of complexity problems entitled Physics in the world of ideas: Complexity as Energy”  , followed by chapters about complexity measures and physical principles, its observation, modeling and its applications, to solving various problems including real-life applications. Further chapters contain recent research about evolution, randomness and complexity, as well as complexity in biological systems and complex networks. All selected papers represent innovative ideas, philosophical overviews and state-of-the-...

  6. Models for B12-conjugated radiopharmaceuticals. Cobaloxime binding to new fac-[Re(CO)3(Me2bipyridine)(amidine)]BF4 complexes having an exposed pyridyl nitrogen. (United States)

    Lewis, Nerissa A; Marzilli, Patricia A; Fronczek, Frank R; Marzilli, Luigi G


    New mononuclear amidine complexes, fac-[Re(CO)3(Me2bipy)(HNC(CH3)(pyppz))]BF4 [(4,4'-Me2bipy (1), 5,5'-Me2bipy (2), and 6,6'-Me2bipy (3)] (bipy = 2,2'-bipyridine), were synthesized by treating the parent fac-[Re(I)(CO)3(Me2bipy)(CH3CN)]BF4 complex with the C2-symmetrical amine 1-(4-pyridyl)piperazine (pyppzH). The axial amidine ligand has an exposed, highly basic pyridyl nitrogen. The reaction of complexes 1-3 with a B12 model, (py)Co(DH)2Cl (DH = monoanion of dimethylglyoxime), in CH2Cl2 yielded the respective dinuclear complexes, namely, fac-[Re(CO)3(Me2bipy)(μ-(HNC(CH3)(pyppz)))Co(DH)2Cl]BF4 [(4,4'-Me2bipy (4), 5,5'-Me2bipy (5), and 6,6'-Me2bipy (6)]. (1)H NMR spectroscopic analysis of all compounds and single-crystal X-ray crystallographic data for 2, 3, 5, and 6 established that the amidine had only the E configuration in both the solid and solution states and that the pyridyl group is bound to Co in 4-6. Comparison of the NMR spectra of 1-3 with spectra of 4-6 reveals an unusually large "wrong-way" upfield shift for the pyridyl H2/6 signal for 4-6. The wrong-way H2/6 shift of (4-Xpy)Co(DH)2Cl (4-Xpy = 4-substituted pyridine) complexes increased with increasing basicity of the 4-Xpy derivative, a finding attributed to the influence of the magnetic anisotropy of the cobalt center on the shifts of the (1)H NMR signals of the pyridyl protons closest to Co. Our method of employing a coordinate bond for conjugating the fac-[Re(I)(CO)3] core to a vitamin B12 model could be extended to natural B12 derivatives. Because B12 compounds are known to accumulate in cancer cells, such an approach is a very attractive method for the development of (99m)Tc and (186/188)Re radiopharmaceuticals for targeted tumor imaging and therapy.

  7. Studies on electro-optical properties of conjugated polymers and novel metal complexes for nanocrystalline titanium oxide photovoltaic cells and sensors (United States)

    Kim, Young-Gi

    Several new approaches towards the development of dye and polymer sensitized photovoltaic cells and fluorescence sensors are the focus of this thesis. A new Ru(II) complex has been designed and synthesized introducing two types of ligands, 5-amino-1,10-phenanthroline and 4,4'-dicarboxylic acid-2,2'-bipyridine. This Ru(II) complex is capable of grafting onto nanocrystalline titanium dioxide and can be incorporated into solid polymer electrolytes. A series of analogous ruthenium complexes have also been synthesized and investigated to compare the effects of functional groups on various ligands by measuring spectroscopic and photovoltaic properties. A mononuclear Ru(II) complex using terpyridine and bipyridine ligands has been synthesized and compared to analogous homometallic dinuclear Ru(II) complex. The photophysical and photovoltaic (PV) properties have been investigated. Carboxylated polythiophenes have also been investigated as photosensitizers and charge transfer mediators for nanocrystalline TiO2 PV cells and show potential as a new class of light harvesting photosensitizers. In the present study, by introducing a chelating group such as a carboxylic acid into the side chain of polythiophenes, enhancements in photovoltaic properties are observed. We believe the carboxylic groups in the side chains enhance the adsorptions of these polythiophenes giving higher solar energy conversion efficiencies. The effects of the chelating group in the side chain of polythiophene have been investigated using a variety of analytical techniques. Cationic nanocrystalline TiO2 particles have been synthesized for which the size and composition of the nanoparticles were analyzed by TEM and EDXS. Multilayered films have been fabricated by sequential adsorption of TiO2 nanoparticles and poly (3-thiophene acetic acid). Each layer of the nanoparticles and PTAA in the thin film has also been characterized by XPS, AFM, and UV-vis spectroscopy. It is believed that these types of

  8. Complex Strategic Choices

    DEFF Research Database (Denmark)

    Leleur, Steen

    resulting in new material stemming from and focusing on practical application of a systemic approach. The outcome is a coherent and flexible approach named systemic planning. The inclusion of both the theoretical and practical aspects of systemic planning makes this book a key resource for researchers......Effective decision making requires a clear methodology, particularly in a complex world of globalisation. Institutions and companies in all disciplines and sectors are faced with increasingly multi-faceted areas of uncertainty which cannot always be effectively handled by traditional strategies....... Complex Strategic Choices provides clear principles and methods which can guide and support strategic decision making to face the many current challenges. By considering ways in which planning practices can be renewed and exploring the possibilities for acquiring awareness and tools to add value...

  9. Complexity is simple! (United States)

    Cottrell, William; Montero, Miguel


    In this note we investigate the role of Lloyd's computational bound in holographic complexity. Our goal is to translate the assumptions behind Lloyd's proof into the bulk language. In particular, we discuss the distinction between orthogonalizing and `simple' gates and argue that these notions are useful for diagnosing holographic complexity. We show that large black holes constructed from series circuits necessarily employ simple gates, and thus do not satisfy Lloyd's assumptions. We also estimate the degree of parallel processing required in this case for elementary gates to orthogonalize. Finally, we show that for small black holes at fixed chemical potential, the orthogonalization condition is satisfied near the phase transition, supporting a possible argument for the Weak Gravity Conjecture first advocated in [1].

  10. Complexes Tickling the $ubject

    Directory of Open Access Journals (Sweden)

    Matthew Gildersleeve


    Full Text Available This article continues my earlier work of reading Jung with Lacan. This article will develop Zizek’s work on Lacan’s concept of objet petit a by relating it to a phenomenological interpretation of Jung. I use a number of different examples, including Zizek’s interpretation of Francis Bacon, Edvard Munch, Hans Holbein and Johann Gottlieb Fichte, to describe the objet petit a and its relationship to a phenomenological interpretation of complexes. By integrating other Lacanian concepts, such as subject, drive, fantasy, jouissance, gaze, desire, and ego as well as the imaginary, symbolic and Real, this work also highlights how Hegel and Heidegger can elucidate the relationship between objet petit a and complexes. Jung’s transcendent function and the Rosarium Philosophorum also elucidate the relationship between Jung and Lacan.

  11. Polystochastic Models for Complexity

    CERN Document Server

    Iordache, Octavian


    This book is devoted to complexity understanding and management, considered as the main source of efficiency and prosperity for the next decades. Divided into six chapters, the book begins with a presentation of basic concepts as complexity, emergence and closure. The second chapter looks to methods and introduces polystochastic models, the wave equation, possibilities and entropy. The third chapter focusing on physical and chemical systems analyzes flow-sheet synthesis, cyclic operations of separation, drug delivery systems and entropy production. Biomimetic systems represent the main objective of the fourth chapter. Case studies refer to bio-inspired calculation methods, to the role of artificial genetic codes, neural networks and neural codes for evolutionary calculus and for evolvable circuits as biomimetic devices. The fifth chapter, taking its inspiration from systems sciences and cognitive sciences looks to engineering design, case base reasoning methods, failure analysis, and multi-agent manufacturing...

  12. Complex Polynomial Vector Fields

    DEFF Research Database (Denmark)

    Dias, Kealey

    The two branches of dynamical systems, continuous and discrete, correspond to the study of differential equations (vector fields) and iteration of mappings respectively. In holomorphic dynamics, the systems studied are restricted to those described by holomorphic (complex analytic) functions...... or meromorphic (allowing poles as singularities) functions. There already exists a well-developed theory for iterative holomorphic dynamical systems, and successful relations found between iteration theory and flows of vector fields have been one of the main motivations for the recent interest in holomorphic...... vector fields. Since the class of complex polynomial vector fields in the plane is natural to consider, it is remarkable that its study has only begun very recently. There are numerous fundamental questions that are still open, both in the general classification of these vector fields, the decomposition...

  13. On complex functions analyticity

    CERN Document Server

    Karavashkin, S B


    We analyse here the conventional definitions of analyticity and differentiability of functions of complex variable. We reveal the possibility to extend the conditions of analyticity and differentiability to the functions implementing the non-conformal mapping. On this basis we formulate more general definitions of analyticity and differentiability covering those conventional. We present some examples of such functions. By the example of a horizontal belt on a plane Z mapped non-conformally onto a crater-like harmonic vortex, we study the pattern of trajectory variation of a body motion in such field in case of field power function varying in time. We present the technique to solve the problems of such type with the help of dynamical functions of complex variable implementing the analytical non-conformal mapping

  14. Complex conductivity of soils

    DEFF Research Database (Denmark)

    Revil, A.; Coperey, A.; Shao, Z.


    The complex conductivity of soil remains poorly known despite the growing importance of this method in hyrogeophysics. In order to fill this gap of knowledge, we investigate the complex conductivity of 71 soils samples (including 4 peat samples) and one clean sand in the frequency range 0.1 Hertz...... to 45 kHz. The soil samples are saturated with 6 different NaCl brines with conductivities (0.031, 0.53, 1.15, 5.7, 14.7, and 22 S m-1, NaCl, 25°C) in order to determine their intrinsic formation factor and surface conductivity. This dataset is used to test the predictions of the dynamic Stern...... polarization model of porous media in terms of relationship between the quadrature conductivity and the surface conductivity. We also investigate the relationship between the normalized chargeability (the difference of in phase conductivity between two frequencies) and the quadrature conductivity...

  15. Operational Shock Complexity Theory (United States)


    Theory : Recommendations For The National Strategy To Defeat Terrorism.” Student Issue Paper, Center for Strategic Leadership , US Army War College, July...Lens of Complexity Theory : Recommendations For The National Strategy To Defeat Terrorism.” (Student Issue Paper, Center for Strategic Leadership , US...planners managed to cause confusion in the enemy’s internal model by operating in an unexpected manner. 140 Glenn E. James, “Chaos Theory : The

  16. Arithmetic of Complex Manifolds

    CERN Document Server

    Lange, Herbert


    It was the aim of the Erlangen meeting in May 1988 to bring together number theoretists and algebraic geometers to discuss problems of common interest, such as moduli problems, complex tori, integral points, rationality questions, automorphic forms. In recent years such problems, which are simultaneously of arithmetic and geometric interest, have become increasingly important. This proceedings volume contains 12 original research papers. Its main topics are theta functions, modular forms, abelian varieties and algebraic three-folds.

  17. Modeling Complex Systems

    International Nuclear Information System (INIS)

    Schreckenberg, M


    This book by Nino Boccara presents a compilation of model systems commonly termed as 'complex'. It starts with a definition of the systems under consideration and how to build up a model to describe the complex dynamics. The subsequent chapters are devoted to various categories of mean-field type models (differential and recurrence equations, chaos) and of agent-based models (cellular automata, networks and power-law distributions). Each chapter is supplemented by a number of exercises and their solutions. The table of contents looks a little arbitrary but the author took the most prominent model systems investigated over the years (and up until now there has been no unified theory covering the various aspects of complex dynamics). The model systems are explained by looking at a number of applications in various fields. The book is written as a textbook for interested students as well as serving as a comprehensive reference for experts. It is an ideal source for topics to be presented in a lecture on dynamics of complex systems. This is the first book on this 'wide' topic and I have long awaited such a book (in fact I planned to write it myself but this is much better than I could ever have written it!). Only section 6 on cellular automata is a little too limited to the author's point of view and one would have expected more about the famous Domany-Kinzel model (and more accurate citation!). In my opinion this is one of the best textbooks published during the last decade and even experts can learn a lot from it. Hopefully there will be an actualization after, say, five years since this field is growing so quickly. The price is too high for students but this, unfortunately, is the normal case today. Nevertheless I think it will be a great success! (book review)

  18. On convex complexity measures

    Czech Academy of Sciences Publication Activity Database

    Hrubeš, P.; Jukna, S.; Kulikov, A.; Pudlák, Pavel


    Roč. 411, 16-18 (2010), s. 1842-1854 ISSN 0304-3975 R&D Projects: GA AV ČR IAA1019401 Institutional research plan: CEZ:AV0Z10190503 Keywords : boolean formula * complexity measure * combinatorial rectangle * convexity Subject RIV: BA - General Mathematics Impact factor: 0.838, year: 2010

  19. Complex geometries in wood

    DEFF Research Database (Denmark)

    Tamke, Martin; Ramsgaard Thomsen, Mette; Riiber Nielsen, Jacob


    The versatility of wood constructions and traditional wood joints for the production of non standard elements was in focus of a design based research. Herein we established a seamless process from digital design to fabrication. A first research phase centered on the development of a robust...... parametric model and a generic design language a later explored the possibilities to construct complex shaped geometries with self registering joints on modern wood crafting machines. The research was carried out as collaboration with industrial partners....



    Nakatoh, Tetsuya; Omori, Keisuke; Yamada, Yasuhiro; Hirokawa, Sachio


    We are developing a search system DAISEn which integrates multiple search engines and generates a metasearch engine automatically. The target search engines of DAISEn are not general search engines, but are search engines specialized in some area. Integration of such engines yields efficiency and quality. There are search engines of new type which accept complex query and return structured data. Integration of such search engines is much harder than that of simple search engines which accept ...