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Sample records for bipyridines

  1. Vinyl Ruthenium-Modified Biphenyl and 2,2 '-Bipyridines

    Czech Academy of Sciences Publication Activity Database

    Scheerer, S.; Rotthowe, N.; Abdel-Rahman, O. S.; He, X.; Rigaut, S.; Kvapilová, Hana; Záliš, Stanislav; Winter, R. F.

    2015-01-01

    Roč. 54, č. 7 (2015), s. 3387-3402. ISSN 0020-1669 R&D Projects: GA MŠk LD14129 Institutional support: RVO:61388955 Keywords : TRANSITION-METAL-COMPLEXES * BRIDGED DIRUTHENIUM COMPLEXES * CARBONYL-BIPYRIDINE COMPLEXES Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 4.762, year: 2014

  2. Synthesis and complexation characteristics of phenanthroline and bipyridine diols

    NARCIS (Netherlands)

    Koning, B.; Boer, J.W. de; Meetsma, A.; Kellogg, R.M.

    2004-01-01

    Neocuproine (2,9-dimethyl-1,10-phenanthroline) 1 was converted to achiral and chiral tetradentate phenanthroline diols 3a-c by addition to benzophenone, adamantanone and camphor, respectively. Analogously 6,6'-dimethyl-2,2'-bipyridine 2 was converted to diol 7a on base-induced addition to benzopheno

  3. Crystal structure of bis(2,2′-bipyridine-κ2N,N′)bis(thiocyanato-κN)manganese(II) 2,2′-bipyridine monosolvate

    OpenAIRE

    Stefan Suckert; Inke Jess; Christian Näther

    2015-01-01

    In the crystal structure of the mononuclear title compound, [Mn(NCS)2(C10H8N2)2]·C10H8N2, the MnII cation is coordinated in an all-cis configuration by two N-bound thiocyanate anions and two 2,2′-bipyridine ligands within a slightly distorted octahedral environment. The asymmetric unit consists of one MnII cation, two thiocyanate anions and two 2,2′-bipyridine ligands, as well as two non-coordinating 2,2′-bipyridine ligands that are each located on centres of inversion. In the crystal structu...

  4. The adsorption of bipyridine molecules on Au(110) as measured by reflection anisotropy spectroscopy

    International Nuclear Information System (INIS)

    The reflection anisotropy spectra of 2, 2'-bipyridine and 4, 4'-bipyridine adsorbed onto an Au(110) surface in an electrochemical cell demonstrate that both systems form ordered structures. It is shown that reflection anisotropy spectroscopy can be used to distinguish between structural isomers adsorbed on the Au(110) surface

  5. 4,4’-Bis(4-octylphenoxy-2,2’-bipyridine

    Directory of Open Access Journals (Sweden)

    Zhen-Ting Du

    2009-12-01

    Full Text Available 4,4’-Bis(4-octylphenoxy-2,2’-bipyridine which can be used in complexes of ruthenium was synthesized. This ligand bears a long chain for the purpose of increasing the solubility of the final complex. The synthesis was achieved through a nucleophilic aromatic substitution reaction of 4,4’-bromo-2,2’-bipyridine and 4-octylphenol.

  6. 4,4’-Bis(4-octylphenoxy)-2,2’-bipyridine

    OpenAIRE

    Zhen-Ting Du; Jun-Ru Wang; Ru Liu; Yan Xu

    2009-01-01

    4,4’-Bis(4-octylphenoxy)-2,2’-bipyridine which can be used in complexes of ruthenium was synthesized. This ligand bears a long chain for the purpose of increasing the solubility of the final complex. The synthesis was achieved through a nucleophilic aromatic substitution reaction of 4,4’-bromo-2,2’-bipyridine and 4-octylphenol.

  7. Planar geometry of 4-substituted-2,2'-bipyridines synthesized by Sonogashira and Suzuki cross-coupling reactions

    Energy Technology Data Exchange (ETDEWEB)

    Luong Thi, T. T., E-mail: thuyltt@hnue.edu.vn; Nguyen Bich, N.; Nguyen, H. [Hanoi National University of Education, Chemistry Department (Viet Nam); Van Meervelt, L., E-mail: luc.vanmeervelt@chem.kuleuven.be [KU Leuven, Chemistry Department (Belgium)

    2015-12-15

    Two 4-substituted 2,2'-bipyridines, namely 4-(ferrocenylethynyl)-2,2'-bipyridine (I) and 4-ferrocenyl-2,2'-bipyridine (II) have been synthesized and fully characterized via single-crystal X-ray diffraction and {sup 1}H and {sup 13}C NMR analyses. The π-conjugated system designed from 2,2'-bipyridine modified with the ferrocenylethynyl and ferrocenyl groups shows the desired planarity. In the crystal packing of I and II, the molecules arrange themselves in head-to-tail and head-to-head motifs, respectively, resulting in consecutive layers of ferrocene and pyridine moieties.

  8. Crystal structure of bis(2,2′-bipyridine-κ2N,N′bis(thiocyanato-κNmanganese(II 2,2′-bipyridine monosolvate

    Directory of Open Access Journals (Sweden)

    Stefan Suckert

    2015-01-01

    Full Text Available In the crystal structure of the mononuclear title compound, [Mn(NCS2(C10H8N22]·C10H8N2, the MnII cation is coordinated in an all-cis configuration by two N-bound thiocyanate anions and two 2,2′-bipyridine ligands within a slightly distorted octahedral environment. The asymmetric unit consists of one MnII cation, two thiocyanate anions and two 2,2′-bipyridine ligands, as well as two non-coordinating 2,2′-bipyridine ligands that are each located on centres of inversion. In the crystal structure, the discrete [Mn(NCS2(C10H8N22] complex molecules are arranged in such a way that cavities are formed, in which the solvent 2,2′-bipyridine molecules are located. Apart from van der Waals forces, there are no remarkable intermolecular interactions present in the crystal structure.

  9. Peculiarities of the SEHRS and SERS Spectra of - Bipyridine Molecule

    CERN Document Server

    Chelibanov, Vladimir P; Polubotko, Aleksey M

    2016-01-01

    The SEHRS and SERS spactra of 4,4 - Bipyridine are analyzed on the base of the Dipole-Quadrupole theory for two possible geometries of the molecule. It is demonstrated that there appear strong lines caused by vibrations transforming after a unit irreducible representation both for the geometry with D2 and D2h symmetry groups, which may probably describe the symmetry properties of the molecule. Appearance of these lines is associated with a strong quadrupole light-molecule interaction, which arises in nano size rregions of sharp roughness of the metal. In addition, there are the lines caused by contributions from both the vibrations transforming after the unit irredicible representations A or Ag and the representations B1 or B1u, respectively, which describe transformational properties of the Ez component of the dipole moment, which is perpendicular to the surface for both geometries. This result is associated with a specific geometry of the molecule, when the indicated vibrations can be nearly degenerated and...

  10. Quantum conductance of 4,4-bipyridine molecular junctions: Role of electrode work function and local d band

    DEFF Research Database (Denmark)

    Rauba, J.M.C.; Strange, Mikkel; Thygesen, Kristian Sommer

    2008-01-01

    We present density-functional theory calculations for the geometry and conductance of 4,4-bipyridine (BPD) nanojunctions with Au and Pt electrodes. The fact that transport takes place via bipyridine's lowest unoccupied molecular orbital (LUMO) suggests that the Au-BPD junction should have larger...

  11. 2,3,4,5-Tetrafluorobenzoic acid–4,4′-bipyridine (2/1

    Directory of Open Access Journals (Sweden)

    Xiaohui Zhu

    2009-08-01

    Full Text Available The asymmetric unit of the title compound, 2C7H2F4O2·C10H8N2, contains one molecule of 2,3,4,5-tetrafluorobenzoic acid (tfb and half of a centrosymmetric 4,4′-bipyridine molecule. Intermolecular O—H...N hydrogen bonds link two tfb molecules and one 4,4′-bipyridine molecule into a trimer. Weak intermolecular C—H...F interactions assemble these trimers into a three-dimensional network structure.

  12. 2,3,4,5-Tetrafluorobenzoic acid–4,4′-bipyridine (2/1)

    OpenAIRE

    Xiaohui Zhu

    2009-01-01

    The asymmetric unit of the title compound, 2C7H2F4O2·C10H8N2, contains one molecule of 2,3,4,5-tetrafluorobenzoic acid (tfb) and half of a centrosymmetric 4,4′-bipyridine molecule. Intermolecular O—H...N hydrogen bonds link two tfb molecules and one 4,4′-bipyridine molecule into a trimer. Weak intermolecular C—H...F interactions assemble these trimers into a three-dimensional network structure.

  13. Crystal structure of poly[[(2,2′-bipyridine)manganese(II)]-di-μ-thiocyanato

    OpenAIRE

    Stefan Suckert; Susanne Wöhlert; Inke Jess; Christian Näther

    2014-01-01

    In the crystal structure of the polymeric title compound, [Mn(NCS)2(C10H8N2)]n, the MnII cations are coordinated by one chelating 2,2′-bipyridine ligand and four thiocyanate anions (two N- and two S-coordinating), forming a distorted [MnN4S2] octahedron. The asymmetric unit consists of one manganese cation located on a twofold rotation axis and half of a 2,2′-bipyridine ligand, the other half being generated by the same twofold rotation axis, as well as one thiocyanate anion in a general posi...

  14. Versatile ruthenium complexes based on 2,2'-bipyridine modified peptoids.

    Science.gov (United States)

    Baskin, Maria; Panz, Larisa; Maayan, Galia

    2016-08-16

    Helical peptoids bearing 2,2'-bipyridine form ruthenium complexes via intermolecular binding to linear peptoid strands or intramolecular binding to a cyclic scaffold. Ru(ii) binding promoted changes in the conformational order of the peptoids, and chiral induction from the peptoids to their metal center was observed. PMID:27349289

  15. DNA interactions and cytotoxic studies of cis-platin analogues of substituted 2,2'-bipyridines

    Science.gov (United States)

    Patel, Mohan N.; Parmar, Pradhuman A.; Gandhi, Deepen S.; Patidar, Anshul P.

    2012-11-01

    Platinum(II) complexes [Pt(4″-fpbpy)Cl2] (1), [Pt(4″-mepbpy)Cl2] (2), [Pt(4″-mpbpy)Cl2] (3) and [Pt(4″-bopbpy)Cl2] (4) {where 4″-fpbpy = 4-(4″-fluorophenyl)-6-phenyl-2,2'-bipyridine, 4″-mepbpy = 4-(4″-methylphenyl)-6-phenyl-2,2'-bipyridine, 4″-mpbpy = 4-(4″-methoxyphenyl)-6-phenyl-2,2'-bipyridine, 4″-bopbpy = 4-(4″-benzyloxyphenyl)-6-phenyl-2,2'-bipyridine} have been synthesized and characterized. The binding strength and binding mode of the complexes with HS DNA (Herring Sperm) have been investigated by absorption titration and viscosity measurement studies. The results have been revealed that the complexes bind to DNA by covalent mode with intrinsic binding constant Kb ranging from 6.05 × 104 M-1 to 3.48 × 105 M-1. The unwinding angle of pUC19 DNA has been evaluated by gel electrophoresis assay. The brine shrimp bioassay has been performed to study the in vitro cytotoxic properties of the synthesized metal complexes.

  16. Photovoltaic performance of ruthenium complex dye associated with number and position of carboxyl groups on bipyridine ligands

    International Nuclear Information System (INIS)

    A series of ruthenium complex dyes with different number and position of carboxyl groups on bipyridine ligands, such as Ru(4-carboxyl-4′-methyl-2,2′-bipyridine)(4,4′-dimethyl-2,2′- bipyridine)(NCS)2 (denoted as Ru1A), Ru(4-carboxyl-4′-methyl-2,2′-bipyridine)2(NCS)2 (Ru11A), Ru(4,4′-dicarboxyl-2,2′-bipyridine)(4,4′-dimethyl-2,2′-bipyridine)(NCS)2 (Ru2A), and Ru(4-carboxyl-4′-methyl-2,2′-bipyridine)(4,4′-dicarboxyl-2,2′-bipyridine) (NCS)2 (Ru3A) were synthesized and compared with Ru(4,4′-dicarboxyl-2,2′-bipyridine)2 (NCS)2, commonly known as N3 dye for the adsorption behavior on the TiO2 surface and photovoltaic properties of dye-sensitized solar cells. The experimental results show that the tilt angle of ruthenium dyes on the TiO2 surface which is dependent on the number and position of their carboxyl groups strongly affected the photovoltaic performance. - Highlights: • Ruthenium dye with different number of carboxyl groups adsorbed on the TiO2 with different tilt angle. • Ruthenium dye injected the electrons to the TiO2 through the carboxyl groups. • Photocurrent of DSSC, increased with the number of carboxyl groups on the ruthenium dye

  17. The intercalation reaction of 2,2'-bipyridine with layered compound MnPS3

    International Nuclear Information System (INIS)

    The intercalation process of 2,2'-bipyridine into layered MnPS3 is studied with powder X-ray powder diffraction (XRD) technology as the monitoring tool. From the XRD results, it is found that the absence or presence of acid greatly influences the existing form and the arranged orientation of the guest. Two series of the reactions are carried out. In Series A, only MnPS3 and 2,2'-bipyridine are present. While in Series B, a variety of acetic acid is added. During the intercalation of Series A, there coexist four phases: the 0 0 l phase (with lattice spacing of 6.47 A) is pristine MnPS3; the 0 0 l' phase (with lattice spacing of 9.81 A), indicating the parallel orientation of the 2,2'-bipyridine molecular ring to the layer; the 0 0 l'' phase (with lattice spacing of 12.20 A), indicating the perpendicular orientation of the 2,2'-bipyridine molecular ring to the layer of the host, which is only an intermediate phase for the formation of the 0 0 l''' phase; the 0 0 l''' phase (with the lattice spacing of 15.33 A), indicating the existence of the complex cation [Mn(bipy)3]2+ coming from the in situ coordination of the inserted guest with intralayered Mn2+ ions between the interlayer space of host. As the intercalation proceeds, the 0 0 l, 0 0 l' and 0 0 l'' phases finally disappear, and 0 0 l''' phase is intensified and a complete intercalate is obtained. In Series B, due to the presence of the acid, the formation of the complex cation [Mn(bipy)3]2+ is inhibited, and the amount of the acid in the intercalation plays a key role in the formation of the guest. With the increase of the acid, the protonated bipyridine becomes the main existing form of the guest, which is arranged in the perpendicular orientation of molecular ring to the layer. From the experimental evidences, the possible intercalation mechanisms are proposed and the novel intercalation phenomenon of in situ coordination of the inserted 2,2'-bipyridine with Mn2+ of the host is elucidated

  18. Bipyridine cardiotonics: the three-dimensional structures of amrinone and milrinone.

    Science.gov (United States)

    Robertson, D W; Beedle, E E; Swartzendruber, J K; Jones, N D; Elzey, T K; Kauffman, R F; Wilson, H; Hayes, J S

    1986-05-01

    The cardiotonic drug milrinone (1,6-dihydro-2-methyl-6-oxo-[3,4'-bipyridine]-5-carbonitrile) is superior to its analogue amrinone (5-amino-[3,4'-bipyridin]-6(1H)-one) by virtue of its greater potency and reduced side effect profile. We confirmed initial reports on the potencies of milrinone and amrinone and found that after intravenous administration to phenobarbital anesthetized dogs, the drugs had cumulative inotropic ED50's of 37 and 1891 micrograms/kg, respectively; relative effects on heart rate and blood pressure were comparable. There are two structural differences between amrinone and milrinone: (1) milrinone has a pyridone 2-methyl substituent and (2) the pyridone 5-amino substituent of amrinone is replaced with a nitrile in milrinone. We confirmed structure-activity studies that indicated that the 2-methyl substituent appears to be primarily responsible for the dramatic difference in the potencies of amrinone and milrinone. A plausible explanation for the effect of the methyl substituent is an altered molecular topology resulting from its steric interaction with the 3',5'-hydrogen atoms. Consequently, we probed the three-dimensional structures of these two compounds by X-ray crystallography. The dihedral angle between the planes formed by the two aromatic rings of amrinone was 1.3 degrees. In marked contrast, the corresponding angle for milrinone was 52.2 degrees. Moreover, 1H NMR studies revealed conformational differences in solution. Whereas the 2-methyl substituent undoubtedly produces some electronic and hydrophobic perturbations in the bipyridine cardiotonic series, the most significant effect, from a global viewpoint, is the altered molecular topology. PMID:3701782

  19. Dibromido(6-methyl-2,2′-bipyridine-κ2N,N′zinc(II

    Directory of Open Access Journals (Sweden)

    Vahid Amani

    2010-10-01

    Full Text Available In the title compound, [ZnBr2(C11H10N2], the ZnII atom is four-coordinated in a distorted tetrahedral configuration by two N atoms from a 6-methyl-2,2′-bipyridine ligand and two terminal Br atoms. Weak intermolecular C—H...Br hydrogen bonds and π–π stacking interactions between the pyridine rings [centroid–centroid distances = 3.763 (5 and 3.835 (6 Å] contribute to crystal-packing effects.

  20. The electronic spectrum of cryogenic ruthenium-tris-bipyridine dications in vacuo

    Science.gov (United States)

    Xu, Shuang; Smith, James E. T.; Weber, J. Mathias

    2016-07-01

    We report the electronic spectrum of the prototypical ruthenium coordination complex Ru(bpy)32+ (bpy = 2, 2'-bipyridine) by messenger tagging with N2 in a cryogenic ion trap and photodissociation spectroscopy of mass selected Ru(bpy)32+ ṡ N2 ions. We observe individual electronic bands and groups of bands with unprecedented detail, particularly in the usually unresolved metal-to-ligand charge transfer region of the spectrum. By comparing our experimental results with time-dependent density functional theory, both with and without spin-orbit interaction [Heully et al., J. Chem. Phys. 131, 184308 (2009)], we are able to assign the spectrum of the isolated ion.

  1. catena-Poly[[diaquabis(diphenylacetatozinc(II]-μ-4,4′-bipyridine

    Directory of Open Access Journals (Sweden)

    2009-03-01

    Full Text Available In the title compound, [Zn(C14H11O22(C10H8N2(H2O2]n, the ZnII ion lies on a crystallographic inversion center and is in a slightly distorted octahedral coordination enviroment. 4,4′-Bipyridine ligands act as bridging ligands, connecting ZnII ions into a chain along the b-axis direction. In the crystal structure, these chains are linked by intermolecular O—H...O hydrogen bonds to form a two-dimensional network parallel to the ab plane.

  2. Synthesis of modified pyridine and bipyridine substituted coumarins as potent antimicrobial agents

    Directory of Open Access Journals (Sweden)

    Lad Hemali B.

    2015-01-01

    Full Text Available In search for new antimicrobial agents a series of new modified pyridine and bipyridine substituted coumarins 5a-y was designed and synthesized by adopting molecular hybridization strategy. All the synthesized compounds were evaluated for their in vitro antimicrobial activity using broth dilution method against selected bacterial (Gram-positive and Gram-negative and fungal strains. Compounds 5a, 5f, 5g, 5n, 5r, 5t, 5w, 5x and 5y demonstrated promising antibacterial activity while other derivatives showed comparable activity to standard drugs used as reference.

  3. Reactivity descriptors and electron density analysis for ligand chemistry: A case study of 2,2'-bipyridine and its analogues

    Indian Academy of Sciences (India)

    Bhakti S Kulkarni; Akhilesh Tanwar; Sourav Pal

    2007-09-01

    In this paper, we study the reactivity of diimines like 2,2'-bipyridine and its analogues using reactivity descriptors. We discuss evaluation of local descriptors using relaxed as well as frozen approximation and characterize the / acceptance/donor characteristics of the above ligands. The intermolecular reactivity sequence for the same systems is examined by the global and local philicity index. In addition, electron density analysis has been carried out to highlight the possible strengths of interaction of the bipyridine and its analogues with metal ions.

  4. Decamethylytterbocene Complexes of Bipyridines and Diazabutadienes: Multiconfigurational Ground States and Open-Shell Singlet Formation

    International Nuclear Information System (INIS)

    Partial ytterbium f-orbital occupancy (i.e., intermediate valence) and open-shell singlet formation are established for a variety of bipyridine and diazabutadiene adducts with decamethylytterbocene, (C5Me5)2Yb, abbreviated as Cp*2Yb. Data used to support this claim include ytterbium valence measurements using Yb LIII-edge X-ray absorption near-edge structure spectroscopy, magnetic susceptibility, and complete active space self-consistent field (CASSCF) multiconfigurational calculations, as well as structural measurements compared to density functional theory calculations. The CASSCF calculations indicate that the intermediate valence is the result of a multiconfigurational ground-state wave function that has both an open-shell singlet f13(π*)1, where π* is the lowest unoccupied molecular orbital of the bipyridine or dpiazabutadiene ligands, and a closed-shell singlet f14 component. A number of other competing theories for the unusual magnetism in these materials are ruled out by the lack of temperature dependence of the measured intermediate valence. These results have implications for understanding chemical bonding not only in organolanthanide complexes but also for f-element chemistry in general, as well as understanding magnetic interactions in nanoparticles and devices

  5. Diazonium salt derivatives of osmium bipyridine complexes: Electrochemical grafting and characterisation of modified surfaces

    Energy Technology Data Exchange (ETDEWEB)

    Garrett, David J. [MacDiarmid Institute for Advanced Materials and Nanotechnology, Department of Chemistry, University of Canterbury, Private Bag 4800, Christchurch (New Zealand); Jenkins, Peter [School of Chemistry, National University of Ireland, Galway (Ireland); Polson, Matthew I.J. [Department of Chemistry, University of Canterbury, Private Bag 4800, Christchurch (New Zealand); Leech, Donal [School of Chemistry, National University of Ireland, Galway (Ireland); Baronian, Keith H.R. [School of Biological Sciences, University of Canterbury, Private Bag 4800, Christchurch (New Zealand); Downard, Alison J., E-mail: alison.downard@canterbury.ac.n [MacDiarmid Institute for Advanced Materials and Nanotechnology, Department of Chemistry, University of Canterbury, Private Bag 4800, Christchurch (New Zealand)

    2011-02-01

    Osmium bipyridine complexes were directly grafted to carbon electrodes through electroreduction of the diazonium salts [Os(bpy-ph-N{sub 2}{sup +}){sub 3}](PF{sub 6}){sub 5} (1) and [Os(bpy-ph-N{sub 2}{sup +}){sub 2}Cl{sub 2}](PF{sub 6}){sub 2} (2). Growth of the films was not self-limiting as is usually found for grafting from diazonium salts. It appears that electron hopping through the bipyridine ligands of the immobilised complexes enables film growth to continue at a constant rate during grafting by potential cycling. The surface concentrations of deposited films were measured electrochemically and the film thicknesses were measured by depth-profiling using the atomic force microscope. Films up to 42 nm thick were prepared with no evidence for slowing of film growth. The grafted films exhibited high stability when repetitively cycled through the Os{sup 2+/3+} couple and electron transfer rate constants of 11.4 s{sup -1} and 35.4 s{sup -1} were measured in ACN and PBS, respectively, for the Os{sup 2+/3+} couple of the film grafted from 1.

  6. Diazonium salt derivatives of osmium bipyridine complexes: Electrochemical grafting and characterisation of modified surfaces

    International Nuclear Information System (INIS)

    Osmium bipyridine complexes were directly grafted to carbon electrodes through electroreduction of the diazonium salts [Os(bpy-ph-N2+)3](PF6)5 (1) and [Os(bpy-ph-N2+)2Cl2](PF6)2 (2). Growth of the films was not self-limiting as is usually found for grafting from diazonium salts. It appears that electron hopping through the bipyridine ligands of the immobilised complexes enables film growth to continue at a constant rate during grafting by potential cycling. The surface concentrations of deposited films were measured electrochemically and the film thicknesses were measured by depth-profiling using the atomic force microscope. Films up to 42 nm thick were prepared with no evidence for slowing of film growth. The grafted films exhibited high stability when repetitively cycled through the Os2+/3+ couple and electron transfer rate constants of 11.4 s-1 and 35.4 s-1 were measured in ACN and PBS, respectively, for the Os2+/3+ couple of the film grafted from 1.

  7. Intermediate-Valence Tautomerism in Decamethylytterbocene Complexes of Methyl-Substituted Bipyridines

    Energy Technology Data Exchange (ETDEWEB)

    Booth, Corwin H.; Kazhdan, Daniel; Werkema, Evan L.; Walter, Marc D.; Lukens, Wayne W.; Bauer, Eric D.; Hu, Yung-Jin; Maron, Laurent; Eisenstein, Odile; Head-Gordon, Martin; Andersen, Richard A.

    2011-01-25

    Multiconfigurational, intermediate valent ground states are established in several methyl-substituted bipyridine complexes of bispentamethylcyclopentadienylytterbium, Cp*{sub 2} Yb(Me{sub x}-bipy). In contrast to Cp*{sub 2} Yb(bipy) and other substituted-bipy complexes, the nature of both the ground state and the first excited state are altered by changing the position of the methyl or dimethyl substitutions on the bipyridine rings. In particular, certain substitutions result in multiconfigurational, intermediate valent open-shell singlet states in both the ground state and the first excited state. These conclusions are reached after consideration of single-crystal x-ray diffraction (XRD), the temperature dependence of x-ray absorption near-edge structure (XANES), extended x-ray absorption fine-structure (EXAFS), and magnetic susceptibility data, and are supported by CASSCF-MP2 calculations. These results place the various Cp*{sub 2}Yb(bipy) complexes in a new tautomeric class, that is, intermediate-valence tautomers.

  8. Decamethylytterbocene Complexes of Bipyridines and Diazabutadienes: Multiconfigurational Ground States and Open-Shell Singlet Formation

    Energy Technology Data Exchange (ETDEWEB)

    Booth, Corwin H.; Walter, Marc D.; Kazhdan, Daniel; Hu, Yung-Jin; Lukens, Wayne W.; Bauer, Eric D.; Maron, Laurent; Eisenstein, Odile; Andersen, Richard A.

    2009-04-22

    Partial ytterbium f-orbital occupancy (i.e., intermediate valence) and open-shell singlet formation are established for a variety of bipyridine and diazabutadiene adducts with decamethylytterbocene, (C5Me5)2Yb, abbreviated as Cp*2Yb. Data used to support this claim include ytterbium valence measurements using Yb LIII-edge X-ray absorption near-edge structure spectroscopy, magnetic susceptibility, and complete active space self-consistent field (CASSCF) multiconfigurational calculations, as well as structural measurements compared to density functional theory calculations. The CASSCF calculations indicate that the intermediate valence is the result of a multiconfigurational ground-state wave function that has both an open-shell singlet f13(?*)1, where pi* is the lowest unoccupied molecular orbital of the bipyridine or dpiazabutadiene ligands, and a closed-shell singlet f14 component. A number of other competing theories for the unusual magnetism in these materials are ruled out by the lack of temperature dependence of the measured intermediate valence. These results have implications for understanding chemical bonding not only in organolanthanide complexes but also for f-element chemistry in general, as well as understanding magnetic interactions in nanoparticles and devices.

  9. catena-Poly[[[triaqua[3-(4-carboxyphenoxyphthalato-κO2]manganese(II]-μ-4,4′-bipyridine-κ2N:N′] 4,4′-bipyridine monosolvate dihydrate

    Directory of Open Access Journals (Sweden)

    Wei Sun

    2013-02-01

    Full Text Available In the title compound, {[Mn(C15H8O7(C10H8N2(H2O3]·C10H8N2·2H2O}n, the bridging mode of the coordinating 4,4′-bipyridine ligands leads to the formation of polymeric zigzag chains parallel to [0-11]. The chains are separated by 4,4′-bipyridine and water solvent molecules. Within a chain, the MnII atom is six-coordinated by two N atoms of the bridging 4,4′-bipyridine ligands, three water O atoms and one carboxylate O atom of a single deprotonated 3-(4-carboxyphenoxyphthalic acid ligand. Both coordinating and solvent 4,4′-bipyridine molecules are situated on centres of inversion. An intricate network of O—H...O and O—H...N hydrogen bonds involving the carboxy group, the coordinating water molecules and the two types of solvent molecules leads to the formation of a three-dimensional network.

  10. Fluorescence property of tris (2, 2'-bipyridine) ruthenium (Ⅱ) dichloride immobilized in the gallery of γ-zirconium phosphates

    Institute of Scientific and Technical Information of China (English)

    Ming Hui Xiang; Xian Bo Shi; Na Li; Ke An Li

    2007-01-01

    Tris (2, 2'-bipyridine) ruthenium (Ⅱ) (Ru(bpy)32+) dichloride was successfully immobilized into the galleria of layered gamma zirconium phosphate (γ-ZrP) preintercalated by butyl amine(BA). The compounds showed extended luminescence lifetime of about four times of unimmobilized metal complex.

  11. Solvation structure around ruthenium(II tris(bipyridine in lithium halide solutions

    Directory of Open Access Journals (Sweden)

    Ida Josefsson

    2016-03-01

    Full Text Available The solvation of the ruthenium(II tris(bipyridine ion ([Ru(bpy3]2+ is investigated with molecular dynamics simulations of lithium halide solutions in polar solvents. The anion distribution around the [Ru(bpy3]2+ complex exhibits a strong solvent dependence. In aqueous solution, the iodide ion forms a solvent shared complex with [Ru(bpy3]2+, but not in the other solvents. Between Cl– and [Ru(bpy3]2+, the strong hydration of the chloride ion results in a solvent separated complex where more than one solvent molecule separates the anion from the metal center. Hence, tailored solvation properties in electrolytes is a route to influence ion-ion interactions and related electron transfer processes.

  12. Solvation structure around ruthenium(II) tris(bipyridine) in lithium halide solutions

    Science.gov (United States)

    Josefsson, Ida; Eriksson, Susanna K.; Rensmo, Håkan; Odelius, Michael

    2016-01-01

    The solvation of the ruthenium(II) tris(bipyridine) ion ([Ru(bpy)3]2+) is investigated with molecular dynamics simulations of lithium halide solutions in polar solvents. The anion distribution around the [Ru(bpy)3]2+ complex exhibits a strong solvent dependence. In aqueous solution, the iodide ion forms a solvent shared complex with [Ru(bpy)3]2+, but not in the other solvents. Between Cl– and [Ru(bpy)3]2+, the strong hydration of the chloride ion results in a solvent separated complex where more than one solvent molecule separates the anion from the metal center. Hence, tailored solvation properties in electrolytes is a route to influence ion-ion interactions and related electron transfer processes. PMID:26798838

  13. Heterogeneous Catalysis for Water Oxidation by an Iridium Complex Immobilized on Bipyridine-Periodic Mesoporous Organosilica.

    Science.gov (United States)

    Liu, Xiao; Maegawa, Yoshifumi; Goto, Yasutomo; Hara, Kenji; Inagaki, Shinji

    2016-07-01

    Heterogenization of metal-complex catalysts for water oxidation without loss of their catalytic activity is important for the development of devices simulating photosynthesis. In this study, efficient heterogeneous iridium complexes for water oxidation were prepared using bipyridine-bridged periodic mesoporous organosilica (BPy-PMO) as a solid chelating ligand. The BPy-PMO-based iridium catalysts (Ir-BPy-PMO) were prepared by postsynthetic metalation of BPy-PMO and characterized through physicochemical analyses. The Ir-BPy-PMOs showed high catalytic activity for water oxidation. The turnover frequency (TOF) values for Ir-BPy-PMOs were one order of magnitude higher than those of conventional heterogeneous iridium catalysts. The reusability and stability of Ir-BPy-PMO were also examined, and detailed characterization was conducted using powder X-ray diffraction, nitrogen adsorption, (13) C DD MAS NMR spectroscopy, TEM, and XAFS methods. PMID:27168492

  14. Gold nanoparticles-decorated silver-bipyridine nanobelts for the construction of mediatorless hydrogen peroxide biosensor.

    Science.gov (United States)

    Boujakhrout, Abderrahmane; Díez, Paula; Sánchez, Alfredo; Martínez-Ruíz, Paloma; Pingarrón, José M; Villalonga, Reynaldo

    2016-11-15

    Au nanoparticles modified with 4-mercaptopyridine and 6-mercapto-1-hexanol were used as coordination agents to prepare a novel hybrid nanomaterial with Ag:4,4'-bipyridine nanobelts. This nanohybrid was employed to modify glassy carbon electrodes and to construct a horseradish peroxidase-based mediatorless amperometric biosensor for H2O2. The electrode, poised at -100mV, exhibited a rapid response within 4s and a linear calibration range from 90pM to 6.5nM H2O2. The biosensor showed a high sensitivity of 283A/Mcm(2) and a very low detection limit of 45pM at a signal-to-noise ratio of 3. The enzyme biosensor showed high stability when stored at 4°C under dry conditions, retaining over 96% and 78% of its initial activity after 15 and 30days of storage at 4°C, respectively. PMID:27497231

  15. Luminescent lanthanide complexes of a bis-bipyridine-phosphine-oxide ligand as tools for anion detection.

    Science.gov (United States)

    Charbonnière, Loïc J; Ziessel, Raymond; Montalti, Marco; Prodi, Luca; Zaccheroni, Nelsi; Boehme, Christian; Wipff, Georges

    2002-07-01

    The Gd(3+), Tb(3+), and Eu(3+) complexes of a bis-bipyridine-phenylphosphine oxide ligand PhP(O)(bipy)(2) 1 (bipy for 6-methylene-6'-methyl-2,2'-bipyridine) have been synthesized. In acetonitrile solutions at room temperature, the Tb(3+) and Eu(3+) complexes show a metal-centered luminescence, indicative of an efficient energy transfer from the two bipy subunits to the Ln center. The photophysical properties drastically depend on the nature of the anions present in solution. In particular, addition of 2 equiv of nitrate anions to a solution containing the [Ln.1](OTf-)(3) leads to an 11-fold increase of the luminescence intensity for the Eu(3+) and a 7-fold increase for the Tb(3+) complexes. Similar effects are provided with Cl-, F-, and CH(3)COO- anions. UV-vis titration experiments were used to determine association constants for binding of, respectively, one, two, and three anions. Stepwise anion addition has also been investigated on the molecular level using quantum mechanical (QM) calculations for the Eu complexes. These calculations reproduce the experimental findings, especially if solvent molecule addition is taken into account. The X-ray crystal structure of the nitrate salt of the Tb complex, as well as QM calculation of a similar Eu complex, demonstrates the coordination of three nitrate anions in a bidentate mode and the step-by-step relegation of the bipy subunits in the second coordination sphere. These features give valuable insights into the mechanism of the overall light amplification process. PMID:12083932

  16. Crystal structure of Cr (III) complex containing nitrilotriacetic acid and 4, 4'-bipyridine

    International Nuclear Information System (INIS)

    The title compound (C10H9N2)[Cr(C6H7NO6)2](C10H8N2).2H2O or (4,4'-bipy H)[Cr(nta H)2](4,4'-bipy). 2H2O (ntaH3 is nitrilotriacetic acid) was synthesized by reaction of Cr(NO3)3.9H2O with 4,4'-bipyridine, and nitrilotriacetic acid with 4:2:1 molar ratio in aqueous solution. The crystal structure of this complex was identified using X-ray crystallography. The unit cell parameters are as follows: a= 9.8501(3) Angstrom, b = 13.157(2) Angstrom, c = 26.842(4) Angstrom, β = 104.807(7)degree. The final R value is 0.041 for 7747 independent reflections. The title compound crystallized in monoclinic system and belongs to P21/c space group. The central CrIII atom is coordinated by two tridentaid (ntaH2) ligands and the resulted CrO4N2 set can be described as distorted octahedral geometry. The asymmetric unit contains two half of anionic complex, one 4, 4'-bipyridinium ion, (4, 4'-bipy H)+, one neutral 4, 4'-bipyridine molecule and two non-coordinated water molecules. Intramolecular hydrogen bonds, π-π [centroid -centroid distances of 3.674 A], C-H...π, O-H...π and N-H...π stacking interactions [with distance of 3.714, 3.736 and 3.270 A respectively], connect the various components into a supramolecular structures.

  17. Determination of Silver(I) by Differential Pulse Voltammetry Using a Glassy Carbon Electrode Modified with Synthesized N-(2-Aminoethyl)-4,4′-Bipyridine

    OpenAIRE

    Gabriel Lucian Radu; Bogdan Bucur; Madalina Petruta Bucur; Medeea Radulescu; Maria-Cristina Radulescu; Ana Chira

    2010-01-01

    A new modified glassy carbon electrode (GCE) based on a synthesized N-(2-aminoethyl)-4,4'-bipyridine (ABP) was developed for the determination of Ag(I) by differential pulse voltammetry (DPV). ABP was covalently immobilized on GC electrodes surface using 4-nitrobenzendiazonium (4-NBD) and glutaraldehyde (GA). The Ag(I) ions were preconcentrated by chemical interaction with bipyridine under a negative potential (−0.6 V); then the reduced ions were oxidized by differential pulse voltammetry and...

  18. μ-4,4′-Bipyridine-κ2N:N′-bis[aqua(4,4′-bipyridine-κN(l-valinato-κ2N,Ocopper(II] dinitrate dihydrate

    Directory of Open Access Journals (Sweden)

    Mao-Chun Hong

    2008-02-01

    Full Text Available In the title dinuclear complex, [Cu2(C5H10NO22(C10H8N23(H2O2](NO32·2H2O, each of the two l-valinate anions chelates a CuII center through the amino N and carboxylate O atom, forming a five-membered ring. A 4,4′-bipyridine molecule bridges two water-coordinated Cu atoms, each of which is connected to another 4,4′-bipyridine, giving rise to a square-pyramidal coordination geometry for the CuII centers. The dinuclear dications, nitrate anions and uncoordinated water molecules are linked into a two-dimensional structure.

  19. Bis[4-amino-N-(pyrimidin-2-yl)benzene­sulfonamidato](2,2′-bipyridine)manganese(II)

    OpenAIRE

    Tian-Jing He; Yan-Shu Tan; Yun-Qiong Gu; Zhen-Feng Chen; Hong Liang

    2010-01-01

    The title compound, [Mn(C10H9N4O2S)2(C10H8N2)], contains a distorted octahedral [Mn(sdz)2(bpy)] (sdz is the sulfadiazine anion and bpy is 2,2′-bipyridine) complex molecule. A three-dimensional network is generated by N—H...N, N—H...O and C—H...O hydrogen bonds from the sulfadiazine ligands.

  20. Study of ruthenium complexation by 22' bipyridine in nitric aqueous solutions

    International Nuclear Information System (INIS)

    Substitution of the NO3-, NO+ ions of RuNO(NO3)x.yH2Osup((3-x)+) complexes by 22'bipyridine (bipy) in nitric aqueous solution was studied by spectrophotometry. In the absence of reducing agent we observe the species RuNO(bipy)(NO3)sub(z)sup((3-z)+) and RuNO(bipy)2NO32+. Most reducing agents give rise to the RuNO(bipy)2NO32+ + e → RuNO(bipy)2NO3+ reaction. The oxydation potential of the reversible couple RuNO(bipy)2NO32+/RuNO(bipy)2NO3+ was measured by cyclic voltamperometry at the platinum electrode. Its value is + 1.02 V/NHE. Substitution of NO+ ions by a (bipy) molecule is only possible in the presence of reducing agents of apparent formal potential below + 0.5 V/NHE, and anti-nitrite agents are also needed; these two functions can be fulfilled by hydrazine and ascorbic acid. The presence of HSO3 NH2 was necessary to obtain the substitution of NO+ and NO3- by bipy during electrochemical reductions. The intermediate complexes RuNO(bipy)2NO32+ and RuNO(bipy)2NO3+ probably include two bipy molecules in the trans position whereas RuNO(bipy)22+ complexes, where the sixth coordination position is occupied by π donors stronger than NO3-, have two bipy molecules in the cis position

  1. Ruthenium(II)-tris-bipyridine/titanium dioxide codoped zeolite Y photocatalyst: performance optimization

    Energy Technology Data Exchange (ETDEWEB)

    Bossmann, S.H.; Woerner, M.; Pokhrel, M.R.; Baumeister, B.; Goeb, S.; Braun, A.M. [Lehrstuhl fuer Umweltmesstechnik am Engler-Bunte Inst. der Univ. Karlsruhe (Germany)

    2003-07-01

    The heterogeneous photocatalysts of the ruthenium(II)-tris-bipyridine/titanium dioxide/zeolite Y ([Ru(bpy){sub 3}]{sup 2+}/TiO{sub 2}/zeolite Y) family perform in a manner very similar to a ''Fenton-catalyst'' in the oxidative degradation of the model pollutant 2,4-xylidine. A distinct percolation behaviour of this AOP reaction was observed, which was dependent on the amount of titanium dioxide, incorporated as nanoparticles into the zeolite Y framework. The maximum of the photocatalytic removal of 2,4-xylidine at pH = 3.0 was found at 34.5{+-}0.5 percent TiO{sub 2} per weight. The optimization of the performance parameters of this particular [Ru(bpy){sub 3}]{sup 2+}/TiO{sub 2}/zeolite Y photocatalyst, obtained in a pilot reactor (V=2.0 L), equipped with a medium pressure mercury lamp, is presented here. Important factors in the apparent photocatalytic efficiency were determined: a) dissolved oxygen, b) substrate concentration and c) concentration of dispersed photocatalyst. The repeated addition of 2,4-xylidine (three times) at a high concentration level (500 mg C L{sup -1}) does not lead to an irreversible loss of photocatalytic activity, if sufficient time intervals are chosen between 3 subsequent additions. (orig.)

  2. 3-Aminobenzoic acid–4,4′-bipyridine (2/3

    Directory of Open Access Journals (Sweden)

    Pornsuda Lhengwan

    2012-08-01

    Full Text Available The asymmetric unit of the title compound, 3C10H8N2·2C7H7NO2, consists of three molecules of 4,4′-bipyridine (bpy and two molecules of 3-aminobenzoic acid (bza. Two molecules of bza and two molecules of bpy are connected via O—H...N, N—H...N and N—H...O hydrogen bonds, forming forming infinite double-stranded zigzag chains along the c axis. The third molecule of bpy is linked to the chain by weak C—H...O interactions. Adjacent chains are linked via π–π interactions [centroid–centroid distances = 3.759 (3–3.928 (3 Å] involving the pyridine rings of bpy molecules, resulting in a sheet-like structure parallel to (100. These sheets are stacked via C—H...π interactions, resulting finally in the formation of a three-dimensional supramolecular structure.

  3. Iridium-bipyridine periodic mesoporous organosilica catalyzed direct C-H borylation using a pinacolborane.

    Science.gov (United States)

    Maegawa, Yoshifumi; Inagaki, Shinji

    2015-08-01

    Heterogeneous catalysis for direct C-H borylation of arenes and heteroarenes in the combination of iridium (Ir) complex fixed on periodic mesoporous organosilica containing bipyridine ligands within the framework (Ir-BPy-PMO) and pinacolborane (HBpin) is reported. Ir-BPy-PMO showed higher catalytic activity toward the borylation of benzene with inexpensive HBpin compared to expensive bis(pinacolato)diboron (B2pin2). The precatalyst could be handled without the use of a glove box. The catalyst was easily recovered from reaction mixtures by simple filtration under air. The recovered catalyst still showed good catalytic activity for at least three more times for the borylation of benzene. A variety of arenes and heteroarenes were successfully borylated with high boron efficiency by Ir-BPy-PMO using HBpin, whereas almost no activity was observed for borylation of some heteroarenes with B2pin2. The system using Ir-BPy-PMO and HBpin was also utilized in syntheses of multi-boronated thiophene-based building blocks containing ladder-, acenefused-, and fused-thiophene skeletons. The combination of a stable and reusable solid catalyst and inexpensive HBpin is expected to be superior to conventional approaches for the development of industrial applications. PMID:25748945

  4. Photoluminescent multilayer film based on polyoxometalate and tris(2,2-bipyridine)ruthenium

    International Nuclear Information System (INIS)

    A photoluminescent multilayer film based on Keggin-type polyoxometalate PMo12O403- (PMo12) and transition metal complex tris(2,2-bipyridine) ruthenium [Ru(bpy)3]2+ (Ru(bpy)) was prepared by using layer-by-layer assembly(LBL). The formation of multilayer film was monitored by ultraviolet absorption spectra. The absorption intensity of characteristic peaks increase with a four-layer cycle, indicating that the LBL assembly film grow linearly and reproducibly from layer to layer. The composition of the film was measured by X-ray photoelectron spectrum (XPS). The data of XPS confirmed the presence of the expected elements. The film exhibited photoluminescence arising from π*-t2g ligand-to-metal transition of Ru(bpy) and redox activity attributing to molybdenum-centered redox processes of PMo12. The surface morphology of multilayer film was characterized by atomic force microscopy (AFM). The result shows that the film had a smooth surface with root-mean-square (rms) roughness ca. 1.363 nm for {PEI/(PSS/PEI/PMo12/Ru(bpy))3}. The grains are homogeneously dispersed in the substrate and have a rather narrow diameter size distribution

  5. Synthesis and characterization of new dn metal complexes with 4,4'-bipyridine and formates

    International Nuclear Information System (INIS)

    New mixed-ligand complexes of the stoichiometric formulae: Mn(4-bpy)2(HCOO)2·2H2O, Co(4-bpy)2(HCOO)2·H2O, Ni(4-bpy)2(HCOO)2·4H2O, Cu(4-bpy)2(HCOO)2·H2O, Zn2(4-bpy)3(HCOO)4, Cd(4-bpy)3(HCOO)2 (where 4-bpy = 4,4'-bipyridine) have been isolated in pure state. The IR and VIS spectra (for compounds Co(II), Ni(II), Cu(II)), molar conductivity measurements and other physical properties of these compounds are discussed. Thermal behaviour of all compounds was studied by means of DTA, DTG, TG techniques under static conditions in air. The resultant final products were the metal oxide in all cases. A coupled TG-MS system was used to analysis of principal volatile thermal decomposition (or fragmentation) products of Co(II) and Ni(II) complexes. The principal volatile mass fragments correspond to: C+, OH+, H2O+, NO+, CO2+ and other. (author)

  6. Quantum processes in 8-Oxo-Guanine-Ru(bipyridine)32+ photosynthetic systems of artificial minimal cells

    Science.gov (United States)

    Tamulis, Arvydas; Grigalavicius, Mantas; Krisciukaitis, Sarunas; Medzevicius, Giedrius

    2011-06-01

    Density functional theory methods were used to investigate various self-assembled photoactive bioorganic systems of interest for artificial minimal cells. The cell systems studied are based on nucleotides or their compounds and consisted of up to 123 atoms (not including the associated water or methanol solvent shells) and are up to 2.5 nm in diameter. The electron correlation interactions responsible for the weak hydrogen and Van derWaals chemical bonds increase due to the addition of a polar solvent (water or methanol). The precursor fatty acid molecules of the system also play a critical role in the quantum mechanical interaction based self-assembly of the photosynthetic center and the functioning of the photosynthetic processes of the artificial minimal cells. The distances between the separated sensitizer, fatty acid precursor, and methanol molecules are comparable to Van derWaals and hydrogen bonding radii. As a result the associated electron correlation interactions compress the overall system, resulting in an even smaller gap between the highest occupied molecular orbital (HOMO), and lowest unoccupied molecular orbital (LUMO) electron energy levels and photoexcited electron tunnelling occurs from the sensitizer (either Ru(bpy)32+ or [Ru(bpy)2(4-Bu-4'-Me-2,2'-bpy)]2++ derivatives) to the precursor fatty acid molecules (notation used: Me = methyl; Bu = butyl; bpy = bipyridine). The shift of the absorption spectrum to the red for the artificial protocell photosynthetic centers might be considered as the measure of the complexity of these systems.

  7. Electrode reactions of ruthenium–bipyridine complex in amide-type ionic liquids

    International Nuclear Information System (INIS)

    The electrode kinetics of [Ru(bpy)3]3+/[Ru(bpy)3]2+ (bpy = 2,2′-bipyridine) on a platinum electrode was investigated in room-temperature ionic liquids, 1-butyl-1-methylpyrrolidinium bis(trifluoromethylsulfonyl)amide (BMPTFSA), 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)amide (EMITFSA), and 1-butyl-1-methylpyrrolidinium bis(perfluoroethylsulfonyl)amide (BMPBETA) over the temperature range from 25 to 45 °C. The diffusion coefficients of [Ru(bpy)3]2+ and [Ru(bpy)3]3+ were found to be affected not only by the viscosity of ionic liquids but also by the charge density of the complex. The activation energy for the diffusion coefficients of these complexes in the ionic liquids were close to that for the viscosity of the ionic liquids. The standard rate constants of [Ru(bpy)3]3+/[Ru(bpy)3]2+ in BMPTFSA, EMITFSA and BMPBETA were estimated by electrochemical impedance spectroscopy. The standard rate constants in the ionic liquids were estimated to be smaller than those in aqueous and organic electrolytes, probably due to the slow dynamics of the ionic liquids.

  8. Decamethylytterbocene complexes of bipyridines and diazabutadines: multiconfigurational ground states and open-shell singlet formation

    Energy Technology Data Exchange (ETDEWEB)

    Bauer, Eric D [Los Alamos National Laboratory; Booth, C H [LBNL; Walter, M D [LBNL; Kazhdan, D [LBNL; Hu, Y - J [LBNL; Lukens, Wayne [LBNL; Maron, Laurent [INSA TOULOUSE; Eisentein, Odile [UNIV MONTPELLIER 2; Anderson, Richard [LBNL

    2009-01-01

    Partial ytterbium f-orbital occupancy (i.e. intermediate valence) and open-shell singlet Draft 12/formation are established for a variety of bipyridine and diazabutadiene adducts to decamethylytterbocene, (C{sub 5}Me{sub 5}){sub 2}Yb or Cp*{sub 2}Yb. Data used to support this claim includes ytterbium valence measurements using Yb Lm-edge x-ray absorption near-edge structure (XANES) spectroscopy, magnetic susceptibility and Complete Active Space Self-Consistent Field (CASSCF) multi configurational calculations, as well as structural measurements compared to density-functional theory (DFT) calculations. The CASSCF calculations indicate that the intermediate valence is the result of a multiconfigurational ground state wave function that has both an open-shell singlet f{sup 13} and a closed-shell singlet f{sup 14} component. A number of other competing theories for the unusual magnetism in these materials are ruled out by the presence of intermediate valence and its lack of any significant temperature dependence. These results have implications for understanding chemical bonding not only in organolanthanide complexes, but also for organometallic chemistry in general, as well as understanding magnetic interactions in nanopartic1es and devices.

  9. Mn(II) complexes with bipyridine, phenanthroline and benzoic acid: Biological and catalase-like activity

    Indian Academy of Sciences (India)

    Ibrahim Kani; Özlem Atlier; Kiymet Güven

    2016-04-01

    Five mononuclear Mn(II) complexes, [Mn(phen)2(ClO4)2] (1), [Mn(phen)3](ClO4)2(H2CO3)2(2), [Mn(bipy)2(ClO4)2] (3), [Mn(bipy)3](ClO4)2) (4), and Mn(phen)2(ba)(H2O)](ClO4)(CH3OH) (5), where bipy = 2,2’-bipyridine, phen = 1,10-phenanthroline, and ba = benzoic acid were prepared and characterized by Xray, IR and UV-Vis spectroscopies, and their catalase-like and biological activities were studied. The presence of two different types and the number of chelating NN-donor neutral ligands allowed for analysis of their effects on the catalase and biological activities. It was observed that the presence and number of phen ligands improved the activity more than the bipy ligand. Complexes 1 and 2, which contain more basic phen ligands, disproportionate H2O2 faster than complexes 3 and 4, which contain less basic bipy ligands. The in vitro antimicrobial activities of all the complexes were also tested against seven bacterial strains by microdilution tests. All the bacterial isolates demonstrated sensitivity to the complexes and the antifungal (anticandidal) activities of the Mn(II) complexes were remarkably higher than the reference drug ketoconazole.

  10. Electronic properties and reactivity of vanadium complexes of bipyridine and cyanometallates

    International Nuclear Information System (INIS)

    This work deals with the chemistry of two types of vanadium compounds. The first one consists of polymeric pigments containing vanadium (III) ions and hexacyanoferrate (II) or substituted pentacyanoferrate (II) complexes. A series of 14 complexes were isolated in solid state, exhibiting the following composition V sub(4) [ Fe (CN) sub(4) ]. 16H sub(2)O or V [ Fe (CN) sub(5) L ]. 4H sub(2)O (L imidazole, pyridine and pyrazine derivatives). These complexes exhibit strong absorption bands in the visible-uv region, ascribed to intervalence transfer transitions. The infrared spectra were assigned, showing a linear correlation of the CN stretching frequencies with the sup(13)C NMR chemical shifts of the cyanide ligands in the complexes. The second system which has been investigated consists of a series of substituted species with vanadium (II) and (III) ions with 2,2 bypyridine ligands, formulated as [V (bipy) 3 - n (H sub(2)O) 6-2n ] sup(2+) and [ Cl (bipy)nVOV(bipy)nCl] sup(4)+ (n= 1-3) respectively. The electronic spectra of these complexes were assigned in parallel with magnetic and vibrational studies. Resonance Raman spectra of the vanadium (II) complexes exhibited strong enhancement of the bipyridine vibrational modes. In contrast, the vibrational modes of the V (III)-O-V(III) chromophore were preferentialy enhanced in the dimeric species. (author)

  11. Crystal structure and physical properties of a ruthenium(II) bipyridine dimethylsulfoxide complex

    International Nuclear Information System (INIS)

    The complex [Ru(bpy)2(DMSO)C1]PF6, where bpy is 2,2prime-bipyridine and DMSO is dimethyl-sulfoxide, crystallizes in the triclinic space group Pbar 1 (numbersign2) with a = 8.873 (2), b = 12.805 (4), c = 12.864 (4) angstrom, α = 97.76(3), β = 106.45(2), γ = 107.88(2); Z = 2, and dcalc = 1.75 mg/m3. The coordination geometry is that of a distorted octahedron with a cis-RuN4SCl arrangement of coordinating atoms. The four Ru-N distances to the bpy ligands are 2.082(5), 2.092(4), 2.044(4), and 2.078(5) angstrom. The Ru-Cl distance is 2.421(2) angstrom and the Ru-S distance to DMSO is 2.260(1) angstrom. The Ru-N bond distance trans to Cl is the shortest; the Ru-N bond distance trans to S is the longest. The complex is oxidized and reduced reversibly at 1.13 and minus1.37 V vs. SSCE, respectively. It displays electronic absorptions at 515, 480 (1.5 x 104), 342 (1.5 X 104), 292 (1.2 X 105), and 240 nm (6.2 x 104) and has a broad emission band centered at 607 nm at 77 K in a 4:1 ethanol/methanol glass. The emission lifetime at room temperature is less than the pulse width of the laser, τ < 20 ns

  12. Synthesis, Spectroscopic and Antibacterial Properties of Some Metal (II Mixed Ligand Complexes of Riboflavin and 2,2'-Bipyridine.

    Directory of Open Access Journals (Sweden)

    Aderoju A Osowole

    2014-03-01

    Full Text Available Mixed ligand complexes of Riboflavin (L and 2,2’ - Bipyridine (L1 wit h Mn(II, Fe(II, Co(II , Ni(II, Cu(II a nd Zn(II ions were synthesized and characterized by , infrared and electronic spectroscopies, room temperature magnetic moments, melting points and conductance measurements . The % me tal analysis confirmed that the complexes analyzed as [ MX 2 (L(L 1 ] where X = Cl /(CH 3 C O 2 /SO 4 . Infrared spectra data confirmed that coordination is via the imine nitrogen and carbonyl oxygen atoms of the riboflavin , and the nitrogen atoms of the 2,2’ - b ipyridine molecules respectively . The room temperature magnetic moment and el ectronic spectra data indic ated that all the metal(II complexes were octahedral , and the Mn(II, Fe(II, Co(II and Ni(II complexes showed high spin low spin octa hedral equilibrium. The conductance measurements of all the metal(II complexes in water and DMSO showed that the complexes were all covalent . Interestingly, t he in - vitro antibacterial studies of these metal(II complexes , riboflavin and 2,2’ - bipyridine a gainst Bacillus cereus, Escherichia coli, Proteus mirabilis, Pseudomonas aeruginosa , Klebsiella oxytoca and Staphylococcus aureus showed that none of the bacteria was sensitive to the former two compounds , with the exception of Proteus mirabilis which had a ctivities of 20 .0 mm and 13 .0 mm against the Cu(II complex and riboflavin. In contrast, all the bacteria were sensitive to 2, 2’ - bipyridine, just like Augmentine , although with higher inhibitory zones range of 24.0 - 47.0 mm proving its potential as a broa d spectrum antibacterial agent .

  13. Crystal structures of bis- and hexakis[(6,6'-di-hydroxy-bipyridine)copper(II)] nitrate coordination complexes.

    Science.gov (United States)

    Gerlach, Deidra L; Nieto, Ismael; Herbst-Gervasoni, Corey J; Ferrence, Gregory M; Zeller, Matthias; Papish, Elizabeth T

    2015-12-01

    Two multinuclear complexes synthesized from Cu(NO3)2 and 6,6'-di-hydroxy-bipyridine (dhbp) exhibit bridging nitrate and hydroxide ligands. The dinuclear complex (6,6'-di-hydroxy-bipyridine-2κ(2) N,N')[μ-6-(6-hy-droxy-pyridin-2-yl)pyridin-2-olato-1:2κ(3) N,N':O (2)](μ-hydroxido-1:2κ(2) O:O')(μ-nitrato-1:2κ(2) O:O')(nitrato-1κO)dicopper(II), [Cu2(C10H7N2O2)(OH)(NO3)2(C10H8N2O2)] or [Cu(6-OH-6'-O-bpy)(NO3)(μ-OH)(μ-NO3)Cu(6,6'-dhbp)], (I), with a 2:1 ratio of nitrate to hydroxide anions and one partially deprotonated dhbp ligand, forms from a water-ethanol mixture at neutral pH. The hexa-nuclear complex bis-(μ3-bi-pyridine-2,2'-diolato-κ(3) O:N,N':O')tetra-kis-(6,6'-di-hydroxy-bipyridine-κ(2) N,N')tetra-kis-(μ-hydroxido-κ(2) O:O')bis-(methanol-κO)tetra-kis-(μ-nitrato-κ(2) O:O')hexa-copper(II), [Cu6(C10H6N2O2)2(CH4O)2(OH)4(NO3)4(C10H8N2O2)4] or [Cu(6,6'-dhbp)(μ-NO3)2(μ-OH)Cu(6,6'-O-bpy)(μ-OH)Cu(6,6'dhbp)(CH3OH)]2, (II), with a 1:1 NO3-OH ratio and two fully protonated and fully deprotonated dhbp ligands, was obtained by methanol recrystallization of material obtained at pH 3. Complex (II) lies across an inversion center. Complexes (I) and (II) both display intra-molecular O-H⋯O hydrogen bonding. Inter-molecular O-H⋯O hydrogen bonding links symmetry-related mol-ecules forming chains along [100] for complex (I) with π-stacking along [010] and [001]. Complex (II) forms inter-molecular O-H⋯O hydrogen-bonded chains along [010] with π-stacking along [100] and [001]. PMID:26870402

  14. cis-Bis(acetonitrile-κNbis(2,2′-bipyridine-κ2N,N′ruthenium(II tetrafluoridoborate

    Directory of Open Access Journals (Sweden)

    Ying Wang

    2012-01-01

    Full Text Available In the cation of the title compound, [Ru(CH3CN2(C10H8N22](BF42, the RuII atom is six-coordinated in a distorted octahedral geometry by the N atoms of the two 2,2′-bipyridine (bpy ligands and two cis-arranged acetonitrile molecules. The dihedral angles formed by the pyridine rings of the bpy ligands are 8.86 (12 and 10.12 (14°. In the crystal, the cations and anions are linked by C—H...F hydrogen bonds into a three-dimensional network.

  15. Bis(2,2′-bipyridine(2-hydroxy-2,2-diphenylacetatocopper(II nitrate dihydrate

    Directory of Open Access Journals (Sweden)

    Xuan Xu

    2010-10-01

    Full Text Available In the title complex, [Cu(C14H11O3(C10H8N22]NO3·2H2O, the CuII atom is coordinated by four N atoms from two 2,2′-bipyridine ligands and two O atoms from one benzilate ligand in a distorted octahedral geometry. A supramolecular network is formed via intermolecular O—H...O and C—H...O hydrogen-bonding interactions. π–π stacking interactions between neighboring pyridine rings are also present, the centroid—centroid distance being 3.808 (2 Å.

  16. (6,6′-Dimethyl-2,2′-bipyridine-κ2N,N′diiodidozinc(II

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    Robabeh Alizadeh

    2009-11-01

    Full Text Available The complete molecule of the title compound, [ZnI2(C12H12N2], is generated by crystallograpic twofold symmetry, with the ZnII atom lying on the rotation axis. The ZnII atom is coordinated by the N,N-bidentate 6,6′-dimethyl-2,2′-bipyridine ligand and two iodide ions, resulting in a distorted ZnN2I2 tetrahedral geometry for the metal. In the crystal, there are weak π–π contacts between the pyridine rings [centroid–centroid distance = 3.978 (3 Å].

  17. (η6-Benzene)(2,2′-bipyridine-κ2 N,N′)chloridoruthenium(II) chloride methanol sesquisolvate

    OpenAIRE

    Polson, Matthew I. J.

    2007-01-01

    In the title compound, [RuCl(C6H6)(C10H8N2)]Cl·1.5CH4O, the RuII atom is in a distorted octahedral environment coordinated by an η6-benzene ring, a chelating 2,2′-bipyridine ligand and a chloride ion. The asymmetric unit is completed by a chloride anion and two methanol molecules, one of which is disordered about a centre of inversion with an occupancy of 0.5. It is an example of a ruthenium complex with a less sterically congested environment than in similar derivatives. In t...

  18. Preparation and Spectroscopic Properties of Tris(2,2′-bipyridine)ruthenium(Ⅱ) Loaded in Siliceous Mesoporous MCM-41

    Institute of Scientific and Technical Information of China (English)

    2000-01-01

    [Ru(bpy)3]2+/MCM-41 composite material obtained by loading tris(2,2′-bipyridine)ruthenium(Ⅱ)([Ru(bpy)3]2+) in siliceous mesoporous MCM-41 was characterized by X-ray powder diffraction, UV-Vis absorption and emission spectroscopies. The absorption spectrum of [Ru(bpy)3]2+/MCM-41 is similar to that of [Ru(bpy)3]2+ aqueous solution, whereas its emission spectrum exhibits hypsochromic shift compared to the solution spectrum. On the other hand, the peak position of the emission spectrum of [Ru(bpy)3]2+/MCM-41 shifts towards longer wavelength when the loading amount increases.

  19. (2,2′-Bipyridine-κ2 N,N′)dibromido(dimethyl sulfoxide-κO)zinc(II)

    OpenAIRE

    Esmhosseini, Majid

    2010-01-01

    In the mol­ecule of the title compound, [ZnBr2(C10H8N2)(C2H6OS)], the ZnII atom is five-coordinated in a distorted trigonal–bipyramidal configuration by two N atoms from one 2,2′-bipyridine, one O atom from one dimethyl­sulfoxide molecule and two Br atoms. Inter­molecular π–π stacking between parallel pyridine rings [face-to-face distance 3.32 (4) Å] and C—H⋯Br and C—H⋯O hydrogen-bonding interactions are present in the crystal structure.

  20. (2,2′-Bipyridine-κ2N,N′dibromido(dimethyl sulfoxide-κOzinc(II

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    Majid Esmhosseini

    2010-06-01

    Full Text Available In the molecule of the title compound, [ZnBr2(C10H8N2(C2H6OS], the ZnII atom is five-coordinated in a distorted trigonal–bipyramidal configuration by two N atoms from one 2,2′-bipyridine, one O atom from one dimethylsulfoxide molecule and two Br atoms. Intermolecular π–π stacking between parallel pyridine rings [face-to-face distance 3.32 (4 Å] and C—H...Br and C—H...O hydrogen-bonding interactions are present in the crystal structure.

  1. trans-cis photoisomerization of azobenzene-conjugated dithiolato-bipyridine platinum(II) complexes: extension of photoresponse to longer wavelengths and photocontrollable tristability.

    Science.gov (United States)

    Sakamoto, Ryota; Kume, Shoko; Sugimoto, Manabu; Nishihara, Hiroshi

    2009-01-01

    Azobenzene derivatives modified with dithiolato-bipyridine platinum(II) complexes were synthesized, revealing their highly extended photoresponses to the long wavelength region as well as unique photocontrollable tristability. The absorptions of trans-1 and trans-2 with one azobenzene group on the dithiolene and bipyridine ligands, respectively, cover the range from 300 to 700 nm. These absorptions are ascribed, by means of time-dependent (TD)DFT calculations, to transitions from dithiolene(pi) to bipyridine(pi*), namely, interligand charge transfer (CT), pi-pi*, and n-pi* transitions of the azobenzene unit, and pi-pi* transitions of the bipyridine ligand. In addition, only trans-1 shows distinctive electronic bands, assignable to transitions from the dithiolene(pi) to azobenzene(pi*), defined as intraligand CT. Complex 1 shows photoisomerization behavior opposite to that of azobenzene: trans-to-cis and cis-to-trans conversions proceed with 405 and 312 nm irradiation, which correspond to excitation with the intraligand CT, and pi-pi* bands of the azobenzene and bipyridine units, respectively. In contrast, complex 2 shows photoisomerization similar to that of azobenzene: trans-to-cis and cis-to-trans transformations occur with 365 and 405 nm irradiation, respectively. Irradiation at 578 nm, corresponding to excitation of the interligand CT transitions, results in cis-to-trans conversion of both 1 and 2, which is the longest wavelength ever reported to effect the photoisomerization of the azobenzene group. The absorption and photochromism of 4, which has azobenzene groups on both the dithiolato and bipyridine ligands, have characteristics quite similar to those of 1 and 2, which furnishes 4 with photocontrollable tristability in a single molecule using light at 365, 405, and 578 nm. We also clarified that 1 and 2 have high photoisomerization efficiencies, and good thermal stability of the cis forms. Complexes 3 and 5 have almost the identical photoresponse to those

  2. π-Stacking and hydrogen bonding in catena-poly[[4,4 '-bipyridine-κN)-dioxouranium(VI)]-di-μ-hydroxo

    International Nuclear Information System (INIS)

    The title compound, [UO2(OH)2(C10H8N2)]n, was obtained under hydrothermal conditions. The U atom is seven-coordinated and its environment is pentagonal bipyramidal, with the oxo atoms in axial positions, and one N atom and four hydroxide groups in the equatorial plane. The hydroxide ions are bridging, which results in the formation of infinite chains with the bipyridine molecules alternately located on either side. Neighbouring chains interpenetrate so that each bipyridine ligand is involved both in hydrogen bonds with two hydroxide ions and in π-stacking with its two neighbours from the next chain. (authors)

  3. Tetrakis[μ-3-(3-hydroxyphenylpropenoato]bis{aqua(2,2′-bipyridine[3-(3-hydroxyphenylpropenoato]neodymium(III} 2,2′-bipyridine disolvate dihydrate

    Directory of Open Access Journals (Sweden)

    Jing-Ke Guo

    2011-12-01

    Full Text Available The dinuclear title compound, [Nd2(C9H7O36(C10H8N22]·2C10H8N2·2H2O, was synthesized under hydrothermal conditions. The centrosymmetric complex consists of two nine-coordinated Nd3+ cations, six 3-hydroxycinnamate anions and two chelating 2,2′-bipyridine molecules. The coordination geometry around the cations can be best described as distorted tricapped trigonal-prismatic. The carboxylate groups show different coordination and bridging modes. Two of them chelate to one Nd3+ cation, two bridge the two cations in a bis-monodentate fashion, and two chelate to one and bridge monodentately to the symmetry-related Nd3+ cation. The dinuclear molecule is surrounded by two 2,2′-bipyridine solvent and two water molecules. Extensive O—H...O and O—H...N hydrogen-bonding interactions between the components lead to the formation of a three-dimensional network.

  4. Synthesis, characterization and crystal structure of 6-Chloro-4,4‧-dimethyl-2,2‧-bipyridine and 4,4‧-Dimethyl 2,2‧-bipyridine N-Oxide

    Science.gov (United States)

    Conterosito, Eleonora; Magistris, Claudio; Barolo, Claudia; Croce, Gianluca; Milanesio, Marco

    2016-03-01

    The synthesis, the NMR characterization and the crystal structure of 6-Chloro 4,4‧-dimethyl 2,2‧-bipyridine and of the reaction intermediate 4,4‧-Dimethyl 2,2‧-bipyridine N-Oxide are here reported. The target compound crystallizes in the orthorhombic system while the intermediate is monoclinic. In both structures, the molecules are linked by weak interactions. The structure of the reaction intermediate N-oxide is characterized by a dihedral angle between the two phenyl rings of 161.77° while the other is almost planar with a dihedral angle of 179.15°. The crystal packing was investigated, also with the aid of Hirshfeld surface analysis. In the N-oxide reaction intermediate the packing is governed by CH-O interactions, while in the product the packing is simply driven by minimizing the voids and thus maximizing the density, with a prevalence of H•••H and C•••H contacts, as indicated by fingerprint decomposition analysis.

  5. Interaction of 2-mercaptopyrimidine and 4,4'-bipyridine and competition experiments between bipyridines and 1,10'-phenanthroline for the thiol layer on Au(1 1 1) by STM

    Science.gov (United States)

    Pinheiro, L. S.; Temperini, M. L. A.

    2001-02-01

    STM was employed to study the coadsorption of 4,4'-bipyridine (4bipy) and 2-mercaptopyrimidine (2MPy) on Au(1 1 1). The adsorption of 4bipy as a single layer was also analyzed. For the single layer STM reveals a molecular structure made of parallel periodic chains with a repeat distance of 11.5-11.7 Å. The mixed layer is formed with a ratio of two molecules of 2MPy to one of 4bipy. 4bipy assumes two different positions in relation to the 2MPy dimer. Competition between 4bipy, 2,2'-bipyridine and 1,10'-phenanthroline was investigated to obtain a qualitative view of the preference of the 2MPy assembly for these molecules. The mixed layers were grown on Au(1 1 1) from ternary molecular solutions containing either 2MPy+4bipy+2bipy or 2MPy+4bipy+phen. STM shows that the resulting layers are made of the 2MPy dimeric assembly plus one of the oligopyridines. A split of the 2MPy dimer or the formation of mixed domains with the three molecules present in the stock solution was not found.

  6. XPS study of ruthenium tris-bipyridine electrografted from diazonium salt derivative on microcrystalline boron doped diamond.

    Science.gov (United States)

    Agnès, Charles; Arnault, Jean-Charles; Omnès, Franck; Jousselme, Bruno; Billon, Martial; Bidan, Gérard; Mailley, Pascal

    2009-12-28

    Boron doped diamond (BDD) functionalization has received an increasing interest during the last few years. Such an infatuation comes from the original properties of BDD, including chemical stability or an electrochemical window, that opens the way for the design of (bio)sensors or smart interfaces. In such a context, diazonium salts appear to be well suited for BDD functionalization as they enable covalent immobilization of functional entities such as enzymes or DNA. In this study we report microcrystalline BDD functionalization with a metallic complex, ruthenium tris(bipyridine), using the p-(tris(bipyridine)Ru(2+))phenyl diazonium salt. Electrografting using cyclic voltammetry (CV) allowed the formation of a ruthenium complex film that was finely characterized using electrochemistry and X-ray photoelectron spectroscopy (XPS). Moreover, we showed that chronopotentiometry (CP) is a convenient tool to monitor Ru complex film deposition through the control of the electrochemical pulse parameters (i.e. current density and pulse duration). Finally, such a control was demonstrated through the correlation between electrochemical and XPS characterizations. PMID:20024438

  7. Time-dependent SERS spectra monitoring the dynamic adsorption behavior of bipyridine isomerides combined with bianalyte method.

    Science.gov (United States)

    Yan, Xiunan; Li, Pan; Yang, Liangbao; Liu, Jinhuai

    2016-08-15

    Based on the bianalyte method, time-dependent surface-enhanced Raman spectrosopy (SERS) spectra were applied to observe and study the competitive adsorption of bipyridine isomerides 2,2'-bpy and 4,4'-bpy. These time-dependent SERS spectra offer a significant advantage for observing the continuous SERS spectra of analyte with 2 s resolution, letting one monitor real-time competitive adsorption and corresponding SERS signal intensity for mixed or pure analyte type events under different concentrations. In this study, we report experimental evidence of competitive adsorption of two bipyridine isomerides using SERS mapping and independent spectra in chronological order. On the one hand, the time-dependent SERS spectra of 2,2'-bpy were prior dominated in the early stage either in high concentration or in low concentration. On the other hand, pure type 2,2'-bpy or 4,4'-bpy events only occurred for strong intensity, whereas weak intensity events exhibited more mixed analytes in low concentration, showing a great difference from those at the higher concentration. In addition, we believe that these results and this evidence can motivate the use of time-dependent SERS spectra for distinguishing the fingerprint information of several molecules from similar isomeride molecules in chemical and biological systems. PMID:27181986

  8. Aqua(2,2′-bipyridine-κ2N,N′bis(thiophene-2-carboxylato-κOcopper(II

    Directory of Open Access Journals (Sweden)

    Christoph Janiak

    2009-08-01

    Full Text Available In the title complex, [Cu(C5H3O2S2(C10H8N2(H2O], the CuII atom is in a distorted square-pyramidal environment, with an Addison τ parameter of 0.07. The coordination geometry is defined by two nitrogen donors from the 2,2′-bipyridine ligand, two O atoms from two monodentate thiophene-2-carboxylate ligands and one O atom from the aqua ligand. The latter occupies the elongated apical position. This is different from the related structure of aqua(1,10-phenanthrolinebis(thiophene-2-carboxylatocopper(II where a carboxylate O atom is in the apical position [Feng et al. (2005. Z. Kristallogr. New Cryst. Struct. 220, 429–430]. The uncoordinated carboxylate O atoms form intra- and intermolecular hydrogen bonds to the aqua ligand. Two neighbouring 2,2′-bipyridine ligands form a π-stack, with a centroid–centroid distance of 3.683 (2 Å.

  9. Metal-organic framework based on copper(I) sulfate and 4,4'-bipyridine catalyzes the cyclopropanation of styrene

    International Nuclear Information System (INIS)

    The hydrothermal synthesis of a new metal-organic framework (MOF) formulated as Cu2(4,4'-bpy)2SO4.6(H2O), [abbreviation: (1); bpy or 4,4'-bpy=4,4'-bipyridine; SO42-=sulfate group] has been reported. The structure of this MOF consists of Cu+ nodes connected via 4,4'-bpy to form infinite chains, with two neighboring chains further bridged on the nodes by SO42-, resulting in a 1-D double chain network. Guest water molecules reside in between the chains and are hydrogen-bonded to the O and S atoms from the nearest sulfate groups, leading to the formation of a 3-D supramolecular framework. This MOF is good heterogeneous catalyst for the cyclopropanation of styrene, with high trans cyclopropane diastereoselectivity and was recycled and reused for three consecutive cycles without a significant loss of catalytic activity. - Graphical Abstract: A new MOF structure built up of 4,4'-bipyridine, sulphate and Cu(I), is an active heterogeneous catalyst for cyclopropanation of styrene with ethyldiazoacetate. Highlights: → The synthesis is different from solvothermal synthesis for other Cu(I) compounds. → The compound and the structure are new. → H bonds form infinite planes among water molecules and sulphate species. → H bonding interaction makes the structure into a 3D supramolecular framework. → Active catalytic property as heterogeneous catalyst for cyclopropanation of styrene.

  10. (2,2′-Bipyridine-κ2N,N′iodido(pyrrolidine-1-dithiocarboxylato-κ2S,S′copper(II

    Directory of Open Access Journals (Sweden)

    Ji-Huai Wu

    2008-05-01

    Full Text Available In the title compound, [Cu(C5H8NS2I(C10H8N2], the CuII ion is coordinated by one iodide ion, two N atoms of the bipyridine ligand and two S atoms from the pyrrolidine-1-dithiocarboxylate ligand in a distorted square-pyramidal environment.

  11. Am3+ complexation with bis-(1,2,4-triazinyl) bipyridine (BTBP)/phenanthroline (BTPhen) derivatives by UV-Vis spectrophotometry and DFT studies

    International Nuclear Information System (INIS)

    Complexation of Am3+ is studied with the tetradentate 'N' donor ligands 5,6-dialkyl bis-(1,2,4- triazinyl)bipyridine (RBTBP) and phenanthroline (RBTPhen) using UV-Vis spectrophotometric titrations. Stronger complexation with RBTBP as compared to RBTPhen is explained with the help of density functional theoretical (DFT) calculations. (author)

  12. Polymer Acceptor Based on Double B←N Bridged Bipyridine (BNBP) Unit for High-Efficiency All-Polymer Solar Cells.

    Science.gov (United States)

    Long, Xiaojing; Ding, Zicheng; Dou, Chuandong; Zhang, Jidong; Liu, Jun; Wang, Lixiang

    2016-08-01

    A novel polymer acceptor based on the double B←N bridged bipyridine building block is reported. All-polymer solar cells based on the new polymer acceptor show a power conversion efficiency of as high as 6.26% at a photon energy loss of only 0.51 eV. PMID:27167123

  13. A Selective Chemosensor for Mercuric Ions Based on 4-Aminothiophenol-Ruthenium(II Bis(bipyridine Complex

    Directory of Open Access Journals (Sweden)

    Amer A. G. Al Abdel Hamid

    2011-01-01

    Full Text Available A new ruthenium(II complex (cis-ruthenium-bis[2,2′-bipyridine]-bis[4-aminothiophenol]-bis[hexafluorophosphate] has been synthesized and characterized using standard analytical and spectroscopic techniques, FTIR, 1H and 13C-NMR, UV/vis, elemental analysis, conductivity measurements, and potentiometric titration. Investigation of the synthesized complex with metal ions showed that this complex has photochemical properties that are selective and sensitive toward the presence of mercuric ion in aqueous solution. The detection limit for mercuric ions using UV/vis spectroscopy was estimated to be ~ 0.4 ppm. The results presented herein may have an important implication in the development of a spectroscopic selective detection for mercuric ions in aqueous solution.

  14. Establishment of structure-conductivity relationship for tris(2,2'-bipyridine) ruthenium ionic C(60) salts.

    Science.gov (United States)

    Hong, Jie; Shores, Matthew P; Elliott, C Michael

    2010-12-20

    Three ionic C(60) salts with [Ru(bpy)(3)](m+) (bpy = 2,2'-bipyridine) as cations were synthesized. The UV-vis-NIR spectra, XPS spectra, and elemental analysis have demonstrated their compositions: [Ru(bpy)(3)](2)(C(60)) (1), [Ru(bpy)(3)](C(60)) (2), and [Ru(bpy)(3)](C(60))(2) (3). Single crystals of polycrystalline compounds 1 and 2 were obtained as solvates. At room temperature, all three salts are semiconducting with the highest four-probe conductivity observed for compound 1 at ∼10 S m(-1). The electronic conduction mechanisms can be described appropriately by an electron hopping model in this immobilized polyvalent redox system. PMID:21070047

  15. Host–guest complexes of mixed glycol-bipyridine cryptands: prediction of ion selectivity by quantum chemical calculations, part V

    Directory of Open Access Journals (Sweden)

    Svetlana Begel

    2013-06-01

    Full Text Available The selectivity of the cryptands [2.2.bpy] and [2.bpy.bpy] for the endohedral complexation of alkali, alkaline-earth and earth metal ions was predicted on the basis of the DFT (B3LYP/LANL2DZp calculated structures and complex-formation energies. The cavity size in both cryptands lay between that for [2.2.2] and [bpy.bpy.bpy], such that the complexation of K+, Sr2+ and Tl3+ is most favorable. While the [2.2.bpy] is moderately larger, preferring Rb+ complexation and demonstrating equal priority for Sr2+ and Ba2+, the slightly smaller [2.bpy.bpy] yields more stable cryptates with Na+ and Ca2+. Although the CH2-units containing molecular bars fixed at the bridgehead nitrogen atoms determine the flexibility of the cryptands, the twist angles associated with the bipyridine and glycol building blocks also contribute considerably.

  16. (2,2′-Bipyridine-κ2N,N′dichloridopalladium(II 1,4-dioxane hemisolvate

    Directory of Open Access Journals (Sweden)

    Ricardo Alfredo Gutiérrez Márquez

    2014-06-01

    Full Text Available The asymmetric unit of the title compound, [PdCl2(C10H8N2]·0.5C4H8O2, consists of one PdII complex molecule and a half-molecule of 1,4-dioxane, the complete molecule being generated by inversion symmetry. The PdII atom has an almost square-planar coordination formed by the 2,2′-bipyridine ligand and two chloride ligands. Two intramolecular C—H...Cl hydrogen bonds occur. In the crystal, the PdII complex and 1,4-dioxane molecules are connected by C—H...O hydrogen bonds, forming a layer parallel to (10-1. Within the layer, weak π–π interactions [centroid–centroid distance = 3.817 (4 Å] are observed between the pyridine rings.

  17. Photoisomerisation in Aminoazobenzene-Substituted Ruthenium(II) Tris(bipyridine) Complexes: Influence of the Conjugation Pathway.

    Science.gov (United States)

    Amar, Anissa; Savel, Paul; Akdas-Kilig, Huriye; Katan, Claudine; Meghezzi, Hacène; Boucekkine, Abdou; Malval, Jean-Pierre; Fillaut, Jean-Luc

    2015-05-26

    Transition-metal complexes containing stimuli-responsive systems are attractive for applications in optical devices, photonic memory, photosensing, as well as luminescence imaging. Amongst them, photochromic metal complexes offer the possibility of combining the specific properties of the metal centre and the optical response of the photochromic group. The synthesis, the electrochemical properties and the photophysical characterisation of a series of donor-acceptor azobenzene derivatives that possess bipyridine groups connected to a 4-dialkylaminoazobenzene moiety through various linkers are presented. DFT and TD-DFT calculations were performed to complement the experimental findings and contribute to their interpretation. The position and nature of the linker (ethynyl, triazolyl, none) were engineered and shown to induce different electronic coupling between donor and acceptor in ligands and complexes. This in turn led to strong modulations in terms of photoisomerisation of the ligands and complexes. PMID:25846371

  18. Stepwise preparation and characterization of molecular wires made of zinc octaethylporphyrin complexes bridged by 4, 4'-bipyridine on HOPG

    International Nuclear Information System (INIS)

    Molecular-scale devices can be made using a step-by-step procedure, in a controllable and highly versatile way. In this report, we describe the growth of molecular wires (MW) from zinc (II) octaethylporphyrin (ZnOEP) assembled on highly oriented pyrolytic graphite (HOPG) by a step-by-step approach using 4, 4'-bipyridine (BP) to bridge the porphyrin units, via coordination of the nitrogen atom to zinc. In order to gain an insight into the molecular self-organization of these wires, we carried out a detailed scanning tunnelling microscopy (STM) analysis of each monolayer, using a solid/liquid interface technique, up to a complete ZnOEP/BP/ZnOEP/BP/ZnOEP-assembled structure. The electrical properties of the MWs were assessed by scanning tunnelling spectroscopy (STS) and by current-sensing atomic force microscopy (CS-AFM), showing an increase of electrical resistance with the length of the MW.

  19. Tetrakis(μ-2,4-difluorobenzoatobis[(2,2′-bipyridine(2,4-difluorobenzoatoterbium(III

    Directory of Open Access Journals (Sweden)

    Xia Liu

    2009-02-01

    Full Text Available In the centrosymmetric dinuclear title compound, [Tb2(C7H3F2O26(C10H8N22], the TbIII ion is coordinated by an N,N′-bidentate 2,2′-bipyridine molecule, and two O,O′-bidentate 2,4-difluorobenzoate (dfb anions. One of the latter also bonds to the second TbIII centre through one of its O atoms. The third dfb anion bonds to one Tb atom from each of its O atoms. Thus, the three dfb species have three different coordination modes. This results in an irregular TbN2O7 coordination sphere for the metal ion. The F atoms and their associated H atoms in the simple bidentate dfb anion are disordered over two sets of sites in a 0.672 (10:0.328 (10 ratio.

  20. Analysis of Peculiarities of the SEHRS Spectrum of - Bipyridine Molecule on the Base of the Dipole-Quadrupole Theory

    CERN Document Server

    Chelibanov, V P; Polubotko, A M

    2015-01-01

    The SEHRS spectrum of 4,4' Bipyridine is analyzed on the base of the Dipole Quadrupole theory. It is demonstrated that there appear strong lines caused by vibrations transforming after a unit irreducible representation of the D2 symmetry group. which is most probably describes the symmetry properties of the molecule. These lines are nearly forbidden for the molecule, adsorbed on rough metal surface. Appearance of these lines is associated with a strong quadrupole light molecule interaction, which exists in this system. In addition, there are lines, caused by contributions from both the vibrations transforming after the unit irreducible representation A and the representation B1, which describes transformational properties of the dz component of the dipole moment, which is perpendicular to the surface. This result is associated with the specific geometry of the molecule, when the indicated vibrations can be nearly degenerated and cannot be resolved by the SEHRS spectra analysis. Analysis of the SEHRS spectra f...

  1. Coordination Complexes of Decamethylytterbocene with 4,4'-Disubstituted Bipyridines: An Experimental Study of Spin Coupling in Lanthanide Complexes

    OpenAIRE

    Walter, Marc D.; Berg, David J.; Andersen, Richard A.

    2005-01-01

    The paramagnetic 1:1 coordination complexes of (C5Me5)2Yb with a series of 4,4'-disubstituted bipyridines, bipy-X, where X is Me, tert-Bu, OMe, Ph, CO2Me, and CO2Et have been prepared. All of the complexes are paramagnetic and the values of the magnetic susceptibility as a function of temperature show that these values are less than expected for the cation, [(C5Me5)2Yb(III)(bipy-X)]+, which have been isolated as the cation-anion ion-pairs [(C5Me5)2Yb(III)(bipy-X)]+[(C5Me5)2YbI2]f fnfn wh...

  2. Synthèse en série bipyridine. Etude de l'interaction avec l'ADN

    OpenAIRE

    Stegarescu-Furdui, Bianca

    2006-01-01

    Nous avons développé la synthèse d'hétérocycles indoliziniques fonctionnalisés par un cation pyridinium et étudié leur interaction avec L'ADN. L'étape-clé pour accéder aux indolizines est la cycloaddition [3+2]-dipolaire des ylures dérivés des sels quaternaires de la 4,4'-bipyridine avec des dipolarophiles. La synthèse a été effectuée par la voie classique (chauffage en solvant) et par irradiation avec des micro-ondes (“chimie verte”). Nous avons étudié les propriétés acido-basiques des sels ...

  3. Disposable biosensor based on cathodic electrochemiluminescence of tris(2,2-bipyridine)ruthenium(II) for uric acid determination

    Energy Technology Data Exchange (ETDEWEB)

    Ballesta-Claver, J.; Rodríguez-Gómez, R. [ECsens, Department of Analytical Chemistry, Campus Fuentenueva, Faculty of Sciences, University of Granada, E-18071 Granada (Spain); Capitán-Vallvey, L.F., E-mail: lcapitan@ugr.es [ECsens, Department of Analytical Chemistry, Campus Fuentenueva, Faculty of Sciences, University of Granada, E-18071 Granada (Spain)

    2013-04-03

    Highlights: ► Cathodic ECL offers conventional and non-aggressive analysis conditions. ► The ECL hydrogen peroxide/ruthenium complex system for uric acid determination is novel. ► The ruthenium complex is electrochemically immobilized on graphite screen-printed electrodes. ► The quantification of the uric acid is based on a Stern–Volmer type equation. ► The use of the cathodic ECL working methodology reduces interferences during analysis. -- Abstract: A new method for uric acid (UA) determination based on the quenching of the cathodic ECL of the tris(2,2-bipyridine)ruthenium(II)–uricase system is described. The biosensor is based on a double-layer design containing first tris(2,2-bipyridine)ruthenium(II) (Ru(bpy){sub 3}{sup 2+}) electrochemically immobilized on graphite screen-printed cells and uricase in chitosan as a second layer. The uric acid biosensing is based on the ECL quenching produced by uric acid over the cathodic ECL caused by immobilized Ru(bpy){sub 3}{sup 2+} in the presence of uricase. The use of a −1.1 V pulse for 1 s with a dwelling time of 10 s makes it possible to estimate the initial enzymatic rate, which is used as the analytical signal. The Stern–Volmer type calibration function shows a dynamic range from 1.0 × 10{sup −5} to 1.0 × 10{sup −3} M with a limit of detection of 3.1 × 10{sup −6} M and an accuracy of 13.6% (1.0 × 10{sup −4} M, n = 5) as relative standard deviation. Satisfactory results were obtained for urine samples, creating an affordable alternative for uric acid determination.

  4. 2,3,4,5-Tetra­fluoro­benzoic acid–4,4′-bipyridine (2/1)

    OpenAIRE

    Zhu, Xiaohui

    2009-01-01

    The asymmetric unit of the title compound, 2C7H2F4O2·C10H8N2, contains one mol­ecule of 2,3,4,5-tetra­fluoro­benzoic acid (tfb) and half of a centrosymmetric 4,4′-bipyridine mol­ecule. Inter­molecular O—H⋯N hydrogen bonds link two tfb mol­ecules and one 4,4′-bipyridine mol­ecule into a trimer. Weak inter­molecular C—H⋯F inter­actions assemble these trimers into a three-dimensional network structure.

  5. catena-Poly[[[tetraaquacobalt(II]-μ-4,4′-bipyridine-κ2N:N′] 2-[4-(2-carboxylatoethylphenoxy]acetate

    Directory of Open Access Journals (Sweden)

    Xi-Fang Wang

    2009-07-01

    Full Text Available In the title complex, {[Co(C10H8N2(H2O4](C11H10O5}n, the unique CoII ion lies on an inversion center and is coordinated by two N atoms from two 4,4′-bipyridine ligands and four O atoms from four water molecules in a slightly distorted octahedral coordination geometry. The 4,4′-bipyridine ligands bridge CoII ions into a one-dimensional chain structure. In the crystal structure, intermolecular O—H...O hydrogen bonds link cations and anions into a three-dimensional network. The dianions are completely disordered about an inversion center.

  6. Conformational isomerism in mixed-ligand complexes of 2,2'-bipyridine and triphenylphosphine with copper(I) halides

    Energy Technology Data Exchange (ETDEWEB)

    Barron, P.F.; Engelhardt, L.M.; Healy, P.C.; Kildea, J.D.; White, A.H.

    1988-05-18

    Mixed-ligand complexes of triphenylphosphine and 2,2'-bipyridine and copper(I) halides have been synthesized. The /sup 31/P NMR spectra of the complexes were measured and are reported along with data for complete structural characterization of the complexes. The results indicate a novel dichotomy of conformational isomers to be present in the chloride lattice. The Cu-P bond length was found to not vary with different halides. 8 refs., 4 figs., 6 tabs.

  7. Luminescent Ruthenium(II) Complex Bearing Bipyridine and N-Heterocyclic Carbene-based C∧N∧C Pincer Ligand for Live-Cell Imaging of Endocytosis

    Science.gov (United States)

    Tsui, Wai-Kuen; Chung, Lai-Hon; Wong, Matthew Man-Kin; Tsang, Wai-Him; Lo, Hoi-Shing; Liu, Yaxiang; Leung, Chung-Hang; Ma, Dik-Lung; Chiu, Sung-Kay; Wong, Chun-Yuen

    2015-03-01

    Luminescent ruthenium(II)-cyanide complex with N-heterocyclic carbene pincer ligand C∧N∧C = 2,6-bis(1-butylimidazol-2-ylidene)pyridine and 2,2'-bipyridine (bpy) shows minimal cytotoxicity to both human breast carcinoma cell (MCF-7) and human retinal pigmented epithelium cell (RPE) in a wide range of concentration (0.1-500 μM), and can be used for the luminescent imaging of endocytosis of the complex in these cells.

  8. Synthesis and Photochemical Properties of a New Substituted Phenol Covalently Linked to Ruthenium (Ⅱ) Tris-bipyridine Containing Four Ester Groups as Sensitizer

    Institute of Scientific and Technical Information of China (English)

    Feng SHI; Hong Yang LI; Xiao Jun PENG; Rong ZHANG; Xiao Qiang CHEN; Jiang Li FAN; Li Cheng SUN

    2004-01-01

    As photosensitizer for solar cell, a new ruthenium (Ⅱ) complex with four ester groups had been synthesized, in which a phenol substituted by {[(2-hydroxy-5-tert-butylbenzyl)(pyridyl2-methyl)amino]methyl} is covalently linked to ruthenium (Ⅱ) tris-bipyridine. The structures of the new compounds were confirmed by NMR and ESI-MS spectra. The electrochemical and photochemical properties were also studied.

  9. Coordination polymers with the chiral ligand N-p-tolylsulfonyl-L-glutamic acid: Influence of metal ions and different bipyridine ligands on structural chirality

    International Nuclear Information System (INIS)

    Four new polymers, namely [Ni(-tsgluO)(2,4'-bipy)2(H2O)2]n.5nH2O (1), [Co(-tsgluO)(2,4'-bipy)2(H2O)2]n.5nH2O (2), [Ni(-tsgluO)(4,4'-bipy)]n.0.5nH2O (3), and [Co(-tsgluO)(4,4'-bipy)]n.0.5nH2O (4), where tsgluO2-=(+)-N-p-tolylsulfonyl-L-glutamate dianion, 2,4'-bipy=2,4'-bipyridine, and 4,4'-bipy=4,4'-bipyridine, have been prepared and structurally characterized. Compounds 1 and 2 are isostructural and mononuclear, and crystallize in the acentric monoclinic space group Cc, forming 1D chain structures. Compound 3 is also mononuclear, but crystallizes in the chiral space group P21, forming a homochiral 2D architecture. In contrast to the other complexes, compound 4 crystallizes in the space group P-1 and is composed of binuclear [Co2O6N2]n4- units, which give rise to a 2D bilayer framework. Moreover, compounds 1, 2, and 4 self-assemble to form 3D supramolecular structures through π-π stacking and hydrogen-bonding interactions, while compound 3 is further hydrogen-bonded to form 3D frameworks. We have demonstrated the influence of the central metal and bipyridine ligands on the framework chirality of the coordination complexes. - Graphical abstract: Four novel polymers based on a chiral ligand were prepared and structurally characterized; it represents the first series of investigations about the effect of central metals and bipyridine ligands on framework chirality.

  10. Synthesis and characterization of 6,6’-bis(2-hydroxyphenyl)-2,2’-bipyridine ligand and its interaction with ct-DNA

    International Nuclear Information System (INIS)

    The tetradentate ligand with four donor atoms OONN was synthesized. Bis(phenoxy)bipyridine ligand was prepared by Suzuki coupling reaction between 6,6’-dibromo-2,2’-bipyridyl and 2-hydroxyphenylboronic acid with presence of palladium (II) acetate. Bis(phenoxy)bipyridine ligand was also synthesized by demethylating of 6,6’-bis(2-methoxyphenyl)-2,2’-bipyridyl ligand through solvent free reaction using pyridine hydrocloride. The formation of both phenoxy and methoxy ligands was confirmed by 1H, 2D cosy and 13C NMR spectroscopy, ESI-MS spectrometry, FTIR spectroscopy. The purity of the ligand was confirmed by melting point. Binding studies of small molecules with DNA are useful to understand the reaction mechanism and to provide guidance for the application and design of new and more efficient drugs targeted to DNA. In this study, the binding interaction between the synthesized ligand with calf thymus-DNA (ct-DNA) has been investigated by UV/Vis DNA titration study. From the UV/Vis DNA study, it shows that bis(phenoxy)bipyridine ligand bind with ct-DNA via outside binding with binding contant Kb = 1.19 × 103 ± 0.08 M−1

  11. Synthesis and characterization of 6,6'-bis(2-hydroxyphenyl)-2,2'-bipyridine ligand and its interaction with ct-DNA

    Science.gov (United States)

    Selamat, Norhidayah; Heng, Lee Yook; Hassan, Nurul Izzaty; Karim, Nurul Huda Abd

    2015-09-01

    The tetradentate ligand with four donor atoms OONN was synthesized. Bis(phenoxy)bipyridine ligand was prepared by Suzuki coupling reaction between 6,6'-dibromo-2,2'-bipyridyl and 2-hydroxyphenylboronic acid with presence of palladium (II) acetate. Bis(phenoxy)bipyridine ligand was also synthesized by demethylating of 6,6'-bis(2-methoxyphenyl)-2,2'-bipyridyl ligand through solvent free reaction using pyridine hydrocloride. The formation of both phenoxy and methoxy ligands was confirmed by 1H, 2D cosy and 13C NMR spectroscopy, ESI-MS spectrometry, FTIR spectroscopy. The purity of the ligand was confirmed by melting point. Binding studies of small molecules with DNA are useful to understand the reaction mechanism and to provide guidance for the application and design of new and more efficient drugs targeted to DNA. In this study, the binding interaction between the synthesized ligand with calf thymus-DNA (ct-DNA) has been investigated by UV/Vis DNA titration study. From the UV/Vis DNA study, it shows that bis(phenoxy)bipyridine ligand bind with ct-DNA via outside binding with binding contant Kb = 1.19 × 103 ± 0.08 M-1.

  12. Comparative studies of pyridine and bipyridine ruthenium dye complexes with different side groups as sensitizers in sol-gel quasi-solid-state dye sensitized solar cells

    International Nuclear Information System (INIS)

    Six ruthenium(II) complexes as charge-transfer sensitizers for dye sensitized solar cells (DSSCs) are synthesized. The absorption and electrochemical properties of newly synthesized ruthenium-dye molecules contained one bipyridine (bpy) ligand with two carboxylic groups have been investigated. Among them, four ruthenium(II) complexes contain a second bpy ligand with branching and non-branching side groups containing C and H only and the remaining two ruthenium(II) complexes instead of a second bipyridine (bpy) ligand, they consisted of a pyridine (py) ligand with side groups containing –C–O–C–molecular group. Dye sensitized solar cells employing quasi-solid state electrolyte and the six ruthenium complexes are constructed and electrically characterized under standard conditions of light irradiance (1000 W/m2, AM 1.5). Their behavior is compared with that of commercially available ruthenium complex D907 in terms of current-voltage characteristic curves under simulated light and dark while electrochemical impedance spectroscopy showed comparable results for local resistance to charge transfer across the TiO2-electrolyte interface and free electron lifetimes for two bipyridine and commercial D907 complexes. The influence of molecular side groups into ruthenium-dye molecules is discussed in terms of the cells' efficiency

  13. Synthesis and characterization of 6,6’-bis(2-hydroxyphenyl)-2,2’-bipyridine ligand and its interaction with ct-DNA

    Energy Technology Data Exchange (ETDEWEB)

    Selamat, Norhidayah; Heng, Lee Yook; Hassan, Nurul Izzaty; Karim, Nurul Huda Abd [School of Chemical Sciences and Food Technology, Faculty of Science and Technology, Universiti Kebangsaan Malaysia, 43650 Bangi, Selangor (Malaysia)

    2015-09-25

    The tetradentate ligand with four donor atoms OONN was synthesized. Bis(phenoxy)bipyridine ligand was prepared by Suzuki coupling reaction between 6,6’-dibromo-2,2’-bipyridyl and 2-hydroxyphenylboronic acid with presence of palladium (II) acetate. Bis(phenoxy)bipyridine ligand was also synthesized by demethylating of 6,6’-bis(2-methoxyphenyl)-2,2’-bipyridyl ligand through solvent free reaction using pyridine hydrocloride. The formation of both phenoxy and methoxy ligands was confirmed by {sup 1}H, 2D cosy and {sup 13}C NMR spectroscopy, ESI-MS spectrometry, FTIR spectroscopy. The purity of the ligand was confirmed by melting point. Binding studies of small molecules with DNA are useful to understand the reaction mechanism and to provide guidance for the application and design of new and more efficient drugs targeted to DNA. In this study, the binding interaction between the synthesized ligand with calf thymus-DNA (ct-DNA) has been investigated by UV/Vis DNA titration study. From the UV/Vis DNA study, it shows that bis(phenoxy)bipyridine ligand bind with ct-DNA via outside binding with binding contant K{sub b} = 1.19 × 10{sup 3} ± 0.08 M{sup −1}.

  14. Synergic extraction of lanthanide(III) ions with 2-thenoyltrifluoroacetone in the presence of 2,2'-bipyridine or pyridine

    International Nuclear Information System (INIS)

    The synergic extraction of various tervalent lanthanides (Ln), La, Ce, Nd, Sm, Gd, Tb, Yb and Lu, with 2-thenoyltrifluoroacetone (Htta) in the presence of a bidentate heterocyclic amine, 2,2'-bipyridine (bipy), in benzene was investigated. The synergic enhancement was attributed to the formation of the adducts, Ln(tta)3(bipy). The synergic extraction of La(III), Sm(III) and Lu(III) with Htta and a unidentate amine, pyridine (py), was also studied and the formation of the adducts, Ln(tta)3py and Ln(tta)3(py)2, was observed. The adduct formation constants, βsub(s,1) and βsub(s,2), were determined. The βsub(s,2) values for py decrease with increasing atomic number of Ln(III), but βsub(s,1) values for bipy increase with increasing atomic number of Ln(III). The synergic extraction constants and the separation factors in the bipy system were also determined. (author)

  15. A second monoclinic polymorph of bis(2,2′-bipyridine-κ2N,N′diiodidomanganese(II

    Directory of Open Access Journals (Sweden)

    Kwang Ha

    2011-10-01

    Full Text Available The MnII ion in the title complex, [MnI2(C10H8N22], is six-coordinated in a distorted cis-N4I2Mn octahedral environment by four N atoms of the two chelating 2,2′-bipyridine ligands and two iodide anions. As a result of the different trans effects of the N and I atoms, the Mn—N bonds trans to the I atom are slightly longer than the Mn—N bonds trans to the N atom. The dihedral angle between the approximately planar ligands [maximum deviation = 0.064 (7 Å] is 75.0 (1°. Numerous inter- and intramolecular π–π interactions between the pyridyl rings are present, the shortest centroid–centroid distance being 3.905 (5 Å. The structure reported herein represents a new monoclinic polymorph of the previously reported monoclinic (P21/c form [Ha (2011. Z. Kristallogr. New Cryst. Struct. 226, 187–188].

  16. Synthesis and biological evaluation of 4-(2-fluorophenoxy)-3,3'-bipyridine derivatives as potential c-met inhibitors.

    Science.gov (United States)

    Zhao, Sijia; Zhang, Yu; Zhou, Hongyang; Xi, Shuancheng; Zou, Bin; Bao, Guanglong; Wang, Limei; Wang, Jiao; Zeng, Tianfang; Gong, Ping; Zhai, Xin

    2016-09-14

    Six series of novel 4-(2-fluorophenoxy)-3,3'-bipyridine derivatives conjugated with aza-aryl formamide/amine scaffords were designed and synthesized through a structure-based molecular hybridization approach. The target compounds were evaluated for c-Met kinase inhibitory activities and cytotoxicity against four cancer cell lines (HT-29, A549, MKN-45 and MDA-MB-231) in vitro. Most compounds exhibited moderate to excellent potency, and the most promising candidate 26c (c-Met kinase IC50 = 8.2 nM) showed a 4.7-fold increase in cytotoxicity against c-Met-addicted MKN-45 cell line in vitro (IC50 = 3 nM), superior to that of Foretinib (IC50 = 23 nM). The preliminary structure-activity relationship indicated that a 1H-benzo [e] [1,3,4]thiadiazine-3-carboxamide-4,4-dioxide moiety as linker contributed to the antitumor potency. PMID:27187857

  17. Quantum processes in 8-Oxo-Guanine-Ru(bipyridine){3/2+} photosynthetic systems of artificial minimal cells

    Science.gov (United States)

    Tamulis, Arvydas; Grigalavicius, Mantas; Krisciukaitis, Sarunas; Medzevicius, Giedrius

    2011-06-01

    Density functional theory methods were used to investigate various self-assembled photoactive bioorganic systems of interest for artificial minimal cells. The cell systems studied are based on nucleotides or their compounds and consisted of up to 123 atoms (not including the associated water or methanol solvent shells) and are up to 2.5 nm in diameter. The electron correlation interactions responsible for the weak hydrogen and Van derWaals chemical bonds increase due to the addition of a polar solvent (water or methanol). The precursor fatty acid molecules of the system also play a critical role in the quantum mechanical interaction based self-assembly of the photosynthetic center and the functioning of the photosynthetic processes of the artificial minimal cells. The distances between the separated sensitizer, fatty acid precursor, and methanol molecules are comparable to Van derWaals and hydrogen bonding radii. As a result the associated electron correlation interactions compress the overall system, resulting in an even smaller gap between the highest occupied molecular orbital (HOMO), and lowest unoccupied molecular orbital (LUMO) electron energy levels and photoexcited electron tunnelling occurs from the sensitizer (either Ru(bpy){3/2+} or [Ru(bpy)2(4-Bu-4'-Me-2,2'-bpy)]2++ derivatives) to the precursor fatty acid molecules (notation used: Me = methyl; Bu = butyl; bpy = bipyridine). The shift of the absorption spectrum to the red for the artificial protocell photosynthetic centers might be considered as the measure of the complexity of these systems.

  18. Crystal structure of 4,4′-(disulfanediyldibutanoic acid–4,4′-bipyridine (1/1

    Directory of Open Access Journals (Sweden)

    Ana María Atria

    2014-09-01

    Full Text Available 4,4′-(Disulfanediyldibutanoic acid (dtba and 4,4′-bipyridine (4,4′-bpy crystallize in an 1:1 ratio, leading to the title co-crystal with composition C8H14O4S2·C10H8N2. A distinctive feature of the crystal structure is the geometry of the dtba moiety, which appears to be stretched [with a 9.98 (1 Å span between outermost carbons] and acts as an hydrogen-bonding connector, forming linear chains along [-211] with the 4,4′-bpy moiety by way of O—H...N hydrogen bonds and C—H...O interactions. The influence of the molecular shape on the hydrogen-bonding pattern is analysed by comparing the title compound and two other 4,4′-bpy co-crystals with closely related molecules of similar formulation but different geometry, showing the way in which this correlates with the packing arrangement.

  19. Redetermination of (2,2′-bipyridine-κ2N,N′dichloridopalladium(II dichloromethane solvate

    Directory of Open Access Journals (Sweden)

    Nam-Ho Kim

    2009-06-01

    Full Text Available In the title compound, [PdCl2(C10H8N2]·CH2Cl2, the Pd2+ ion is four-coordinated in a slightly distorted square-planar environment by two N atoms of the 2,2′-bipyridine (bipy ligand and two chloride ions. The compound displays intramolecular C—H...Cl hydrogen bonds and pairs of complex molecules are connected by intermolecular C—H...Cl hydrogen bonds. Intermolecular π–π interactions are present between the pyridine rings of the ligand, the shortest centroid–centroid distance being 4.096 (3 Å. As a result of the electronic nature of the chelate ring, it is possible to create π–π interactions to its symmetry-related counterpart [3.720 (2 Å] and also with a pyridine ring [3.570 (3 Å] of the bipy unit. The present structure is a redetermination of a previous structure [Vicente et al. (1997. Private communication (refcode PYCXMN02. CCDC, Cambridge, England]. In the new structure refinement all H atoms were located in a difference Fourier synthesis. Their coordinates were refined freely, together with isotropic displacement parameters.

  20. Redetermination of (2,2'-bipyridine-κN,N')dichlorido-palladium(II) dichloro-methane solvate.

    Science.gov (United States)

    Kim, Nam-Ho; Hwang, In-Chul; Ha, Kwang

    2009-01-01

    In the title compound, [PdCl(2)(C(10)H(8)N(2))]·CH(2)Cl(2), the Pd(2+) ion is four-coordinated in a slightly distorted square-planar environment by two N atoms of the 2,2'-bipyridine (bipy) ligand and two chloride ions. The compound displays intra-molecular C-H⋯Cl hydrogen bonds and pairs of complex mol-ecules are connected by inter-molecular C-H⋯Cl hydrogen bonds. Inter-molecular π-π inter-actions are present between the pyridine rings of the ligand, the shortest centroid-centroid distance being 4.096 (3) Å. As a result of the electronic nature of the chelate ring, it is possible to create π-π inter-actions to its symmetry-related counterpart [3.720 (2) Å] and also with a pyridine ring [3.570 (3) Å] of the bipy unit. The present structure is a redetermination of a previous structure [Vicente et al. (1997 ▶). Private communication (refcode PYCXMN02). CCDC, Cambridge, England]. In the new structure refinement all H atoms were located in a difference Fourier synthesis. Their coordinates were refined freely, together with isotropic displacement parameters. PMID:21582986

  1. The excited triplet (T{sub 1}) state structure and vibrational properties of 2,2'-bipyridine

    Energy Technology Data Exchange (ETDEWEB)

    Lapouge, C.; Buntinx, G. [Laboratoire de Spectrochimie Infrarouge et Raman, UMR 8516 de l' Universite et du CNRS, Centre d' Etudes et de Recherches Lasers et Applications (FR 2416 du CNRS), Bat. C5, Universite des Sciences et Technologies de Lille, 59655 Villeneuve d' Ascq (France); Poizat, O. [Laboratoire de Spectrochimie Infrarouge et Raman, UMR 8516 de l' Universite et du CNRS, Centre d' Etudes et de Recherches Lasers et Applications (FR 2416 du CNRS), Bat. C5, Universite des Sciences et Technologies de Lille, 59655 Villeneuve d' Ascq (France)], E-mail: olivier.poizat@univ-lille1.fr

    2008-06-02

    The geometry of the lowest lying excited triplet state (T{sub 1}) of 2,2'-bipyridine (22BPY) was optimized by using the time-dependent density functional theory (TD-DFT) with the B3LYP functional and the SVP basis set. The T{sub 1} state is of {sup 3}B{sub u} symmetry and results from a nearly one-electron {pi}{pi}* transition from the 3b{sub g} HOMO to the 4a{sub u} LUMO. Its geometry is trans-planar and essentially characterized by a reinforcement of the interring CC bond and a quinoidal distortion of the rings. This calculated triplet structure is firmly validated by an unequivocal agreement, for four 22BPY isotopomers, between the derived theoretical vibrational frequencies and previously reported experimental time-resolved resonance Raman (TR3) spectra. Moreover, vertical transitions to the 10 lowest energy triplet states T{sub n} were calculated and the corresponding T{sub 1} state resonance Raman intensities estimated, in the short-time dynamics approximation of the Franck-Condon scattering mechanism, from the gradient of the T{sub n} potential surfaces at the T{sub 1} geometry along the totally symmetric modes. Excellent agreement with the experimental resonance Raman intensities was observed for a 4a{sub u} (LUMO) {yields} 5b{sub g} (LUMO + 3) T{sub 1} {yields} T{sub n} transition. This analysis provides a further support of the TD-DFT optimized T{sub 1} state structure of 22BPY.

  2. Electrode Kinetics of the Redox Reaction of Tris(2,2′-bipyridine)nickel Complexes in an Ionic Liquid

    International Nuclear Information System (INIS)

    Electrode reaction of tris(2,2′-bipyridine)nickel complexes, [Ni(bpy)3]3+ and [Ni(bpy)3]2+, was investigated in an aprotic ionic liquid, 1-butyl-1-methylpyrrolidinium bis(trifluoromethylsulfonyl)amide (BMPTFSA) using AC impedance spectroscopy. The formal potential of [Ni(bpy)3]3+/2+ was 1.37 V vs. ferrocene/ferrocenium at 25 °C. The diffusion coefficients of [Ni(bpy)3]3+ and [Ni(bpy)3]2+ at 25 °C were 4.2 and 7.0 × 10−8 cm2 s−1, respectively, which are close to those of [M(bpy)3]3+ and [M(bpy)3]2+ (M = Ru and Fe) due to the similarity in the charge densities. The activation energies for the diffusion coefficients were close to that for the viscosity of the ionic liquid, indicating the viscosity is a major factor that determine the diffusion of the complexes. The rate constant of [Ni(bpy)3]3+/2+ was 8.3 × 10−6 cm s−1, which is smaller by two orders of magnitude than those for [Ru(bpy)3]3+/2+ and [Fe(bpy)3]3+/2+, reflecting the slow electron transfer caused by participation of the anti-bonding molecular orbital in the redox reaction. The apparent activation energy for the rate constant of [Ni(bpy)3]3+/2+ is considered determined not only by the activation energy for the viscosity but also by the reorganization energy, of which the inner component is larger than those in [Ru(bpy)3]3+/2+ and [Fe(bpy)3]3+/2+

  3. CuCl-Catalyzed Aerobic Oxidation of Allylic and Propargylic Alcohols to Aldehydes or Ketones with 1 : 1 Combination of Phenanthroline and Bipyridine as the Ligandst%CuCl-Catalyzed Aerobic Oxidation of Allylic and Propargylic Alcohols to Aldehydes or Ketones with 1 : 1 Combination of Phenanthroline and Bipyridine as the Ligandst

    Institute of Scientific and Technical Information of China (English)

    刘宇; 麻生明

    2012-01-01

    We developed a modified protocol for the oxidation of 2,3-allenyl alcohols using CuCI with l : 1 combination of phenanthroline and bipyridine as the catalyst. To further investigate the applicability of this system, other types of alcohols such as allylic and propargylic alcohols have been tested: we found that both allylic and propargylic alcohols may be oxidized to the corresponding aldehydes or ketones using molecular oxygen in air as the oxidant with moderate to excellent yields.

  4. Investigation of torsional potentials, molecular structure, vibrational properties, molecular characteristics and NBO analysis of some bipyridines using experimental and theoretical tools

    Science.gov (United States)

    Prashanth, J.; Reddy, B. Venkatram; Rao, G. Ramana

    2016-08-01

    The Fourier Transform Infrared (FTIR) and Fourier Transform Raman (FT-Raman) spectra of 2,2‧-bipyridine (2BPE); 4,4‧-bipyridine (4BPE); and 2,4‧-bipyridine (24BPE) were measured in the range 4000-450 cm-1 and 4000-50 cm-1, respectively. Torsional potentials were evaluated at various angles of rotation around the C-C inter-ring bond for the three molecules in order to arrive at the molecular conformation of lowest energy. This conformation was further optimized to get ground state geometry. Vibrational frequencies along with infrared and Raman intensities were computed. In the above calculations, DFT employing B3LYP functional with 6311++G(d,p) basis set was used. The rms error between observed and calculated frequencies was 10.0, 10.9 and 10.2 cm-1 for 2BPE, 4BPE and 24BPE, respectively. A 54-parameter modified valence force field was derived by solving inverse vibrational problem using Wilson's GF matrix method. The force constants were refined using 117 experimental frequencies of the three molecules in overlay least-squares technique. The average error between observed and computed frequencies was 12.44 cm-1. PED and eigen vectors calculated in the process were used to make unambiguous vibrational assignments of all the fundamental vibrations. The values of dipole moment, polarizability and hyperpolarizability were computed to determine the NLO behaviour of these molecules. The HOMO and LUMO energies, thermodynamic parameters and molecular electrostatic surface potentials (MESP) were also evaluated. Stability of the molecules arising from hyper conjugative interactions, charge delocalization have been analyzed using natural bond orbital (NBO) analysis.

  5. A two-dimensional zinc(II) coordination polymer based on mixed dimethyl succinate and bipyridine ligands: synthesis, structure, thermostability and luminescence properties.

    Science.gov (United States)

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

    2016-04-01

    From the viewpoint of crystal engineering, the construction of crystalline polymeric materials requires a rational choice of organic bridging ligands for the self-assembly process. Multicarboxylate ligands are of particular interest due to their strong coordination activity towards metal ions, as well as their various coordination modes and versatile conformations. The structural chemistry of dicarboxylate-based coordination polymers of transition metals has been developed through the grafting of N-containing organic linkers into carboxylate-bridged transition metal networks. A new luminescent two-dimensional zinc(II) coordination polymer containing bridging 2,2-dimethylsuccinate and 4,4'-bipyridine ligands, namely poly[[aqua(μ2-4,4'-bipyridine-κ(2)N:N')bis(μ3-2,2-dimethylbutanedioato)-κ(4)O(1),O(1'):O(4):O(4');κ(5)O(1):O(1),O(4):O(4),O(4')-dizinc(II)] dihydrate], {[Zn2(C6H8O4)2(C10H8N2)(H2O)]·2H2O}n, has been synthesized under hydrothermal conditions and characterized by single-crystal X-ray diffraction and elemental, IR and thermogravimetric analyses. In the structure, the 2,2-dimethylsuccinate ligands link linear tetranuclear Zn(II) subunits into one-dimensional chains along the c axis. 4,4'-Bipyridine acts as a tethering ligand expanding these one-dimensional chains into a two-dimensional layered structure. Hydrogen-bonding interactions between the water molecules (both coordinated and free) and carboxylate O atoms strengthen the packing of the layers. Furthermore, the luminescence properties of the complex were investigated. The compound exhibits a blue photoluminescence in the solid state at room temperature and may be a good candidate for potential hybrid inorganic-organic photoactive materials. PMID:27045181

  6. “Covalent Hydration” Reactions in Model Monomeric Ru 2,2'-Bipyridine Complexes: Thermodynamic Favorability as a Function of Metal Oxidation and Overall Spin States

    Energy Technology Data Exchange (ETDEWEB)

    Ozkanlar, Abdullah; Cape, Jonathan L.; Hurst, James K.; Clark, Aurora E.

    2011-09-05

    Density functional theory (DFT) has been used to investigate the plausibility of water addition to the simple mononuclear ruthenium complexes, [(NH{sub 3}){sub 3}(bpy)Ru=O]{sup 2+}/{sup 3+} and [(NH{sub 3}){sub 3}(bpy)RuOH]{sup 3+}, in which the OH fragment adds to the 2,2{prime}-bipyridine (bpy) ligand. Activation of bpy toward water addition has frequently been postulated within the literature, although there exists little definitive experimental evidence for this type of 'covalent hydration'. In this study, we examine the energetic dependence of the reaction upon metal oxidation state, overall spin state of the complex, as well as selectivity for various positions on the bipyridine ring. The thermodynamic favorability is found to be highly dependent upon all three parameters, with free energies of reaction that span favorable and unfavorable regimes. Aqueous addition to [(NH{sub 3}){sub 3}(bpy)Ru=O]{sup 3+} was found to be highly favorable for the S = 1/2 state, while reduction of the formal oxidation state on the metal center makes the reaction highly unfavorable. Examination of both facial and meridional isomers reveals that when bipyridine occupies the position trans to the ruthenyl oxo atom, reactivity toward OH addition decreases and the site preferences are altered. The electronic structure and spectroscopic signatures (EPR parameters and simulated spectra) have been determined to aid in recognition of 'covalent hydration' in experimental systems. EPR parameters are found to uniquely characterize the position of the OH addition to the bpy as well as the overall spin state of the system.

  7. catena-Poly[[[tetraaquazinc(II]-μ-4,4′-bipyridine-κ2N:N′] benzene-1,4-dicarboxylate

    Directory of Open Access Journals (Sweden)

    Ming-Bo Ruan

    2009-07-01

    Full Text Available In the title compound, {[Zn(C10H8N2(H2O4](C8H4O4}n, the ZnII atoms, lying on a twofold rotation axis, are bridged by 4,4′-bipyridine ligands, resulting in a linear chain along the b axis. In the chain, the ZnII atom adopts a slightly distorted octahedral coordination geometry involving four water molecules at the equatorial positions. The noncoordinated benzene-1,4-dicarboxylate anion, which is also located on a twofold rotation axis, bridges adjacent chains through O—H...O hydrogen bonds, forming a three-dimensional supramolecular network.

  8. (2,2′-Bipyridine-κ2N,N′iodido(piperidine-1-carbodithioato-κ2S,S′copper(II

    Directory of Open Access Journals (Sweden)

    Le-Qing Fan

    2009-01-01

    Full Text Available In the title compound, [Cu(C6H10NS2I(C10H8N2], the CuII ion is coordinated by one iodide ion, two N atoms of the bipyridine ligand and two S atoms from the piperidinecarbodithioate ligand in a distorted square-pyramidal environment. π–π stacking interactions, with centroid–centroid distances of 3.643 (4 Å, between pyridyl rings of the bipyridyl ligands of neighbouring molecules lead to chains propagating parallel to the a axis.

  9. catena-Poly[[(4,4′-dimethyl-2,2′-bipyridine-κ2N,N′cadmium]-di-μ-bromido

    Directory of Open Access Journals (Sweden)

    Sadif A. Shirvan

    2012-12-01

    Full Text Available In the crystal of the title polymeric compound, [CdBr2(C12H12N2]n, the CdII cation is located on a twofold rotation axis and is six-coordinated in a distorted octahedral geometry formed by two N atoms from the 4,4′-dimethyl-2,2′-bipyridine ligand and by four bridging Br− anions. The bridging function of the Br− anions leads to a polymeric chain running along the c axis. Weak C—H...π interactions observed between adjacent chains are effective in the stabilization of the three-dimensional packing.

  10. catena-Poly[[(4,4'-dimethyl-2,2'-bipyridine-κ(2) N,N')cadmium]-di-μ-bromido].

    Science.gov (United States)

    Shirvan, Sadif A; Haydari Dezfuli, Sara; Khazali, Fereydoon; Borsalani, Ali

    2012-12-01

    In the crystal of the title polymeric compound, [CdBr2(C12H12N2)] n , the Cd(II) cation is located on a twofold rotation axis and is six-coordinated in a distorted octa-hedral geometry formed by two N atoms from the 4,4'-dimethyl-2,2'-bipyridine ligand and by four bridging Br(-) anions. The bridging function of the Br(-) anions leads to a polymeric chain running along the c axis. Weak C-H⋯π inter-actions observed between adjacent chains are effective in the stabilization of the three-dimensional packing. PMID:23468712

  11. catena-Poly[[(5,5′-dimethyl- 2,2′-bipyridine-κ2N,N′cadmium(II]-di-μ-chlorido

    Directory of Open Access Journals (Sweden)

    Hamid Reza Khavasi

    2008-10-01

    Full Text Available The asymmetric unit of the title compound, [CdCl2(C12H12N2]n, contains one half-molecule; a twofold rotation axis passes through the Cd atom. The CdII atom is six-coordinated in a distorted octahedral configuration by two N atoms from 2,2′-bipyridine-5,5′-dimethyl and four bridging Cl atoms. The bridging function of the chloro atoms leads to a one-dimensional chain structure. There is a π–π contact between the pyridine rings [centroid–centroid distance = 3.9807 (9 Å].

  12. CuCl-catalyzed aerobic oxidation of 2,3-allenols to 1,2-allenic ketones with 1:1 combination of phenanthroline and bipyridine as ligands

    Directory of Open Access Journals (Sweden)

    Shengming Ma

    2011-04-01

    Full Text Available A protocol has been developed to prepare 1,2-allenyl ketones using molecular oxygen in air or pure oxygen as the oxidant from 2,3-allenylic alcohols with moderate to good yields under mild conditions. In this reaction CuCl (20 mol % with 1,10-phenanthroline (10 mol % and bipyridine (10 mol % was used as the catalyst. It is interesting to observe that the use of the mixed ligands is important for the higher yields of this transformation: With the monoligand approach developed by Markó et al., the yields are relatively lower.

  13. Study on the Interaction of Ternary Complex Pd(Ⅱ)-2,2'-bipyridine-L-asparagic acid with DNA

    Institute of Scientific and Technical Information of China (English)

    高恩君; 赵淑敏; 张丹; 刘祁涛

    2005-01-01

    The ternary complex Pd(Ⅱ)-2,2'-bipyridine-L-asparagic acid was synthesized and characterized by elemental analysis, IR-spectra and molar conductance. The formula of the complex is Pd(bipy)(L-asp). The interaction of the complex with DNA has been studied by UV-spectra, fluorescence spectra, CD-spectra and gel electrophoresis. The results showed that the interaction of the complex with DNA performed mainly in intercalative mode and the extent of interaction was dependent on the concentration of the complex.

  14. (2,2′-Bipyridine-κ2N,N′)[2-tert-butylanilinato(2−)]dichloridooxidomolybdenum(VI) dichloromethane hemisolvate

    OpenAIRE

    Alastair J. Nielson; Waters, Joyce M.

    2010-01-01

    The MoVI atom in the title structure, [Mo(C10H13N)Cl2O(C10H8N2)]·0.5CH2Cl2, has a distorted octahedral coordination sphere with cis-orientated oxide and imide ligands, trans-chloride ligands and the 2,2′-bipyridine (bipy) ligand N atoms lying trans to the oxide and imide ligands. An imide-ligand tert-butyl-methyl-group H atom makes a close approach with the oxide ligand (distance = 2.53 Å) and the imide-ligand N atom (distance = 2.41 Å)...

  15. (2,2′-Bipyridine-κ2N,N′)dibromido(dimethyl sulfoxide-κO)zinc(II)

    OpenAIRE

    Majid Esmhosseini

    2010-01-01

    In the molecule of the title compound, [ZnBr2(C10H8N2)(C2H6OS)], the ZnII atom is five-coordinated in a distorted trigonal–bipyramidal configuration by two N atoms from one 2,2′-bipyridine, one O atom from one dimethylsulfoxide molecule and two Br atoms. Intermolecular π–π stacking between parallel pyridine rings [face-to-face distance 3.32 (4) Å] and C—H...Br and C—H...O hydrogen-bonding interact...

  16. Poly[μ-4,4′-bipyridine-κ2N:N′-μ-thiocyanato-κ2N:S-copper(I)

    OpenAIRE

    Mario Wriedt; Sina Sellmer; Christian Näther

    2008-01-01

    In the crystal structure of the title compound, [Cu(NCS)(C10H8N2)]n, the CuI atom is coordinated by two N atoms from two symmetry-related 4,4′-bipyridine (bipy) ligands and one N and one S atom from two symmetry-related thiocyanate ligands in a distorted tetrahedral environment. The thiocyanate ligands bridge the CuI atoms into a zigzag [CuSCN]n chain running parallel to the a axis. These chains are further connected through two bipy ligands that bridge the CuI centers to generate a two...

  17. catena-Poly[[(5-phenyl-2,2′-bipyridine-κ2N,N′copper(I]-μ-thiocyanido-κ2N:S

    Directory of Open Access Journals (Sweden)

    Shuxin Cui

    2012-02-01

    Full Text Available The title compound, [Cu(NCS(C16H12N2]n, was synthesised under hydrothermal conditions. The CuI ion shows distorted tetrahedral geometry being coordinated by two N atoms from a 5-phenyl-2,2′-bipyridine ligand and by the N and S atoms from two different thiocyanate anions. The CuI ions are bridged by thiocyanide groups, forming a one-dimensional coordination polymer along the b axis. The crystal packing is through van der Waals contacts and C—H...π interactions.

  18. Amphiphilic ruthenium bipyridine complex containing long-chain azopyridine group and the mechanism of electron transfer in Langmuir-Blodgett films

    International Nuclear Information System (INIS)

    We synthesized the amphiphilic bis(bipyridine) ruthenium complex [Ru(bipy)2Cl(L)]+ (bipy= 2,2′-bipyridine, L = 4-(4-dodecyloxyphenylazo) pyridine). The long-chain ligand contributed to the self-assembly of the complex at the liquid-air interface, enabling its deposition by the Langmuir-Blodgett technique. The UV-vis, Raman, and specular reflectance FTIR spectroscopies revealed the molecular organization in the LB films: in the free ligand LB film the alkoxyphenylazopyridine species were oriented in parallel to each other and parallel to the normal plane of the substrate, whilst in the ruthenium complex film the alkoxyphenylazopyridine species were oriented in parallel to each other and perpendicular to the normal plane of the substrate. We then prepared multilayer films consisting of layers of ligand L supporting a monolayer of the ruthenium complex and characterized them by electrochemistry. This hybrid film structure led to optimal orientation of the ruthenium centers for electrochemical response. The results indicated that the phenylazo low-lying π-orbital participated in the hopping mechanism that mediated the electron transfer in the LB films with few molecular layers

  19. A Novel 3D Supramolecular Network Constructed from [Cu(4,4'-bipyridine)(O2CMe)2]2 Molecular Ladders by Hydrogen Bonding

    Institute of Scientific and Technical Information of China (English)

    YANG E; WANG Xiao-Qin; QIN Ye-Yan

    2006-01-01

    The title complex, {[Cu2(4,4'-bipyridine)2(μ-O2CMe)2(O2CMe)2](H2O}n 1, was synthesized and structurally characterized by X-ray crystallography. It crystallizes in monoclinic, space group C2/c with a = 13.4474(5), b = 11.7566(2), c = 19.5380(6) (A), β = 92.930(2)°, V = 3084.84(16) (A)3, Z = 4, Cu2C28N4O9H30, Mr = 693.64, Dc = 1.494 g/cm3, F(000) = 1424 and μ(MoKa) = 1.436 mm-1. With the use of 2062 observed reflections (Ⅰ>2σ(Ⅰ)), the structure was refined to R = 0.0769 and wR = 0.2154. In complex 1, the dimeric copper acetate units are linked through 4,4'-bipyridine to yield 1D molecular ladders. These ladders are connected via O-H···O hydrogen bonds to generate 2D layers, which are further linked through C-H···O hydrogen bonds to give a 3D supramolecular network.

  20. Synthesis, structure and photoluminescence of (PLAGH)2[ZnCl4] and comparative analysis of photoluminescence properties with tris(2,2′-bipyridine)ruthenium(II)

    International Nuclear Information System (INIS)

    Highlights: • New zinc(II) complex with pyridoxalaminoguanidine was synthesized. • The enhancement of the photoluminescence due to the compound formation was achieved. • Very high photoluminescence of Zn(II) compound was noticed. • Comparative analysis of photoluminescence with tris(2,2′-bipyridine) ruthenium(II) was provided. - Abstract: The first compound of zinc(II) containing pyridoxalaminoguanidine has been synthesized and characterized by elemental analysis, infrared spectra, conductometric measurements and X-ray crystallography. Single crystals of the compound were obtained in the reaction of methanolic solution of zinc(II) chloride and pyridoxalaminoguanidine hydrochloride. In this compound the coordination of chelate ligand is absent and tetrachlorido complex of zinc(II) with pyridoxalaminuguanidinium cation as contraion is obtained. Photoluminescence spectra were measured. Lorentzian multipeak technique was used to determine peak wavelengths and their intensities. Photoluminescence spectroscopy upon 325, 488 and 514 nm laser excitation light was used to obtain results. This novel compound of zinc(II) was compared to the well-known organic light emitting diode material—ruthenium(II) complex with bypiridine i.e., tris(2,2′-bipyridine)ruthenium(II), under the same circumstances and the identical experimental setup. A scheme of energy levels and transitions is proposed to explain the obtained experimental results

  1. Bis(2,2′-bipyridine-κ2N,N′(maleato-κ2O1,O1′nickel(II 7.34-hydrate

    Directory of Open Access Journals (Sweden)

    Klaus Harms

    2008-12-01

    Full Text Available The title compound, [Ni(C4H2O4(C10H8N22]·7.34H2O, was obtained by crystallization from an aqueous ethanolic reaction mixture containing nickel(II acetate, maleic acid, bipyridine, sodium hydroxide and ammonia. The asymmetric unit contains one independent complex molecule and 7.34 water molecules occupying eight crystallographically independent positions. Two of these water molecules are disordered. The nickel(II atom is coordinated in a distorted octahedral geometry by two O atoms from one carboxylate group of the maleato ligand and by four N atoms from two 2,2′-bipyridine (bipy ligands. The water molecules, along with the O atoms of the uncoordinated carboxylate group, form an extended hydrophilic three-dimensional hydrogen-bonded system with large cavities in which the hydrophobic bipy ligands are located. One H atom of the maleate ligand is involved in a weak hydrogen bond of the C—H...O type. Stacking interactions between the pyridyl rings of the bipy ligands [centroid–centroid distance = 3.549 (15 Å] lead to the formation of pairs of complex molecules.

  2. Tris(2,2'-bipyridine)ruthenium Derivatives with Multiple Viologen Acceptors: Quadratic Dependence of Photocatalytic H2 Evolution Rate on the Local Concentration of the Acceptor Site.

    Science.gov (United States)

    Kitamoto, Kyoji; Sakai, Ken

    2016-08-22

    Three Ru(bpy)3 (2+) derivatives tethered to multiple viologen acceptors, [Ru(bpy)2 (4,4'-MV2)](6+) , [Ru(bpy)2 (4,4'-MV4)](10+) , and [Ru(bpy)(4,4'-MV4)2 ](18+) [bpy=2,2'-bipyridine, 4,4'-MV2=4-ethoxycarbonyl-4'-(N-G1 -carbamoyl)-2,2'-bipyridine, and 4,4'-MV4=4,4'-bis(N-G1 -carbamoyl)-2,2'-bipyridine, where G1 =Asp(NHG2 )-NHG2 and G2 =-(CH2 )2 -N(+) C5 H4 -C5 H4 N(+) -CH3 ] were prepared as "photo-charge separators (PCSs)". Photoirradiation of these complexes in the presence of a sacrificial electron donor (EDTA) results in storage of electrons per PCS values of 1.3, 2.7, and 4.6, respectively. Their applications in the photochemical H2 evolution from water in the presence of a colloidal Pt H2 -evolving catalyst were investigated, and are discussed along with those reported for [Ru(bpy)2 (5,5'-MV4)](10+) , [Ru(4,4'-MV4)3 ](26+) , and [Ru(5,5'-MV4)3 ](26+) (Inorg. Chem. Front. 2016, 3, 671-680). The PCSs with high dimerization constants (Kd =10(5) -10(6)  m(-1) ) are superior in driving H2 evolution at pH 5.0, whereas those with lower Kd values (10(3) -10(4)  m(-1) ) are superior at pH 7.0, where Kd =[(MV(+) )2 ]/[MV(+) (.) ](2) . The (MV(+) )2 site can drive H2 evolution only at pH 5.0 as a result of its 0.15 eV lower driving force for H2 evolution relative to MV(+) (.) , whereas the PCSs with lower Kd values exhibit higher performance at pH 7.0 owing to the higher population of free MV(+) (.) . Importantly, the rate of electron charging over the PCSs is linear to the apparent H2 evolution rate, and shows an intriguing quadratic dependence on the number of MV(2+) units per PCS. PMID:27434613

  3. ITO电极上催化伏安法测定锇联吡啶的研究%Determination of Osmium Bipyridine at ITO Electrode by Catalytic Voltammetry

    Institute of Scientific and Technical Information of China (English)

    邹蕊

    2012-01-01

    An electron transfer mediator osmium bipyridine was synthesized. The electrochemical behaviors of osmi- um bipyridine at ITO electrode were studied and the catalytic reaction kinetics of it in system of glucose/glucose ox- idase was measured. The homogeneous reaction rate constant (Ks ) is 2.07 ×10^-2cm/s, and the first- order reac- tion rate constant (Kf) and second -order reaction rate constant (Kmed) in catalyzed reaction are 1.05 × 10^-3s-1 and 1.57× 10^4 L/( mol. s), respectively. The detection limited is 0. 016 μmol/L. Therefore, as an electrochemical label, osmium bipyridine can be used to construct biosensor for the catalyzed signal amplification.%合成了电子转移介体锇联吡啶Os(bpy)3,采用催化伏安法研究了Os(bpy)3在ITO电极上的电化学行为,并对Os(bpy)3在葡萄糖一葡萄糖氧化酶体系中的催化反应动力学常数进行了测定。Os(bpy)3的均相反应速率常数Ks为2.07×10^-2cm/s,催化反应中一级反应速率常Kf为1.05×10^-3s^-1,二级反应速率常数kmed为1.57×10^4L/(mol.s)。并采用催化伏安法测定Os(bpy)3的检出限为为0.016μmol/L。因此,Os(bpy)3作为电化学标记物,能够用于生物传感器的构建。

  4. Crystal structure of poly[[μ3-4,4′-(4,4′-bipyridine-2,6-diyl)dibenzoato]{μ2-4-[6-(4-carboxyphenyl)-4,4′-bipyridin-4′-ium-2-yl]benzoato}manganese(II)] hemihydrate

    OpenAIRE

    Yaping Li; Dajun Sun; Julia Ming; Liying Han; Guanfang Su

    2014-01-01

    The title compound, {[Mn(C24H14N2O4)(C24H16N2O4)]·0.5H2O}n, was obtained by the reaction of manganese nitrate with the ligand 4,4′-(4,4′-bipyridine-2,6-diyl) dibenzoic acid under hydrothermal conditions. The water O atom is located on a twofold rotation axis. The Mn2+ ion is heptacoordinated by six O atoms and one N atom from the ligands. In this structure, the ligands adopts two different forms, one completely deprotonated and one with a protonated N atom (pyridinium) and a carboxylic acid f...

  5. 4-(2,4-Dichlorophenyl-6-(1H-indol-3-yl-2,2′-bipyridine-5-carbonitrile

    Directory of Open Access Journals (Sweden)

    M. N. Ponnuswamy

    2009-05-01

    Full Text Available The title compound, C25H14Cl2N4, crystallizes with two independent molecules in the asymmetric unit. The two pyridine rings are almost coplanar, making dihedral angles of 3.2 (1 and 8.6 (1° in the two independent molecules. The dichlorophenyl and indole rings are twisted away from the bipyridine ring by 64.32 (5 and 18.46 (4°, respectively in the first molecule and by 51.0 (1 and 27.99 (5°, respectively in the second molecule. The crystal packing is stabilized by C—H...N, C—H...Cl, N—H...N and C—H...π interactions.

  6. (2,2′-Bipyridine-κ2N,N′bromido(1,4,7-trithiacyclononane-κ3S,S′,S′′ruthenium(II hexafluoridophosphate

    Directory of Open Access Journals (Sweden)

    José A. Fernandes

    2011-02-01

    Full Text Available The title compound, [RuBr(C10H8N2(C6H12S3]PF6 or [RuBr(bpy([9]aneS3]PF6 ([9]aneS3 is 1,4,7-trithiacyclononane and bpy is 2,2′-bipyridine, exhibits a very similar octahedral coordination geometry for the Ru2+ atom to that of its [RuCl(bpy([9]aneS3]+ analogue, with only the chloride ligand being substituted by a bromide ligand. The presence of a PF6− anion (alongside with the coordinated bromide ligand promotes the existence of an extensive network of weak C—H...X (X = F, Br interactions.

  7. (4,4')-Bipyridine in Vacuo and in Solvents: A Quantum Chemical Study of a Prototypical Floppy Molecule From a Molecular Transport Perspective

    CERN Document Server

    Bâldea, Ioan; Wenzel, Wonfgang

    2015-01-01

    We report results of quantum chemical calculations for the neutral and anionic species of (4,4{'})-bipyridine (44BPY), a prototypical molecule with a floppy degree of freedom, placed in vacuo and in solvents. In addition to equilibrium geometries and vibrational frequencies and spectra, we present adiabatic energy curves for the vibrational modes with significant intramolecular reorganization upon charge transfer. Special attention is paid to the floppy strongly anharmonic degree of freedom of 44BPY, which is related to the most salient structural feature, namely the twist angle $\\theta$ between the two pyridine rings. The relevance of the present results for molecular transport will be emphasized. We show that the solvent acts as an effective gate electrode and propose a scissor operator to account for solvent effects on molecular transport. Our result on the conductance $G$ vs. $\\cos^2\\theta$ is consistent with a significant transmission in perpendicular conformation indicated by previous microscopic analys...

  8. Synthesis and characterization of a new photoluminescent material (8-hydroxy quinoline) bis (2-2'bipyridine) lanthanum La(Bpy)2q

    Science.gov (United States)

    Kumar, Rahul; Bhargava, Parag

    2016-05-01

    A new photoluminescence material, (8-hydroxy quinoline) bis (2-2'bipyridine) lanthanum has been synthesized and characterized by different techniques. The prepared material La(Bpy)2q was characterized for structural, thermal and photoluminescence analysis. Structural analysis of this material was done by Fourier transformed infrared spectroscopy (FTIR) and mass spectroscopy. Thermal analysis of this material was done by thermal gravimetric analysis (TGA) shows the thermal stability up to 190°C.Absorption and emission spectra of the material was measured by UV-visible spectroscopy and photoluminescence spectroscopy. Solution of this material La(Bpy)2q in ethanol showed absorption peak at 385nm, which may be attributed due to (π - π*) transitions. The photoluminescence spectra of La(Bpy)2q in ethanol solution showed intense peak at 490 nm

  9. Synthesis, Characterization Studies and Bond Valence Sum (BVS) analysis on 2:1 Adducts involving Zinc(II)dithiocarbamates and 4,4’-Bipyridine

    OpenAIRE

    Arumugam Manohar; Kuppukannu Ramalingam; Kottamalai Karpagavel

    2015-01-01

    2:1 adducts involving [Zn(dtc)2]2 (dtc- = pipdtc-, H10C5NCS-2; dnpdtc-, (H3CCH2CH2)2NCS-2; dedtc-, (H5C2)2NCS-2; dmdtc-, (H3C)2NCS-2; nmedtc-, HOCH2CH2(CH)3NCS-2; deadtc-, (HOCH2CH2)2NCS-2) and 4,4' – bipyridine were prepared and characterized by elemental analyses, IR, UV-Visible, Cyclic voltammetric and thermal studies. IR spectra of the complexes show the reduction in the thioureide stretching frequency due to the increase in coordination around the zinc ion and the resultant increase in e...

  10. Electrogenerated chemiluminescence quenching of Ru(bpy)32+ (bpy=2,2′-bipyridine) in the presence of acetaminophen, salicylic acid and their metabolites

    International Nuclear Information System (INIS)

    Quenching of Ru(bpy) 32+ (bpy=2,2′-bipyridine) coreactant electrogenerated chemiluminescence (ECL) has been observed in the presence of acetaminophen, salicylic acid and related complexes. However, no quenching is observed with the acetylsalicylic acid. In most instances, quenching is observed with 100-fold excess of quencher (compared to ECL luminophore) with complete quenching observed between 10,000 and 100,000 fold excess. Fluorescence and UV–vis experiments coupled with bulk electrolysis support the formation of benzoquinone products upon electrochemical oxidation. The mechanism of quenching may involve the interaction of the electrochemically generated benzoquinone species with (i) the ⁎Ru(bpy)32+ excited state or (ii) highly energetic coreactant radicals. - Highlights: ▶ Efficient quenching of the electrogenerated chemiluminescence is observed. ▶ Acetaminophen, salicylic acid and related compounds can be detected. ▶ The mechanism of quenching involves benzoquinones formed upon electrolysis.

  11. Synthesis and fluorescence properties of Eu(Ⅲ), Tb(Ⅲ) and Sm(Ⅲ) with β-diketone and 2,2'- bipyridine

    Institute of Scientific and Technical Information of China (English)

    LIU Xingwang; JIANG Jiadong; YONG Shengli; GUO Yuwei; YANG Kun; WANG Li

    2012-01-01

    Three new rare earth ternary complexes,RE(PPP)3bpy (RE=Sm3+,Eu3+,Tb3+),were synthcsized by the reaction of 1-phenyl-3-(p-phenylethynylphenyl)-1,3-propanedione (HPPP) and 2,2'-bipyridine(bpy) with rare earth chloride RECl3,respectively,in alcohol solution.The compositions were characterized by means of infrared (IR) spectra,chemical analysis,elemental analysis,and thermodynamic analysis.Luminescent properties of the three complexes were studied.At room temperature,under UV light excitation,the Sm3+,Eu3+ and Tb3+ complexes exhibited characteristic emission of the central ions.The fluorescence spectra showed that the fluorescence emission intensity of Eu3+ complex was the strongest.The narrow strongest emission band of Eu3+ complex was considered to be a valuable material with bright red fluorescence.

  12. (Bipyridine-κ2N,N′chlorido[N-(2-hydroxyethyl-N-isopropyldithiocarbamato-κ2S,S′]zinc(II

    Directory of Open Access Journals (Sweden)

    Fatin Allia Mohamad

    2012-07-01

    Full Text Available The ZnII atom in the title compound, [Zn(C6H12NOS2Cl(C10H8N2], is coordinated by a chelating N-2-hydroxyethyl-N-isopropyldithiocarbamate ligand, a 2,2′-bipyridine ligand and a Cl atom. The resulting ClN2S2 donor set defines a distorted square-pyramidal coordination geometry. Helical supramolecular chains sustained by O—H...S hydrogen bonds and propagating along the b axis feature in the crystal packing. A three-dimensional architecture is stabilized by C—H...O, C—H...S and C—H...Cl interactions.

  13. Poly[μ-4,4′-bipyridine-κ2N:N′-μ-thiocyanato-κ2N:S-copper(I

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    Mario Wriedt

    2008-11-01

    Full Text Available In the crystal structure of the title compound, [Cu(NCS(C10H8N2]n, the CuI atom is coordinated by two N atoms from two symmetry-related 4,4′-bipyridine (bipy ligands and one N and one S atom from two symmetry-related thiocyanate ligands in a distorted tetrahedral environment. The thiocyanate ligands bridge the CuI atoms into a zigzag [CuSCN]n chain running parallel to the a axis. These chains are further connected through two bipy ligands that bridge the CuI centers to generate a two-dimensional brick-like network. The pyridyl planes of the ligands exhibit a dihedral angle of 37.35 (12°.

  14. cis-Bis(2,2'-bipyridine-κN,N')bis-(dimethyl sulfoxide-κO)zinc bis-(tetra-phenyl-borate) dimethyl sulfoxide monosolvate.

    Science.gov (United States)

    Tomyn, Stefania; Gumienna-Kontecka, Elżbieta; Usenko, Natalia I; Iskenderov, Turganbay S; Prisyazhnaya, Elena V

    2011-12-01

    In the mononuclear title complex, [Zn(C(10)H(8)N(2))(2)(C(2)H(6)OS)(2)](C(24)H(20)B)(2)·C(2)H(6)OS, the Zn(II) ion is coordinated by four N atoms of two bidentate 2,2'-bipyridine mol-ecules and by the O atoms of two cis-disposed dimethyl sulfoxide mol-ecules in a distorted octa-hedral geometry. The S atom and the methyl groups of one of the coordinated dimethyl sulfoxide mol-ecules are disordered in a 0.509 (2):0.491 (2) ratio. The crystal packing is stabilized by C-H⋯O hydrogen bonds between the dimethyl sulfoxide solvent mol-ecules and tetra-phenyl-borate anions. PMID:22199567

  15. Coordination Complexes of Decamethylytterbocene with4,4'-Disubstituted Bipyridines: An Experimental Study of Spin Coupling inLanthanide Complexes

    Energy Technology Data Exchange (ETDEWEB)

    Walter, Marc D.; Berg, David J.; Andersen, Richard A.

    2005-12-08

    The paramagnetic 1:1 coordination complexes of (C5Me5)2Ybwith a series of 4,4'-disubstituted bipyridines, bipy-X, where X is Me,tert-Bu, OMe, Ph, CO2Me, and CO2Et have been prepared. All of thecomplexes are paramagnetic and the values of the magnetic susceptibilityas a function of temperature show that these values are less thanexpected for the cation, [(C5Me5)2Yb(III)(bipy-X)]+, which have beenisolated as the cation-anion ion-pairs[(C5Me5)2Yb(III)(bipy-X)]+[(C5Me5)2YbI2]f fnfn where X is CO2Et, OMe andMe. The 1H NMR chemical shifts (293 K) for the methine resonances locatedat the 6,6' site in the bipy-X ring show a linear relationship with thevalues of chiT (300 K) for the neutral complexes which illustrates thatthe molecular behavior does not depend upon the phase with one exception,viz., (C5Me5)2Yb(bipy-Me). Single crystals of the 4,4'-dimethylbipyridinecomplex undergo an irreversible, abrupt first order phase change at 228 Kthat shatters the single crystals. The magnetic susceptibility,represented in a delta vs. T plot, on this complex, in polycrystallineform undergoes reversible abrupt changes in the temperature regime 205 -212 K, which is suggested to be due to the way the individual molec ularunits pack in the unit cell. A qualitative model is proposed thataccounts for the sub-normal magnetic moments in theseytterbocene-bipyridine complexes.

  16. Nonadiabatic molecular dynamics with solvent effects: A LR-TDDFT QM/MM study of ruthenium (II) tris (bipyridine) in water

    International Nuclear Information System (INIS)

    Graphical abstract: The previously developped TDDFT-based nonadiabatic molecular dynamics scheme [E. Tapavicza, I. Tavernelli, U. Rothlisberger, Phys. Rev. Lett. 98 (2007) 023001] is extended to include the coupling of the quantum system with a classically described environment. The resulting LR-TDDFT/MM-TSH approach is applied to the study of the ultrafast relaxation of the photoexcited singlet metal-to-ligand-charge-transfer state (1MLCT) of [Ru(bpy)3]2+ (bpy=2,2’-bipyridine) in water. Highlights: ► LR-TDDFT-based trajectory surface hopping with explicit solvent interactions. ► Excited states energies, forces, and nonadiabatic couplings within LR-TDDFT. ► Study of the ultrafast excited state dynamics of [Ru(bpy)3]2+ in water. - Abstract: The previously derived trajectory-based nonadiabatic molecular dynamics scheme [E. Tapavicza, I. Tavernelli, U. Rothlisberger, Phys. Rev. Lett. 98 (2007) 023001] is extended to include the coupling of the quantum system with a classically described environment. The dynamics is performed using LR-TDDFT energies and forces computed on-the-fly together with the nonadiabatic coupling vectors needed for the propagation of the nuclear coefficients according to Tully’s fewest-switches surface hopping algorithm. The resulting LR-TDDFT-QM/MM approach is applied to the study of the ultrafast relaxation of the photoexcited singlet metal-to-ligand-charge-transfer state (1MLCT) of [Ru(bpy)3]2+ (bpy = 2,2′-bipyridine) in water. The observed intersystem crossing dynamics with the triplet MLCT is in good agreement with available experimental results.

  17. Synthesis and Electrochemical and Photophysical Characterization of New 4,4'-π-Conjugated 2,2'-Bipyridines that are End-Capped with Cyanoacrylic Acid/Ester Groups.

    Science.gov (United States)

    Fingerhut, Anja; Wu, Yanlin; Kahnt, Axel; Bachmann, Julien; Tsogoeva, Svetlana B

    2016-04-20

    Two new functionalized 4,4'-disubstituted 2,2'-bipyridines that were end-capped with cyanoacrylic acid or cyanoacrylic acid ester anchoring groups, which might allow their efficient functionalization on TiO2 or other metal-oxide semiconductor surfaces, have been synthesized and characterized by electrochemical, photophysical, and spectroscopic measurements. The electrochemical and photophysical properties of these 4,4'-disubstituted 2,2'-bipyridines with extended π systems, in particular their LUMO energies, make them promising candidates to build up inorganic-organic hybrid photosensitizers for the sensitization of metal-oxide semiconductors (e.g., TiO2 nanoparticles and/or nanotubes). PMID:27101254

  18. Bis(2,2′-bipyridine-κ2N,N′bis(1H-indole-2-carboxylato-κ2O,O′cadmium–2,2′-bipyridine–water (1/0.5/2

    Directory of Open Access Journals (Sweden)

    Yun-Xia Li

    2011-07-01

    Full Text Available The asymmetric unit of title compound, [Cd(C9H6NO22(C10H8N22]·0.5C10H8N2·2H2O, consists of one complex molecule, one half of an uncoordinated 2,2′-bipyridine molecule and two solvent water molecules. The uncoordinated 2,2′-bipyridine molecule is located on a center of symmetry. Within the complex molecule, the CdII atom is coordinated by four N atoms from two 2,2′-bipyridine ligands and three O atoms from two 1H-indole-2-carboxylate anion ligands, completing a distorted CdN4O3 pentagonal bipyramid. The molecules are assembled into one-dimensional chains along the [100] direction through classical hydrogen bonds (O—H...N, N—H...O and O—H...O. The resulting chains are further connected into two-dimensional supramolecular layers parallel to the (110 direction by intermolecular classical hydrogen bonds (N—H...O and O—H...O from adjacent chains. A three-dimensional supramolecular network is formed via interlayer and O—H...O hydrogen bonds.

  19. Oxovanadium(IV) Compounds of cis-[VOCl(N-N)2]+ (N-N = 4,4'- and 5,5'-dimethyl-2,2'-bipyridine); Crystal Structure and Biological Activity

    International Nuclear Information System (INIS)

    Vanadium(IV) complexes in a general formula of cis-[VOX(N-N)2]0/+1, (X=Cl., OH., SO4-2 and N-N = phen, bipy) have been reported. We considered the methyl-substituted bipyridine analogues, 4,4'-dimethyl-2,2'-bipyridine (4dmbpy) and 5,5'-dimethyl-2,2'-bipyridine (5dmbpy) as ligands since our last studies on cytotoxicity of oxovanadium(IV) exhibited that introduction of a methyl group into N-N ligands causes further enhanced cytotoxicity of the related complex. Totally, two new oxovanadium(IV), [VOCl(4dmbpy)2]·Cl·H2O·C2H5OH (1) and [VOCl(5dmbpy)2]·Cl·H2O·CH3OH (2) were synthesized, proposing anticancer activity of the cationic part of the complexes, as ionic vanadium compounds show to increase membrane permeability with a potential for dose reduction.4 Both complexes were fully characterized by means of elemental analysis, IR and UV-Vis. spectroscopy as well as the X-ray diffraction method. Furthermore their cytotoxicity were assayed in three cell cultures, colorectal adenocarcinoma (Caco-2), colon carcinoma (HT-29) and breast ductal carcinoma (T47D) by means of MTT assay (MTT=3-(4,5-dimethylthiazol-2-yl) 2,5-diphenyl tetrazolium bromide) and the results were compared with cisplatin, an anticancer drugs which shows limited activity on colon and breast cancers

  20. Crystal structures of 2,2′-bipyridin-1-ium 1,1,3,3-tetracyano-2-ethoxyprop-2-en-1-ide and bis(2,2′-bipyridin-1-ium 1,1,3,3-tetracyano-2-(dicyanomethylenepropane-1,3-diide

    Directory of Open Access Journals (Sweden)

    Zouaoui Setifi

    2015-05-01

    Full Text Available In 2,2′-bipyridin-1-ium 1,1,3,3-tetracyano-2-ethoxyprop-2-en-1-ide, C10H9N2+·C9H5N4O−, (I, the ethyl group in the anion is disordered over two sets of atomic sites with occupancies 0.634 (9 and 0.366 (9, and the dihedral angle between the ring planes in the cation is 2.11 (7°. The two independent C(CN2 groups in the anion make dihedral angles of 10.60 (6 and 12.44 (4° with the central propenide unit, and the bond distances in the anion provide evidence for extensive electronic delocalization. In bis(2,2′-bipyridin-1-ium 1,1,3,3-tetracyano-2-(dicyanomethylenepropane-1,3-diide [alternative name bis(2,2′-bipyridin-1-ium tris(dicyanomethylenemethanediide], 2C10H9N2+·C10N62− (II, the dihedral angles between the ring planes in the two independent cations are 7.7 (2 and 10.92 (17°. The anion exhibits approximate C3 symmetry, consistent with extensive electronic delocalization, and the three independent C(CN2 groups make dihedral angles of 23.8 (2, 27.0 (3 and 27.4 (2° with the central plane. The ions in (I are linked by an N—H...N hydrogen bond and the resulting ion pairs are linked by two independent C—H...N hydrogen bonds, forming a ribbon containing alternating R44(18 and R44(26 rings, where both ring types are centrosymmetric. The ions in (II are linked by two independent N—H...N hydrogen bonds and the resulting ion triplets are linked by a C—H...N hydrogen bond, forming a C21(7 chain containing anions and only one type of cation, with the other cation linked to the chain by a further C—H...N hydrogen bond.

  1. SYNTHESIS, CHARACTERIZATION AND ANTIMICROBIAL STUDIES ON MIXED LIGAND COMPLEXES OF CO (II, NI (II AND CU (II WITH ISOXAZOLE SCHIFF BASE AND 1, 10-PHENANTHROLINE/ 2, 2' -BIPYRIDINE LIGANDS Synthese, Charakterisierung und antimikrobiellen STUDIES ON MIXED Ligand-Komplexe von Co (II, Ni (II und Cu (II MIT Isoxazol SCHIFF BASE AND 1, 10-Phenanthrolin / 2, 2 '-Bipyridin-Liganden

    Directory of Open Access Journals (Sweden)

    R.Shakru, N.J.P.Subhashini, Shivaraj

    2011-08-01

    Full Text Available Synthesis, Characterization and antimicrobial studies of Cobalt (II, Nickel (II and Copper (II ternary complexes of mixed ligands with Schiff base derived from 3-amino 5-methyl isoxazole with 2-hydroxy 1-naphthaldehyde and 1, 10-phenanthroline/ 2, 2' bipyridine. The micro analytical, magnetic moment, IR and electronic spectral data analysis have been used to confirm the structure of these complexes, their lower electrical conductance values indicates that all the complexes are non- electrolytes. The magnetic moment values and electronics spectral data of the Co (II and Ni (II complexes further indicates the octahedral geometry and Cu (II complexes are tetragonal geometry. The synthesized compounds have been tested against microorganisms such as (bacillus and pseudomonas bacteria and (R.Saloni and A. niger fungi. A comparative study of the MIC (minimum inhibitory concentration values of the ligands and their complexes indicates that the complexes exhibit higher antimicrobial activity than the free ligand and control.

  2. Crystal structure of poly[[μ3-4,4′-(4,4′-bipyridine-2,6-diyldibenzoato]{μ2-4-[6-(4-carboxyphenyl-4,4′-bipyridin-4′-ium-2-yl]benzoato}manganese(II] hemihydrate

    Directory of Open Access Journals (Sweden)

    Yaping Li

    2014-11-01

    Full Text Available The title compound, {[Mn(C24H14N2O4(C24H16N2O4]·0.5H2O}n, was obtained by the reaction of manganese nitrate with the ligand 4,4′-(4,4′-bipyridine-2,6-diyl dibenzoic acid under hydrothermal conditions. The water O atom is located on a twofold rotation axis. The Mn2+ ion is heptacoordinated by six O atoms and one N atom from the ligands. In this structure, the ligands adopts two different forms, one completely deprotonated and one with a protonated N atom (pyridinium and a carboxylic acid function. In the crystal, N—H...O and O—H...O hydrogen bonds consolidate the packing, forming a three-dimensional framework.

  3. Ruthenium-bipyridine complexes bearing fullerene or carbon nanotubes: synthesis and impact of different carbon-based ligands on the resulting products.

    Science.gov (United States)

    Wu, Zhen-yi; Huang, Rong-bin; Xie, Su-yuan; Zheng, Lan-sun

    2011-09-01

    This paper discusses the synthesis of two carbon-based pyridine ligands of fullerene pyrrolidine pyridine (C(60)-py) and multi-walled carbon nanotube pyrrolidine pyridine (MWCNT-py) via 1,3-dipolar cycloaddition. The two complexes, C(60)-Ru and MWCNT-Ru, were synthesized by ligand substitution in the presence of NH(4)PF(6), and Ru(II)(bpy)(2)Cl(2) was used as a reaction precursor. Both complexes were characterized by mass spectroscopy (MS), elemental analysis, nuclear magnetic resonance (NMR) spectroscopy, infrared spectroscopy (IR), ultraviolet/visible spectroscopy (UV-VIS) spectrometry, Raman spectroscopy, X-ray photoelectron spectroscopy (XPS), thermogravimetric analysis (TGA), and cyclic voltammetry (CV). The results showed that the substitution way of C(60)-py is different from that of MWCNT-py. The C(60)-py and a NH(3) replaced a Cl(-) and a bipyridine in Ru(II)(bpy)(2)Cl(2) to produce a five-coordinate complex of [Ru(bpy)(NH(3))(C(60)-py)Cl]PF(6), whereas MWCNT-py replaced a Cl(-) to generate a six-coordinate complex of [Ru(bpy)(2)(MWCNT-py)Cl]PF(6). The cyclic voltammetry study showed that the electron-withdrawing ability was different for C(60) and MWCNT. The C(60) showed a relatively stronger electron-withdrawing effect with respect to MWCNT. PMID:21769337

  4. Three silver-based complexes constructed from organic carboxylic acid and 4,4‧-bipyridine-like ligands: Syntheses, structures and photocatalytic properties

    Science.gov (United States)

    Wang, Chong-chen; Jing, Huan-ping; Wang, Peng

    2014-09-01

    The reactions of AgNO3 with combinations of 4,4‧-bipyridine (bpy)/1,2-di(4-pyridyl)ethylene (dpe), and 5-aminophthalic acid (H2ap)/2,6-Naphthalenedicarboxylic acid (H2npdc)/4,4‧-stilbenedicarboxylic acid (H2sbdc) in aqueous alcohol/ammonia at room temperature produce crystals of [Ag4(bpy)4](ap)2·11H2O (1), [Ag2(bpy)2](npdc)·2H2O (2) and [Ag2(dpe)1.5(sbdc)0.5](sbdc)0.5·7H2O (3). All complexes 1, 2 and 3 consist of 1D infinite silver-ligand cationic chains, interspersed with organic carboxylate anions that provide charge compensation in the crystal structures. The lattice water molecules are situated among the framework of the crystal structure and show rich hydrogen-bonding interactions, which serve to orientate of the organic carboxylate anions in the crystal packing, while the presence of Ag⋯N and Ag⋯Ag contacts strengthens the frameworks. In addition, complexes 1-3 exhibit good photocatalytic activities for dye decolorization under UV light.

  5. Electrochemiluminescent determination of methamphetamine based on tris(2,2'-bipyridine)ruthenium(II) ion-association in organically modified silicate films

    Energy Technology Data Exchange (ETDEWEB)

    Yi Changqing [Key Laboratory of Analytical Sciences of Ministry of Education, Department of Chemistry, Xiamen University, Xiamen 361005 (China); Tao Yin [Key Laboratory of Analytical Sciences of Ministry of Education, Department of Chemistry, Xiamen University, Xiamen 361005 (China); Wang Bo [Institute of Criminal Science and Technology of Xiamen, Xiamen 361005 (China); Chen Xi [Key Laboratory of Analytical Sciences of Ministry of Education, Department of Chemistry, Xiamen University, Xiamen 361005 (China)]. E-mail: xichen@xmu.edu.cn

    2005-06-13

    Tetramethoxysilane (TMOS) and dimethyldimethoxysilane (DiMe-DiMOS) were used as co-precursor to immobilize poly(p-styrenesulfonate) (PSS), then tris(2,2'-bipyridine)ruthenium(II) (Ru(bpy){sub 3} {sup 2+}) was successfully immobilized on a glass carbon electrode via ion-association. The immobilized Ru(bpy){sub 3} {sup 2+} shows good electrochemical and photochemical activities. Electrochemical and electrochemiluminescence (ECL) characterizations of the organically modified silicates (ORMOSILs) modified film electrodes were made by means of cyclic voltammetry and chronocoulometry. The ORMOSIL films were investigated by atomic force microscopy, scanning electrochemical microscope, tunnelling electrochemical microscope, X-ray photoelectron spectroscopy (XPS), UV-vis spectroscopy and fluorescence spectroscopy. XPS in-depth profiles revealed a homogeneous distribution of Ru(bpy){sub 3} {sup 2+} inside the silica thin layers. The modified electrode was used for the ECL determination of methamphetamine (METH) and showed high sensitivity. Detection limit was 2.0 x 10{sup -7} mol l{sup -1} for METH (S/N = 3) with a linear range from 5.0 x 10{sup -7} to 1.0 x 10{sup -3} mol l{sup -1} (R = 0.986). The relative standard deviation (n = 6) was 1.1% for the determination of 1.0 x 10{sup -5} mol l{sup -1} METH. Furthermore, the Ru(bpy){sub 3} {sup 2+} immobilized modified electrode was applied in the ECL determination of methamphetamine (METH) in scout cases.

  6. Crystal structure of bis(2,2′-bipyridine[N′-(quinolin-2-ylmethylidenepyridine-2-carbohydrazide]ruthenium(II bis(tetrafluoridoborate dichloromethane trisolvate

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    Asami Mori

    2015-02-01

    Full Text Available The title compound, [Ru(C10H8N22(C16H12N4O](BF42·3CH2Cl2, crystallizes with one complex dication, two BF4− counter-anions and three dichloromethane solvent molecules in the asymmetric unit. The central RuII atom adopts a distorted octahedral coordination sphere with two 2,2′-bipyridine (bpy and one quinoline-2-carbaldehyde (pyridine-2-carbonylhydrazone (HL ligand. The hydrazone ligand has a Z form and coordinates to the RuII atom via the amide-O and imine-N atoms, affording a planar five-membered chelate ring, while its pyridine-N and quinoline-N donor atoms in the substituents are non-coordinating. The hydrazone N—H group forms an intramolecular hydrogen bond with the quinoline-N atom. In the crystal, the quinoline moiety of HL shows the shortest π–π stacking interaction with the pyridine substituent of HL in a neighbouring complex, the centroid-to-centroid distance being 3.793 (3 Å.

  7. Tris(bipyridineMetal(II-Templated Assemblies of 3D Alkali-Ruthenium Oxalate Coordination Frameworks: Crystal Structures, Characterization and Photocatalytic Activity in Water Reduction

    Directory of Open Access Journals (Sweden)

    Alla Dikhtiarenko

    2016-02-01

    Full Text Available A series of 3D oxalate-bridged ruthenium-based coordination polymers with the formula of {[ZII(bpy3][MIRu(C2O43]}n (ZII = Zn2+ (1, Cu2+ (3, 4, Ru2+ (5, 6, Os2+ (7, 8; MI = Li+, Na+; bpy = 2,2’-bipyridine and {[ZnII(bpy3](H2O[LiRu(C2O43]}n (2 has been synthesized at room temperature through a self-assembly reaction in aqueous media and characterized by single-crystal and powder X-ray diffraction, elemental analysis, infrared and diffuse reflectance UV–Vis spectroscopy and thermogravimetric analysis. The crystal structures of all compounds comprise chiral 3D honeycomb-like polymeric nets of the srs-type, which possess triangular anionic cages where [ZII(bpy3]2+ cationic templates are selectively embedded. Structural analysis reveals that the electronic configuration of the cationic guests is affected by electrostatic interaction with the anionic framework. Moreover, the MLCT bands gaps values for 1–8 can be tuned in a rational way by judicious choice of [ZII(bpy3]2+ guests. The 3D host-guest polymeric architectures can be used as self-supported heterogeneous photocatalysts for the reductive splitting of water, exhibiting photocatalytic activity for the evolution of H2 under UV light irradiation.

  8. Experimental and theoretical studies on the DNA-binding of cationic yttrium(III) complex containing 2,2‧-bipyridine

    Science.gov (United States)

    Khorasani-Motlagh, Mozhgan; Noroozifar, Meissam; Akbari, Alireza; Mirkazehi-Rigi, Sohaila

    2015-03-01

    The interaction of DNA with [Y(bpy)(OH2)6]+3, where bpy is 2,2‧-bipyridine has been studied at physiological pH in Tris-HCl buffer. Fluorescence and absorption spectroscopy, agarose gel electrophoresis as well as EB quenching experiments are used to study DNA binding of the complex. The results reveal that DNA have the strong ability to bind with Y(III) complex. The binding constant, Kb and the Stern-Volmer quenching constant, KSV are determined. For characterization of the binding mode between the Y(III) complex and DNA various procedures such as: iodide quenching assay, salt effect and thermodynamical investigation are used. The results suggest that minor groove binding should be the interaction mode of complex to DNA. A gel electrophoresis assay demonstrates the ability of the complex to cleave the DNA via oxidative pathway. Electronic structure of [Y(bpy)(OH2)6]+3 was also carried out applying the density functional theory (DFT) method and applied to explain some obtained experimental observations.

  9. Complexation of different transition metals with 4,4'-dimethyl-2,2'-bipyridine: Crystal structure, UV spectra and Hirshfeld surfaces.

    Science.gov (United States)

    Yang, Li-Jing; Liu, Qing-Ling; Wang, Ming-Xin; Gu, Lian-Shuai; Luo, Yang-Hui; Sun, Bai-Wang

    2016-09-01

    Four new complexes, [Co(dmbpy)2(dca)2]·CH3OH (1), [Ni(dmbpy)2(dca)2]·CH3OH (2), [Zn(dmbpy)2(dca)2]·(3) and [Cu(dmbpy)2(OH)2]·5H2O (4) (dca=dicyanamide), derived from 4,4'-dimethyl-2,2'-bipyridine (dmbpy) have been synthesized and characterized by elemental analysis, TGA and single-crystal X-ray diffraction. Crystal structures and Hirshfeld surfaces analysis revealed that the complexes 1-3 were mainly supported by OH⋯N, CH⋯N and π⋯π intermolecular interactions, and for complex 4, the uncoordinated water molecules play a key role in the construction of the 3D stacking motif. UV spectrum measurements demonstrate that all of the complexes show typical metal to ligand charge transfer (MLCT) absorption bands between 301 and 306nm. Moreover, after complexation, the absorption maximum bands about intraligand π→π* transitions similarly show slightly red shift compared to dmbpy ligand, consisting with the DFT calculations. PMID:27176132

  10. Synthesis, Characterization Studies and Bond Valence Sum (BVS analysis on 2:1 Adducts involving Zinc(IIdithiocarbamates and 4,4’-Bipyridine

    Directory of Open Access Journals (Sweden)

    Arumugam Manohar

    2015-06-01

    Full Text Available 2:1 adducts involving [Zn(dtc2]2 (dtc- = pipdtc-, H10C5NCS-2; dnpdtc-, (H3CCH2CH22NCS-2; dedtc-, (H5C22NCS-2; dmdtc-, (H3C2NCS-2; nmedtc-, HOCH2CH2(CH3NCS-2; deadtc-, (HOCH2CH22NCS-2 and 4,4' – bipyridine were prepared and characterized by elemental analyses, IR, UV-Visible, Cyclic voltammetric and thermal studies. IR spectra of the complexes show the reduction in the thioureide stretching frequency due to the increase in coordination around the zinc ion and the resultant increase in electron density. The charge transfer transitions are observed in the region 260 – 320 nm by electronic spectra. Thermal studies show a single stage weight loss. The cyclic voltammetric study on the complexes show an increase of electron density on zinc in the adducts compared to [Zn(dtc2]2. The bond valence sum(BVS analysis shows the values to be close to '2', which is equivalent to the formal oxidation state of zinc in the zinc complexes.

  11. Synthesis and electroluminescence characterization of a new aluminum complex, [8-hydroxyquinoline] bis [2, 2'bipyridine] aluminum Al(Bpy)2q

    Science.gov (United States)

    Rahul, Kumar; Ritu, Srivastava; Punita, Singh

    2016-01-01

    We have synthesized and characterized a new electroluminescent material, [8-hydroxyquinoline] bis [2,2'bipyridine] aluminum. A solution of this material Al(Bpy)2q in toluene showed absorption maxima at 380 nm, which was attributed to the moderate energy (π-π*) transitions of the aromatic rings. The photoluminescence spectrum of Al(Bpy)2q in the toluene solution showed a peak at 518 nm. This material shows thermal stability up to 300 °C. The structure of the device is ITO/F4-TCNQ (1 nm)/α-NPD (35 nm)/Al(Bpy)2q (35 nm)/ BCP (6 nm)/Alq3 (28 nm)/LiF (1 nm)/Al (150 nm). This device exhibited a luminescence peak at 515 nm (CIE coordinates, x = 0.32, y = 0.49). The maximum luminescence of the device was 214 cd/m2 at 21 V. The maximum current efficiency of OLED was 0.12 cd/A at 13 V and the maximum power efficiency was 0.03 lm/W at 10 V.

  12. Redetermined structure of 4,4'-bi-pyridine-1,4-phenyl-enedi-acetic acid (1/1) co-crystal.

    Science.gov (United States)

    Paul, Rima; Bora, Sanchay Jyoti

    2015-10-01

    The asymmetric unit of the title 1:1 co-crystal, C10H8N2·C10H10O4, consists of one half-mol-ecule each of 4,4'-bi-pyridine and 1,4-phenyl-enedi-acetic acid: the complete mol-ecules are generated by crystallographic inversion centres. The dihedral angle between the -CO2H group and the benzene ring in the diacid is 73.02 (7)°. In the crystal, the components are linked by O-H⋯N hydrogen bonds, generating [1-2-1] chains of alternating amine and carb-oxy-lic acid mol-ecules. The chains are cross-linked by C-H⋯O inter-actions. This structure was previously incorrectly described as a (C10H10N2)(2+)·(C10H8O4)(2-) mol-ecular salt [Jia et al. (2009 ▸). Acta Cryst. E65, o2490-o2490]. PMID:26594486

  13. Electrogenerated chemiluminescence quenching of Ru(bpy){sub 3} {sup 2+} (bpy=2,2 Prime -bipyridine) in the presence of acetaminophen, salicylic acid and their metabolites

    Energy Technology Data Exchange (ETDEWEB)

    Haslag, Catherine S. [Department of Chemistry, Missouri State University, Springfield, Missouri 65897 (United States); Richter, Mark M., E-mail: MarkRichter@missouristate.edu [Department of Chemistry, Missouri State University, Springfield, Missouri 65897 (United States)

    2012-03-15

    Quenching of Ru(bpy) {sub 3}{sup 2+} (bpy=2,2 Prime -bipyridine) coreactant electrogenerated chemiluminescence (ECL) has been observed in the presence of acetaminophen, salicylic acid and related complexes. However, no quenching is observed with the acetylsalicylic acid. In most instances, quenching is observed with 100-fold excess of quencher (compared to ECL luminophore) with complete quenching observed between 10,000 and 100,000 fold excess. Fluorescence and UV-vis experiments coupled with bulk electrolysis support the formation of benzoquinone products upon electrochemical oxidation. The mechanism of quenching may involve the interaction of the electrochemically generated benzoquinone species with (i) the {sup Low-Asterisk }Ru(bpy){sub 3}{sup 2+} excited state or (ii) highly energetic coreactant radicals. - Highlights: Black-Right-Pointing-Triangle Efficient quenching of the electrogenerated chemiluminescence is observed. Black-Right-Pointing-Triangle Acetaminophen, salicylic acid and related compounds can be detected. Black-Right-Pointing-Triangle The mechanism of quenching involves benzoquinones formed upon electrolysis.

  14. μ-Oxido-bis-[chlorido(4,4'-di-tert-butyl-2,2'-bipyridine-κN,N')dioxido-molybdenum(VI)] 0.2-hydrate.

    Science.gov (United States)

    Gomes, Ana C; Fernandes, José A; Gamelas, Carla A; Gonçalves, Isabel S; Almeida Paz, Filipe A

    2011-12-01

    The title hydrate, [Mo(2)Cl(2)O(5)(C(18)H(24)N(2))(2)]·0.2H(2)O, has been isolated as the oxidation product of [Mo(η(3)-C(3)H(5))Cl(CO)(2)(di-t-Bu-bipy)] (where di-t-Bu-bipy is 4,4'-di-tert-butyl-2,2'-bipyridine). A μ-oxide ligand bridges two similar MoCl(di-t-Bu-bipy)O(2) units, having the terminal oxide ligands mutually cis, and the chloride and μ-oxide trans to each other. In the binuclear complex, the coordination geometries of the metal atoms can be described as highly distorted octa-hedra. Individual complexes co-crystallize with a partially occupied water mol-ecule of crystallization (occupancy factor = 0.20; H atoms not located), with the crystal packing being mediated by the need to effectively fill the available space. A number of weak C-H⋯O and C-H⋯Cl inter-actions are present. PMID:22199539

  15. (2,2′-Bipyridine-κ2N,N′[2-tert-butylanilinato(2−]dichloridooxidomolybdenum(VI dichloromethane hemisolvate

    Directory of Open Access Journals (Sweden)

    Alastair J. Nielson

    2010-12-01

    Full Text Available The MoVI atom in the title structure, [Mo(C10H13NCl2O(C10H8N2]·0.5CH2Cl2, has a distorted octahedral coordination sphere with cis-orientated oxide and imide ligands, trans-chloride ligands and the 2,2′-bipyridine (bipy ligand N atoms lying trans to the oxide and imide ligands. An imide-ligand tert-butyl-methyl-group H atom makes a close approach with the oxide ligand (distance = 2.53 Å and the imide-ligand N atom (distance = 2.41 Å. Another imide-ligand tert-butyl-methyl-group H atom makes a close approach to a chloride ligand (distance = 2.82 Å. One bipy-ligand α-H atom makes a close approach to the oxide ligand (distance = 2.4 Å and the other α-H atom makes a close approach to the imide-ligand phenyl-ring ortho-H atom (distance = 2.52 Å. These close approaches suggest the presence of weak intramolecular hydrogen bonds. The solvent molecule has been modelled under consideration of half-occupancy.

  16. The kinetics of substitution reaction of oxydiacetate and thiodiacetate copper(II) complexes with 1,10-phenanthroline and 2,2’-bipyridine

    Indian Academy of Sciences (India)

    Joanna Pranczk; Dagmara Jacewicz; Dariusz Wyrzykowski; Aleksandra Tesmar; Lech Chmurzyński

    2015-10-01

    The kinetics of substitution reactions of the CuODA and CuTDA binary complexes (ODA = oxydiacetate, TDA = thiodiacetate) with 1,10-phenanthroline (phen) and 2,2’-bipyridine (bipy) were studied in aqueous and DMSO solutions. These reactions were monitored spectrometrically using the stopped-flow method in the UV range. The studies were carried out at three temperatures - 298.15, 303.15 and 308.15 K. The concentrations of the binary complexes were kept within the range of 0.2–0.5 mmol L−1, whereas the concentration of phen or bipy was constant = 0.05 mmol L−1. The values of the reaction rate constants were calculated based on the A → B reaction model. A linear relationship of the rate of the substitution reaction versus the concentration of the binary complex as well as temperature was observed. The impact of the type of the primary (ODA and TDA) and auxiliary ligands (phen and bipy) as well as the effect of solvent on the rate of substitution reaction have been discussed.

  17. Preparation, physicochemical analysis and molecular modeling investigation of 2,2‧-Bipyridine: β-Cyclodextrin inclusion complex in solution and solid state

    Science.gov (United States)

    Periasamy, R.; Kothainayaki, S.; Sivakumar, K.

    2015-11-01

    Supramolecular interaction between 2,2‧-Bipyridine (BPY) and β-Cyclodextrin (β-CD) has been investigated in solution and solid state. Non-covalent interaction between BPY and β-CD was studied in solution using absorption and fluorescence spectroscopy. Inclusion complex of BPY and β-CD was prepared in solid state by co-precipitation method and it was characterized using Fourier Transform Infra-red spectroscopy (FT-IR), Thermal analysis, Scanning Electron Microscopy (SEM), Powder X-ray diffractometry (XRD) and Atomic Force Microscopy (AFM). Binding constant values and 1:1 stoichiometry of the inclusion complex were calculated using Benesi-Hildebrand plots at 303 K. Using continuous variation method the 1:1 stoichiometry has been confirmed for BPY: β-CD complex. Thermodynamic parameter, ΔG of inclusion complex formation was determined and the negative value indicated that the inclusion process was an exergonic and spontaneous process. The most probable model of BPY: β-CD inclusion complex suggested by molecular docking studies was in good agreement with the results obtained by experimental methods.

  18. Hydrothermal Synthesis, Crystal Structure and Magnetic Properties of a Cobalt(Ⅱ) Coordination Polymer Assembled by 4-Sulfophthalate and 4,4'-Bipyridine

    Institute of Scientific and Technical Information of China (English)

    WANG Qing-Wei; LI Xiu-Mei; HAN Jing

    2006-01-01

    A novel metal-organic coordination polymer {[Co2(4-sphth)2(4,4'-bpy)4(H2O)4]- [Co(4,4'-bpy)2(H2O)4]}n (4-sphth = 4-sulfophthalic acid, 4,4'-bpy = 4,4'-bipyridine) 1 has been hydrothermally synthesized and structurally characterized by single-crystal X-ray diffraction, elemental analyses, IR spectroscopy, and magnetic susceptibility measurements. The complex crystallizes in monoclinic, space group C2/c with a = 18.893(6), b = 23.080(7), c = 22.473(7) (A), β = 107.311(4)o, V = 9356(5) (A)3, C76H70Co3N12O22S2, Mr = 1744.35, Dc = 1.238 g/cm3, μ(MoKα) = 0.640 mm(1, F(000) = 3596, Z = 4, the final R = 0.0444 and wR = 0.0846 for 9178 observed reflections (Ⅰ>2б(Ⅰ)). It exhibits a novel three-dimensional supramolecular network formed by hydrogen-bonding and π-π interactions. Variable-temperature magnetic measure shows an overall anti-ferromagnetic behavior for compound 1.

  19. Exploring the Mechanism of Ultrafast Intersystem Crossing in Rhenium(I) Carbonyl Bipyridine Halide Complexes: Key Vibrational Modes and Spin-Vibronic Quantum Dynamics.

    Science.gov (United States)

    Harabuchi, Yu; Eng, Julien; Gindensperger, Etienne; Taketsugu, Tetsuya; Maeda, Satoshi; Daniel, Chantal

    2016-05-10

    The mechanism of ultrafast intersystem crossing in rhenium(I) carbonyl bipyridine halide complexes Re(X)(CO)3(bpy) (X = Cl, Br, I) is studied by exploring the structural deformations when going from Franck-Condon (FC) to critical geometries in the low-lying singlet and triplet excited states and by selecting the key vibrational modes. The luminescent decay observed in [Re(Br)(CO)3(bpy)] is investigated by means of wavepacket propagations based on the multiconfiguration time-dependent Hartree (MCTDH) method. The dominant coordinates underlying the nonradiative decay process are extracted from minima, minimum energy seam of crossing (MESX) and minimum energy conical intersection (MECI) geometries obtained by the seam model function (SMF)/single-component artificial force induced reaction (SC-AFIR) approach. By choosing the normal modes used in MCTDH from the MECI and MESX geometries, not only the degenerate energy points but also the low-energy-gap regions are included. For this purpose a careful vibrational analysis is performed at each critical geometry and analyzed under the light of the pertinent nonadiabatic coupling terms obtained from the linear vibronic coupling (LVC) model augmented by spin-orbit coupling (SOC) in the electronic diabatic representation. PMID:27045949

  20. Characterization of the low-oxidation-potential electrogenerated chemiluminescence of tris(2,2'-bipyridine)ruthenium(II) with tri-n-propylamine as coreactant

    Energy Technology Data Exchange (ETDEWEB)

    Zu Yanbing [Department of Chemistry, University of Hong Kong, Pokfulam, Hong Kong (China)]. E-mail: ybzu@hku.hk; Li Feng [Department of Chemistry, University of Hong Kong, Pokfulam, Hong Kong (China)

    2005-09-26

    The electrogenerated chemiluminescence (ECL) of the Ru(bpy){sub 3} {sup 2+} (bpy, 2,2'-bipyridine)/tri-n-propylamine (TPrA) system can be produced at an oxidation-potential well before the oxidation of Ru(bpy){sub 3} {sup 2+}. Here, we describe the unique features of the low-oxidation-potential (LOP) ECL. The LOP ECL exhibited strong dependence on solution pH with the maximum emission at pH {approx} 7.7. Compared with the conventional ECL, the LOP ECL was much more significantly diminished at high pH (>10), probably due to the short lifetime of TPrA cation radical which is a crucial intermediate for the LOP emission. It was also found that the preceding deprotonation step played an important role in TPrA oxidation at neutral pH and would remarkably influence the emission intensity. As excess intermediate radicals were produced upon rapid TPrA oxidation, only 5 mM TPrA was needed to achieve the maximum LOP ECL intensity in detecting trace Ru(bpy){sub 3} {sup 2+} (<{approx}1 {mu}M) and the LOP ECL response to Ru(bpy){sub 3} {sup 2+} concentration was linear. Compared with the conventional Ru(bpy){sub 3} {sup 2+}/TPrA ECL, the LOP ECL technique not only produces higher emission intensity at lower oxidation-potential, but also significantly reduces the amount of the coreactant.

  1. Characterization of the low-oxidation-potential electrogenerated chemiluminescence of tris(2,2'-bipyridine)ruthenium(II) with tri-n-propylamine as coreactant

    International Nuclear Information System (INIS)

    The electrogenerated chemiluminescence (ECL) of the Ru(bpy)32+ (bpy, 2,2'-bipyridine)/tri-n-propylamine (TPrA) system can be produced at an oxidation-potential well before the oxidation of Ru(bpy)32+. Here, we describe the unique features of the low-oxidation-potential (LOP) ECL. The LOP ECL exhibited strong dependence on solution pH with the maximum emission at pH ∼ 7.7. Compared with the conventional ECL, the LOP ECL was much more significantly diminished at high pH (>10), probably due to the short lifetime of TPrA cation radical which is a crucial intermediate for the LOP emission. It was also found that the preceding deprotonation step played an important role in TPrA oxidation at neutral pH and would remarkably influence the emission intensity. As excess intermediate radicals were produced upon rapid TPrA oxidation, only 5 mM TPrA was needed to achieve the maximum LOP ECL intensity in detecting trace Ru(bpy)32+ (32+ concentration was linear. Compared with the conventional Ru(bpy)32+/TPrA ECL, the LOP ECL technique not only produces higher emission intensity at lower oxidation-potential, but also significantly reduces the amount of the coreactant

  2. Photochemistry and photophysics of a Pd(II) metalloporphyrin: Re(I) tricarbonyl bipyridine molecular dyad and its activity toward the photoreduction of CO2 to CO.

    Science.gov (United States)

    Schneider, Jacob; Vuong, Khuong Q; Calladine, James A; Sun, Xue-Zhong; Whitwood, Adrian C; George, Michael W; Perutz, Robin N

    2011-12-01

    The photochemistry and photophysics of the cationic molecular dyad, 5-{4-[rhenium(I)tricarbonylpicoline-4-methyl-2,2'-bipyridine-4'-carboxyamidyl]phenyl}-10,15,20-triphenylporphyrinatopalladium(II) ([Re(CO)(3)(Pic)Bpy-PdTPP][PF(6)]) have been investigated. The single crystal X-ray structure for the thiocyanate analogue, [Re(CO)(3)(NCS)Bpy-PdTPP], exhibits torsion angles of 69.1(9)°, 178.1(7)°, and 156.8(9)° between porphyrin plane, porphyrin-linked C(6)H(4) group, amide moiety, and Bpy, respectively. Steady-state photoexcitation (λ(ex) = 520 nm) of [Re(CO)(3)(Pic)Bpy-PdTPP][PF(6)] in dimethylformamide (DMF) results in substitution of Pic by bromide at the Re(I)Bpy core. When [Re(CO)(3)(Pic)Bpy-PdTPP][PF(6)] is employed as a photocatalyst for the reduction of CO(2) to CO in DMF/NEt(3) solution with λ(ex) > 420 nm, 2 turnovers (TNs) CO are formed after 4 h. If instead, a two-component mixture of PdTPP sensitizer and mononuclear [Re(CO)(3)(Pic)Bpy][PF(6)] catalyst is used, 3 TNs CO are formed. In each experiment however, CO only forms after a slight induction period and during the concurrent photoreduction of the sensitizer to a Pd(II) chlorin species. Palladium(II) meso-tetraphenylchlorin, the hydrogenated porphyrin analogue of PdTPP, has been synthesized independently and can be substituted for PdTPP in the two-component system with [Re(CO)(3)(Pic)Bpy][PF(6)], forming 9 TNs CO. An intramolecular electron transfer process for the dyad is supported by cyclic voltammetry and steady-state emission studies, from which the free energy change was calculated to be ΔG(ox)* = -0.08 eV. Electron transfer from Pd(II) porphyrin to Re(I) tricarbonyl bipyridine in [Re(CO)(3)(Pic)Bpy-PdTPP][PF(6)] was monitored using time-resolved infrared (TRIR) spectroscopy in the ν(CO) region on several time scales with excitation at 532 nm. Spectra were recorded in CH(2)Cl(2) with and without NEt(3). Picosecond TRIR spectroscopy shows rapid growth of bands assigned to the π-π* excited

  3. Synthesis, crystal structures, and magnetic properties of two three-dimensional octacyanotungstate(Ⅳ)-based bimetallic frameworks with 4,4'-bipyridine dioxide (4,4'-dpdo)

    Institute of Scientific and Technical Information of China (English)

    YUAN Mei; GAO Song; ZHAO Fei; ZHANG Wen; WANG Zhe-Ming

    2009-01-01

    The reaction of [HN(n-C4H9)3]3[WⅤ(CN)8]·4H2O, 4,4'-bipyridine dioxide(4,4'-dpdo), end MnCl2·4H2O or crystallizes in the orthorhombic system, space group P21212 with cell constants α=10.397(2) A, b=11.321(2) A, c=12.295(3) A and Z=2, whereas 2 crystallizes in the monoclinic system, space group P21/c with cell constants a=13.038(3) A, b=13.784(3) A, c=13.225(3) A, β=93.44(3)g and Z=4. In complex 1, each [WⅣ(CN)8]4- unit with a square antiprismatic geometry is connected to four Mn2 dimers through four bridging CN- ions forming wavelike alternating -W-Mn2-W-Mn2- layers, which are further linked through 4,4'-dpdo ligands coordinated to the Mn ions into a three-dimensional open framework. In complex 2, each [WⅣ(CN)8]4- ion still adopts a square antiprismallc geometry, whereas it bonds to seven copper ions through seven CN- ions leading to cage-like undulate layers further bridged by 4,4'-dpdo ligands into a three-dimensional network. Due to the bridging role of the long rigid 4,4"-dpdo ligand, there exist plenty of large cavities in the open frameworks of complexes 1 and 2 occupied by solvent clusters containing H2O or CH3OH molecules. To our knowledge, it is noted that 4,4'-dpdo displays a μ-4,4,4',4' mode, which was first experimentally observed, although predicted before. Magnetic studies show that complex 1 displays an antiferromagnetic coupling between MnⅡ ions, while complex 2 ex-hibits a weak ferromagnetic interaction between CuⅡ ions.

  4. Synthesis and Reactivity of a Cerium(III Scorpionate Complex Containing a Redox Non-Innocent 2,2′-Bipyridine Ligand

    Directory of Open Access Journals (Sweden)

    Fabrizio Ortu

    2015-11-01

    Full Text Available The Ce(III hydrotris(3,5-dimethylpyrazolylborate complex [Ce(TpMe22(κ2-dmpz] (1 (TpMe2 = {HB(dmpz3}−; dmpz = 3,5-dimethylpyrazolide was isolated in fair yield from the reaction of [Ce(I3(THF4] with two equivalents of [K(TpMe2] via the facile decomposition of TpMe2. [Ce(TpMe22(bipy] (2 was synthesized in poor yield by the “one-pot” reaction of [Ce(I3(THF4], bipy (bipy = 2,2′-bipyridine, KC8 and two equivalents of [K(TpMe2] in tetrahydrofuran (THF. The reaction of 2 with N-methylmorpholine-N-oxide produced the known decomposition product [Ce(TpMe2(μ-BOpMe2]2 (3 (BOpMe2 = {HBO(dmpz2}2− in poor yield, presumably by N–O and B–N bond cleavage of a reactive intermediate. The reaction of 2 with trimethylsilylazide gave [Ce(TpMe22(N3] (4 in poor yield; the fate of bipy and the trimethylsilyl group is unknown. Complexes 1–4 were characterized by single crystal XRD, NMR and FTIR spectroscopy and elemental analysis. Complex 2 was additionally probed by UV/Vis/NIR and Electron Paramagnetic Resonance (EPR spectroscopies, Cyclic Voltammetry (CV and magnetometry, which together indicate a formal 4f1 Ce(III center coordinated by a bipy·− radical anion in this system.

  5. Assembly and property research on seven 0D-3D complexes derived from imidazole dicarboxylate and 1,2-bi(pyridin-4-yl)ethene

    Science.gov (United States)

    Mu, Bao; Li, Qian; Lv, Lei; Yang, Dan-Dan; Wang, Qing; Huang, Ru-Dan

    2015-03-01

    The hydrothermal reaction of transition metals, 1H-imidazole-4,5-dicarboxylic acid (H3ImDC) and 1,2-bi(pyridin-4-yl)ethene (bpe) affords a series of new complexes, namely, [Mn(HImDC)(bpe)(H2O)] (1), [M(H2ImDC)2(H2O)2]·(bpe) (M=Fe(2), Co(3), Zn(4), Cd(6)), [Zn3(ImDC)2(bpe)(H2O)]·3H2O (5) and [Cd(H2ImDC)(bpe)] (7), which are characterized by elemental analyses, IR, TG, XRPD and single crystal X-ray diffraction. Complex 1 exhibits a one dimensional (1D) zigzag chain with two types of irregular rings, and the 1D chains are linked to form a three dimensional (3D) supramolecular framework by the hydrogen bonding interactions (O-H•••O and O-H•••N). Complexes 2-4 and 6 are isomorphous, and they display the mononuclear structures. In these complexes, the O-H•••O and O-H•••N hydrogen bonds play an important role in sustaining the whole 3D supramolecular frameworks. Complex 5 shows a (3,3)-connected 3D framework with (103) topology, and the lattice water molecules as guest molecules exist in the 3D framework. Complex 7 is a wave-like two dimensional (2D) structure, in which the adjacent 1D chains point at the opposite directions. Moreover, the fluorescent properties of complexes 1-7 and the magnetic property of 1 have been investigated. The water vapor adsorption for complex 5 has been researched at 298 K.

  6. Ligand field and intermolecular interactions tuning the magnetic properties of spin-crossover Fe(II) polymer with 4,4′-bipyridine

    International Nuclear Information System (INIS)

    A new spin crossover coordination polymer (SCO-CPs) of Fe(II)-4,4′-bipyridine (4,4′-bipy) family: (Fe(4,4′-bipy)2(H2O)2)·(4,4′-bipy)· 8(H2O)·2(ClO4) (3), which displays half spin transitions between 100 and 300 K, has been synthesized and structurally characterized. Compound 3 featured with two-dimensional (2-D) grids connected by hydrogen bonds and π…π packing between one-dimensional (1-D) chains, the 2-D grids expand to three-dimensional (3-D) architecture supported by a “S-shaped holder” involving lattice 4-4′-bipy, water molecules and perchlorate anion. We compared 3 with the other two analogous complexes: ((Fe(4,4′-bipy) (H2O)2 (NCS)2)·4,4′-bipy, 1 and (Fe(4,4′-bipy)2(NCS)2)·mSolv, 2) through Hirshfeld surfaces analysis, which revealed that the low ligand field strength (NCS−) and lone-pair…H contacts contribute to the stabilization of HS (high-spin) state of the Fe(II) ion, while the high ligand field strength (4,4′-bipy) and strong intermolecular contacts (hydrogen bonds and π…π packing interactions) make for the LS (low-spin) state. - Highlights: ●A new member of Fe(||)-4,4′-bipy family has been prepared. ●It displays half spin transitions tuned by ligand field and intermolecular interactions. ●We have made a detailed comparison of this new member with two other analogous complexes

  7. Oxovanadium(IV) Compounds of cis-[VOCl(N-N){sub 2}]{sup +} (N-N = 4,4'- and 5,5'-dimethyl-2,2'-bipyridine); Crystal Structure and Biological Activity

    Energy Technology Data Exchange (ETDEWEB)

    Nasser Ostad, S.; Tavajohi, Shohreh [Univ. of Medical Sciences, Tehran (Iran, Islamic Republic of); Masoomeh Emadi, S.; Amani, Vahid; Abedi, Anita [Islamic Azad Univ., Tehran (Iran, Islamic Republic of)

    2012-11-15

    Vanadium(IV) complexes in a general formula of cis-[VOX(N-N){sub 2}]{sup 0/+1}, (X=Cl., OH., SO{sub 4}{sup -2} and N-N = phen, bipy) have been reported. We considered the methyl-substituted bipyridine analogues, 4,4'-dimethyl-2,2'-bipyridine (4dmbpy) and 5,5'-dimethyl-2,2'-bipyridine (5dmbpy) as ligands since our last studies on cytotoxicity of oxovanadium(IV) exhibited that introduction of a methyl group into N-N ligands causes further enhanced cytotoxicity of the related complex. Totally, two new oxovanadium(IV), [VOCl(4dmbpy){sub 2}]·Cl·H{sub 2}O·C{sub 2}H{sub 5}OH (1) and [VOCl(5dmbpy){sub 2}]·Cl·H{sub 2}O·CH{sub 3}OH (2) were synthesized, proposing anticancer activity of the cationic part of the complexes, as ionic vanadium compounds show to increase membrane permeability with a potential for dose reduction.4 Both complexes were fully characterized by means of elemental analysis, IR and UV-Vis. spectroscopy as well as the X-ray diffraction method. Furthermore their cytotoxicity were assayed in three cell cultures, colorectal adenocarcinoma (Caco-2), colon carcinoma (HT-29) and breast ductal carcinoma (T47D) by means of MTT assay (MTT=3-(4,5-dimethylthiazol-2-yl) 2,5-diphenyl tetrazolium bromide) and the results were compared with cisplatin, an anticancer drugs which shows limited activity on colon and breast cancers.

  8. 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

    2015-08-01

    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.

  9. A hydrostable and twofold interpenetrating three-dimensional zinc-organic framework with rob topology based on 4,4'-oxydibenzoate and 3,3'-dimethyl-4,4'-bipyridine ligands.

    Science.gov (United States)

    Liang, Feng Lan; Ma, De Yun; Qin, Liang

    2016-05-01

    Metal-organic frameworks (MOFs) are a new class of porous materials that have received widespread attention due to their potential applications in gas storage and/or separation, catalysis, luminescence, and so on. The title compound, poly[[(μ2-3,3'-dimethyl-4,4'-bipyridine-κ(2)N:N')bis(μ4-4,4'-oxydibenzoato-κ(4)O:O':O'':O''')dizinc] tetrahydrate], {[Zn2(C14H8O5)2(C12H12N2)]·4H2O}n, has been prepared by the solvothermal assembly of Zn(NO3)2·6H2O, 4,4'-oxydi(benzoic acid) and 3,3'-dimethyl-4,4'-bipyridine. The two Zn(II) atoms adopt the same five-coordinated distorted square-pyramidal geometry (i.e. ZnO4N), bonding to four O atoms from four different 4,4'-oxydibenzoate (oba) ligands and one N atom from a 3,3'-dimethyl-4,4'-bipyridine (dmbpy) ligand. The supramolecular secondary building unit (SBU) is a paddle-wheel [Zn2(COO)4] unit and these units are linked by oba ligands within the layer to form a two-dimensional net parallel to the b axis, with the dmbpy ligands pointing alternately up and down, which is further extended by dmbpy ligands to form a three-dimensional framework with rob topology. The single net leaves voids that are filled by mutual interpenetration of an independent equivalent framework in a twofold interpenetrating architecture. The title compound shows thermal stability up to 673 K and is stable in aqueous solutions in the pH range 5-9. Excitation and luminescence data observed at room temperature show that it emits a bright-blue fluorescence. PMID:27146564

  10. A QSPR Study for the Prediction of the pKa of N-Base Ligands and Formation Constant Kc of Bis(2,2′-bipyridine)Platinum(II)-N-Base Adducts Using Quantum Mechanically Derived Descriptors

    OpenAIRE

    Selami Palaz; Baki Türkkan; Erol Eroğlu

    2012-01-01

    Quantitative structure-property relationship (QSPR) study on the acid dissociation constant, pKa of various 22 N-base ligands including pyridines, pyrimidines, purines, and quinolines has been carried out using Codessa Pro methodology and software. In addition, the formation constant, Kc of these ligands with Pt(II)(bpy)2 2+ (bpy = 2,2′-bipyridine) ion has also been modelled with the same methodology. Linear regression QSPR models of pKa and Kc were established with descriptors derived from A...

  11. Di(isothiocyanato)bis(4-methyl-4’-vinyl-2,2’-bipyridine) Ruthenium(II) Films Deposited on Titanium Oxide-Coated, Fluorine-Doped Tin Oxide for an Efficient Solar Cell

    OpenAIRE

    Liu, Yi; Sugimoto, Ryuichi; Sumi, Katsuhiro

    2013-01-01

    Dye-sensitized titanium oxide electrodes were prepared by immobilizing a novel ruthenium complex, di(isothiocy- anato)bis(4-methyl-4’-vinyl-2,2’-bipyridine)ruthenium(II) [(NCS)_2(mvbpy)_2Ru(II)] or the ruthenium complex/sodium 4-vinylbenzenesulfonate onto the surface of a titanium oxide-coated, fluorine-doped tin oxide (TiO_2/FTO) electrode through a new electrochemically initiated film formation method, in which the electrolysis step and the film deposition step were individually performed. ...

  12. Redox and catalytic properties of new polypyrrole modified electrodes functionalized by [Ru(bpea)(bpy)H2O]2+ complexes; bpea=N,N'-bis(2-pyridylmethyl)ethylamine, bpy=2,2'-bipyridine

    International Nuclear Information System (INIS)

    New ruthenium(II) complexes containing one or two pyrrole-functionalized polypyridylic ligands have been prepared in order to study their electrochemical behaviour in heterogeneous phase, after anodic polymerization from CH2Cl2 solution on an electrode surface. Complexes containing one pyrrole unit have general formula [Ru(bpea-pyr)(bpy)(L)]2+ (bpea-pyr=N-[3-bis(2-pyridylmethyl)aminopropyl]pyrrole, bpy=2,2'-bipyridine, L=Cl, complex 3, or L=H2O, complex 1), whereas compounds having two pyrrole units correspond to [Ru(bpea-pyr)(bpy-pyr)(L)]2+ (bpy-pyr=4-methyl-4'-pyrrolylbutyl-2,2'-bipyridine, L=Cl, complex 4, or L=H2O, complex 2). Upon oxidative polymerization, all complexes form highly stable polypyrrolic films on a graphite disk electrode surface. An electrode modified with complex 2 polypyrrole coating film, C/poly-2, has been tested as heterogeneous catalyst for the oxidation of benzyl alcohol, showing a remarkably high efficiency and notably improving the results obtained with analogous complexes in homogeneous phase

  13. Synthesis, structure and photoluminescence of (PLAGH){sub 2}[ZnCl{sub 4}] and comparative analysis of photoluminescence properties with tris(2,2′-bipyridine)ruthenium(II)

    Energy Technology Data Exchange (ETDEWEB)

    Radanović, Mirjana M. [University of Novi Sad, Faculty of Sciences, Novi Sad (Serbia); Jelić, Miodrag G., E-mail: jelicmgm@uns.ac.rs [University of Novi Sad, Faculty of Technical Sciences, Novi Sad (Serbia); Romčević, Nebojša Ž. [University of Belgrade, Institute of Physics, Belgrade (Serbia); Boukos, Nikos [National Centre for Scientific Research “Demokritos”, Institute of Materials Science, Athens (Greece); Vojinović-Ješić, Ljiljana S.; Leovac, Vukadin M. [University of Novi Sad, Faculty of Sciences, Novi Sad (Serbia); Hadžić, Branka B. [University of Belgrade, Institute of Physics, Belgrade (Serbia); Bajac, Branimir M. [University of Novi Sad, Faculty of Technology, Novi Sad (Serbia); Nađ, Laslo F. [University of Novi Sad, Faculty of Technical Sciences, Novi Sad (Serbia); Chandrinou, Chrysoula [National Centre for Scientific Research “Demokritos”, Institute of Materials Science, Athens (Greece); Baloš, Sebastian S. [University of Novi Sad, Faculty of Technical Sciences, Novi Sad (Serbia)

    2015-10-15

    Highlights: • New zinc(II) complex with pyridoxalaminoguanidine was synthesized. • The enhancement of the photoluminescence due to the compound formation was achieved. • Very high photoluminescence of Zn(II) compound was noticed. • Comparative analysis of photoluminescence with tris(2,2′-bipyridine) ruthenium(II) was provided. - Abstract: The first compound of zinc(II) containing pyridoxalaminoguanidine has been synthesized and characterized by elemental analysis, infrared spectra, conductometric measurements and X-ray crystallography. Single crystals of the compound were obtained in the reaction of methanolic solution of zinc(II) chloride and pyridoxalaminoguanidine hydrochloride. In this compound the coordination of chelate ligand is absent and tetrachlorido complex of zinc(II) with pyridoxalaminuguanidinium cation as contraion is obtained. Photoluminescence spectra were measured. Lorentzian multipeak technique was used to determine peak wavelengths and their intensities. Photoluminescence spectroscopy upon 325, 488 and 514 nm laser excitation light was used to obtain results. This novel compound of zinc(II) was compared to the well-known organic light emitting diode material—ruthenium(II) complex with bypiridine i.e., tris(2,2′-bipyridine)ruthenium(II), under the same circumstances and the identical experimental setup. A scheme of energy levels and transitions is proposed to explain the obtained experimental results.

  14. Di-μ-acetato-κ4O:O′-μ-oxido-κ2O:O′-bis[cis-(2,2′-bipyridine-κ2N,N′-trans-(pyridine-κNruthenium(III] bis(hexafluoridophosphate

    Directory of Open Access Journals (Sweden)

    Akira Nagasawa

    2013-03-01

    Full Text Available The hemerythrin-type dinuclear title complex, [Ru2(CH3COO2O(C10H8N22(C5H5N2](PF62, consists of two RuIII ions with a six-coordinate octahedral geometry, bridged by an oxide and two acetate ligands, with a bidentate 2,2′-bipyridine ligand and a pyridine ligand bonding at terminal positions. The Ru—Ru distance and Ru—O—Ru angle are 3.2838 (3 Å and 121.79 (7°, respectively, and the average Ru—N(pyridine bond length is 2.164 (8 Å. Several C—H...F, C—H...O and C—H...N interactions generate a three-dimensional network in the crystal structure. π–π stacking interactions [centroid–centroid distance = 3.6389 (3 Å] between inversion-related 2,2′-bipyridine rings are also observed.

  15. Comparative solution equilibrium studies on pentamethylcyclopentadienyl rhodium complexes of 2,2'-bipyridine and ethylenediamine and their interaction with human serum albumin.

    Science.gov (United States)

    Enyedy, Éva A; Mészáros, János P; Dömötör, Orsolya; Hackl, Carmen M; Roller, Alexander; Keppler, Bernhard K; Kandioller, Wolfgang

    2015-11-01

    Complex formation equilibrium processes of the (N,N) donor containing 2,2'-bipyridine (bpy) and ethylenediamine (en) with (η(5)-pentamethylcyclopentadienyl)rhodium(III) were investigated in aqueous solution via pH-potentiometry, (1)H NMR spectroscopy, and UV-vis spectrophotometry in the absence and presence of chloride ions. The structure of [RhCp*(en)Cl]ClO4 (Cp*, pentamethylcyclopentadienyl) was also studied by single-crystal X-ray diffraction. pKa values of 8.56 and 9.58 were determined for [RhCp*(bpy)(H2O)](2+) and [RhCp*(en)(H2O)](2+), respectively resulting in the formation of negligible amount of mixed hydroxido complexes at pH 7.4. Stability and the H2O/Cl(-) co-ligand exchange constants of bpy and en complexes considerably exceed those of the bidentate O-donor deferiprone. The strong affinity of the bpy and en complexes to chloride ions most probably contributes to their low antiproliferative effect. Interactions between human serum albumin (HSA) and [RhCp*(H2O)3](2+), its complexes formed with deferiprone, bpy and en were also monitored by (1)H NMR spectroscopy, ultrafiltration/UV-vis and spectrofluorometry. Numerous binding sites (≥ 8) are available for [RhCp*(H2O)3](2+); and the interaction takes place most probably via covalent bonds through the imidazole nitrogen of His. According to the various fluorescence studies [RhCp*(H2O)3](2+) binds on sites I and II, and coordination of surface side chain donor atoms of the protein is also feasible. The binding of the bpy and en complex is weaker and slower compared to that of [RhCp*(H2O)3](2+), and formation of ternary HSA-RhCp*-ligand adducts was proved. In the case of the deferiprone complex, the RhCp* fragment is cleaved off when HSA is loaded with low equivalents of the compound. PMID:26364131

  16. Assembly and property research on seven 0D–3D complexes derived from imidazole dicarboxylate and 1,2-bi(pyridin-4-yl)ethene

    Energy Technology Data Exchange (ETDEWEB)

    Mu, Bao; Li, Qian; Lv, Lei; Yang, Dan-Dan; Wang, Qing; Huang, Ru-Dan, E-mail: huangrd@bit.edu.cn

    2015-03-15

    The hydrothermal reaction of transition metals, 1H-imidazole-4,5-dicarboxylic acid (H{sub 3}ImDC) and 1,2-bi(pyridin-4-yl)ethene (bpe) affords a series of new complexes, namely, [Mn(HImDC)(bpe)(H{sub 2}O)] (1), [M(H{sub 2}ImDC){sub 2}(H{sub 2}O){sub 2}]·(bpe) (M=Fe(2), Co(3), Zn(4), Cd(6)), [Zn{sub 3}(ImDC){sub 2}(bpe)(H{sub 2}O)]·3H{sub 2}O (5) and [Cd(H{sub 2}ImDC)(bpe)] (7), which are characterized by elemental analyses, IR, TG, XRPD and single crystal X-ray diffraction. Complex 1 exhibits a one dimensional (1D) zigzag chain with two types of irregular rings, and the 1D chains are linked to form a three dimensional (3D) supramolecular framework by the hydrogen bonding interactions (O–H∙∙∙O and O–H∙∙∙N). Complexes 2–4 and 6 are isomorphous, and they display the mononuclear structures. In these complexes, the O–H∙∙∙O and O–H∙∙∙N hydrogen bonds play an important role in sustaining the whole 3D supramolecular frameworks. Complex 5 shows a (3,3)-connected 3D framework with (10{sup 3}) topology, and the lattice water molecules as guest molecules exist in the 3D framework. Complex 7 is a wave-like two dimensional (2D) structure, in which the adjacent 1D chains point at the opposite directions. Moreover, the fluorescent properties of complexes 1–7 and the magnetic property of 1 have been investigated. The water vapor adsorption for complex 5 has been researched at 298 K. - Graphical abstract: Seven new complexes based on different structural characteristics have been hydrothermally synthesized by the mixed ligands. The fluorescent properties, the magnetic property and the water vapor adsorption have been investigated. - Highlights: • The semi-rigid ligand with C=C bonds and imidazole dicarboxylates with some advantages have been used. • A series of new complexes with different structural characteristics have been discussed in detail. • The fluorescent properties, the magnetic property and the water vapor adsorption have been

  17. Assembly and property research on seven 0D–3D complexes derived from imidazole dicarboxylate and 1,2-bi(pyridin-4-yl)ethene

    International Nuclear Information System (INIS)

    The hydrothermal reaction of transition metals, 1H-imidazole-4,5-dicarboxylic acid (H3ImDC) and 1,2-bi(pyridin-4-yl)ethene (bpe) affords a series of new complexes, namely, [Mn(HImDC)(bpe)(H2O)] (1), [M(H2ImDC)2(H2O)2]·(bpe) (M=Fe(2), Co(3), Zn(4), Cd(6)), [Zn3(ImDC)2(bpe)(H2O)]·3H2O (5) and [Cd(H2ImDC)(bpe)] (7), which are characterized by elemental analyses, IR, TG, XRPD and single crystal X-ray diffraction. Complex 1 exhibits a one dimensional (1D) zigzag chain with two types of irregular rings, and the 1D chains are linked to form a three dimensional (3D) supramolecular framework by the hydrogen bonding interactions (O–H∙∙∙O and O–H∙∙∙N). Complexes 2–4 and 6 are isomorphous, and they display the mononuclear structures. In these complexes, the O–H∙∙∙O and O–H∙∙∙N hydrogen bonds play an important role in sustaining the whole 3D supramolecular frameworks. Complex 5 shows a (3,3)-connected 3D framework with (103) topology, and the lattice water molecules as guest molecules exist in the 3D framework. Complex 7 is a wave-like two dimensional (2D) structure, in which the adjacent 1D chains point at the opposite directions. Moreover, the fluorescent properties of complexes 1–7 and the magnetic property of 1 have been investigated. The water vapor adsorption for complex 5 has been researched at 298 K. - Graphical abstract: Seven new complexes based on different structural characteristics have been hydrothermally synthesized by the mixed ligands. The fluorescent properties, the magnetic property and the water vapor adsorption have been investigated. - Highlights: • The semi-rigid ligand with C=C bonds and imidazole dicarboxylates with some advantages have been used. • A series of new complexes with different structural characteristics have been discussed in detail. • The fluorescent properties, the magnetic property and the water vapor adsorption have been investigated

  18. Ruthenium nitrosyl complexes with 1,4,7-trithiacyclononane and 2,2'-bipyridine (bpy) or 2-phenylazopyridine (pap) coligands. Electronic structure and reactivity aspects.

    Science.gov (United States)

    De, Prinaka; Maji, Somnath; Chowdhury, Abhishek Dutta; Mobin, Shaikh M; Mondal, Tapan Kumar; Paretzki, Alexa; Lahiri, Goutam Kumar

    2011-12-14

    The present article describes ruthenium nitrosyl complexes with the {RuNO}(6) and {RuNO}(7) notations in the selective molecular frameworks of [Ru(II)([9]aneS(3))(bpy)(NO(+))](3+) (4(3+)), [Ru(II)([9]aneS(3))(pap) (NO(+))](3+) (8(3+)) and [Ru(II)([9]aneS(3))(bpy)(NO˙)](2+) (4(2+)), [Ru(II)([9]aneS(3))(pap)(NO˙)](2+) (8(2+)) ([9]aneS(3) = 1,4,7-trithiacyclononane, bpy = 2,2'-bipyridine, pap = 2-phenylazopyridine), respectively. The nitrosyl complexes have been synthesized by following a stepwise synthetic procedure: {Ru(II)-Cl} → {Ru(II)-CH(3)CN} → {Ru(II)-NO(2)} → {Ru(II)-NO(+)} → {Ru(II)-NO˙}. The single-crystal X-ray structure of 4(3+) and DFT optimised structures of 4(3+), 8(3+) and 4(2+), 8(2+) establish the localised linear and bent geometries for {Ru-NO(+)} and {Ru-NO˙} complexes, respectively. The crystal structures and (1)H/(13)C NMR suggest the [333] conformation of the coordinated macrocyclic ligand ([9]aneS(3)) in the complexes. The difference in π-accepting strength of the co-ligands, bpy in 4(3+) and pap in 8(3+) (bpy < pap) has been reflected in the ν(NO) frequencies of 1945 cm(-1) (DFT: 1943 cm(-1)) and 1964 cm(-1) (DFT: 1966 cm(-1)) and E°({Ru(II)-NO(+)}/{Ru(II)-NO˙}) of 0.49 and 0.67 V versus SCE, respectively. The ν(NO) frequency of the reduced {Ru-NO˙} state in 4(2+) or 8(2+) however decreases to 1632 cm(-1) (DFT: 1637 cm(-1)) or 1634 cm(-1) (DFT: 1632 cm(-1)), respectively, with the change of the linear {Ru(II)-NO(+)} geometry in 4(3+), 8(3+) to bent {Ru(II)-NO˙} geometry in 4(2+), 8(2+). The preferential stabilisation of the eclipsed conformation of the bent NO in 4(2+) and 8(2+) has been supported by the DFT calculations. The reduced {Ru(II)-NO˙} exhibits free-radical EPR with partial metal contribution revealing the resonance formulation of {Ru(II)-NO˙}(major)↔{Ru(I)-NO(+)}(minor). The electronic transitions of the complexes have been assigned based on the TD-DFT calculations on their DFT optimised structures. The

  19. New ruthenium nitrosyl complexes with tris(1-pyrazolyl)methane (tpm) and 2,2'-bipyridine (bpy) coligands. Structure, spectroscopy, and electrophilic and nucleophilic reactivities of bound nitrosyl.

    Science.gov (United States)

    Videla, Mariela; Jacinto, Julian S; Baggio, Ricardo; Garland, María T; Singh, Priti; Kaim, Wolfgang; Slep, Leonardo D; Olabe, José A

    2006-10-16

    The new compound [Ru(bpy)(tpm)NO](ClO4)3 [tpm = tris(1-pyrazolyl)methane; bpy = 2,2'-bipyridine] has been prepared in a stepwise procedure that involves the conversion of [Ru(bpy)(tpm)Cl]+ into the aqua and nitro intermediates, followed by acidification. The diamagnetic complex crystallizes to exhibit distorted octahedral geometry around the metal, with the Ru-N(O) bond length 1.774(12) A and the RuNO angle 179.1(12) degrees , typical for a {RuNO}6 description. The [Ru(bpy)(tpm)NO]3+ ion (I) has been characterized by 1H NMR and IR spectroscopies (nu(NO) = 1959 cm(-1)) and through density functional theory calculations. Intense electronic transitions in the 300-350-nm region are assigned through time-dependent (TD)DFT as intraligand pi --> pi for bpy and tpm. The dpi --> pi(bpy) metal-to-ligand charge-transfer transitions appear at higher energies. Aqueous cyclic voltammetric studies show a reversible wave at 0.31 V (vs Ag/AgCl, 3 M Cl-), which shifts to 0.60 V in MeCN, along with the onset of a wave of an irreversible process at -0.2 V. The waves are assigned to the one- and two-electron reductions centered at the NO ligand, leading to species with {RuNO}(7) and {RuNO}(8) configurations, respectively. Controlled potential reduction of I in MeCN led to the [Ru(bpy)(tpm)NO]2+ ion (II), revealing a significant downward shift of nu(NO) to 1660 cm(-1) as well as changes in the electronic absorption bands. II was also characterized by electron paramagnetic resonance, showing an anisotropic signal at 110 K that arises from an S = 1/2 electronic ground state; the g-matrix components and hyperfine coupling tensor resemble the behavior of related {RuNO}7 complexes. Both I and II were characterized through their main reactivity modes, electrophilic and nucleophilic, respectively. The addition of OH- into I generated the nitro complex, with k(OH) = 3.05 x 10(6) M(-1) s(-1) (25 degrees C). This value is among the highest obtained for related nitrosyl complexes and correlates

  20. (2,2′-Bipyridine-κ2N,N′{[(3-methoxy-2-oxidobenzylidene-κO2hydrazono]methanolato-κ2N2,O}dimethyltin(IV

    Directory of Open Access Journals (Sweden)

    Islam Ullah Khan

    2008-04-01

    Full Text Available In the crystal structure of the title compound, [Sn(CH32(C9H8N2O3(C10H8N2], the Sn atom exhibits a pentagonal bipyramidal coordination geometry defined by two C, three N and two O atoms. The bond distances for Sn—C, Sn—N and Sn—O are in the ranges 2.097 (3–2.098 (3, 2.298 (2–2.623 (2 and 2.157 (2–2.266 (2 Å, respectively. The molecular structure of the monomeric compound is stabilized by three intramolecular C—H...O hydrogen bonds, all involving bipyridine C—H groups.

  1. Magnetic properties of S= 1/2 J1-J2 one-dimensional magnets, VO(XO4)(2,2'-bpy) (X=S, Mo; bpy = bipyridine)

    International Nuclear Information System (INIS)

    Magnetic susceptibility, high field magnetization and specific heat of S = 1/2 J1-J2 spin chain compounds VO(XO4)(2,2'-bpy) (X=S, Mo; bpy = bipyridine) are measured. VO(SO4)(2,2'-bpy) is found to be a one-dimensional Heisenberg antiferromagnet with J1/kB = 6.5 K and J2 =0. A ratio j = J2/J1 of VO(MoO4)(2,2'-bpy) is estimated to be about 0.2 with J1/kB = 51 K. Spin gap is not observed in both the compounds, which is consistent with the theoretical prediction

  2. Synthesis and Near IR Photoluminescence of Os(II) Bis(2,2'-bipyridine) (3,8-Diarylethynyl-1,10-phemanthroline) Complexes: Anomalous Behavior of the 3,8-Dinitrophenylethynyl-substituted Homologue

    Science.gov (United States)

    Yang, Jinhua; Dass, Amala; Sotiriou-Leventis, Chariklia; Tyson, Daniel S.; Leventis, Nicholas

    2005-01-01

    A large bathochromic shift (50 nm) and emission in the near infrared is observed by attaching arylethynyl groups at the 3,8-positions of the 1,10-phenanthroline ligand (phen) of [Os(bipy)2(phen)]2+ (where bipy = 2,2'-bipyridine). Thus [Os(bipy)2(3,8-di-4-methoxyphenylethynyl-1,10-phenathroline)]2+ emits at 795 nm, while [Os(bipy)2(3,8-diphenylethynyl-1,10-phenanthroline)]2+ emits at 815 nm. According to this trend it would have been expected that [Os(bipy)2(3,8-di-4-nitrophenylethynyl-1,10-phenathroline)]2+ emits farther in the near infrared. Nevertheless, this complex is not photoluminescent because of intramolecular electron transfer quenching of the MLCT excited state by the nitroaromatic group. These results set structural and redox potential standards in the design of near infrared emitters based on [Os(bipy)2(phen)]2+ type complexes.

  3. Synthesis, structural modelling and luminescence of a novel erbium(III) complex with 2,4-nonanedione and 2,2‧-bipyridine ligands for chitosan matrices doping

    Science.gov (United States)

    Martín-Ramos, P.; Chamorro-Posada, P.; Ramos Silva, M.; Pereira da Silva, P. S.; Martín, I. R.; Lahoz, F.; Lavín, V.; Martín-Gil, J.

    2015-03-01

    We report the synthesis, the Sparkle/PM7 semi-empirical quantum model for the ground state geometry and the absorption/luminescent properties of the Er3+ ternary complex [Er(nd)3(bipy)] (where Hnd is 2,4-nonanedione and bipy is 2,2‧-bipyridine). The solid-state electronic absorption spectra and the photoluminescent spectra show long-wavelength 4f-4f transitions which provide a potential use of the compound as a NIR-emitting material for the doping of polymer-based matrices for waveguides or for bio-analytical applications. The dispersion of the novel complex in a biocompatible chitosan film has been assessed.

  4. Poly[[(μ4-benzene-1,3,5-tricarboxylato-κ4O1:O1′:O2:O3bis(2,2-bipyridine-κ2N,N′(μ2-hydroxidodicopper(II] trihydrate

    Directory of Open Access Journals (Sweden)

    Mohamed N. El-kaheli

    2014-07-01

    Full Text Available In the title two-dimensional coordination polymer, {[Cu2(C9H3O6(OH(C10H8N22]·3H2O}n, each of the two independent CuII atoms is coordinated by a bridging OH group, two O atoms from two benzene-1,3,5-tricarboxylate (L ligands and two N atoms from a 2,2- bipyridine (bipy ligand in a distorted square-pyramidal geometry. Each L ligand coordinates four CuII atoms, thus forming a polymeric layer parallel to the bc plane with bipy molecules protruding up and down. The lattice water molecules involved in O—H...· O hydrogen bonding are situated in the inner part of each layer. The crystal packing is consolidated by π–π interactions between the aromatic rings of bipy ligands from neigbouring layers [intercentroid distance = 3.762 (3 Å].

  5. Poly[[aqua(μ2-4,4′-bipyridine-κ2N:N′[μ3-3-bromo-2-(carboxylatomethylbenzoato-κ3O1:O1′:O2]cadmium] monohydrate

    Directory of Open Access Journals (Sweden)

    Yangmei Liu

    2012-08-01

    Full Text Available In the title compound, {[Cd(C9H5BrO4(C10H8N2(H2O]·H2O}n, the CdII atom has a distorted octahedral coordination geometry. Two N atoms from two 4,4′-bipyridine (bipy ligands occupy the axial positions, while the equatorial positions are furnished by three carboxylate O atoms from three 3-bromo-2-(carboxylatomethylbenzoate (bcb ligands and one O atom from a water molecule. The bipy and bcb ligands link the CdII atoms into a three-dimensional network. O—H...O hydrogen bonds and π–π interactions between the pyridine and benzene rings [centroid–centroid distance = 3.736 (4 Å] are present in the crystal.

  6. Binary copper(II) and uranyl(VI) complexes of glycocyamine, taurine and pyridoxal and ternary complexes involving 2,2'-bipyridine, 1,10-phenanthroline or nitrilotriacetic acid

    International Nuclear Information System (INIS)

    Chelating tendencies of several biologically important compounds viz. glycocyamine (GCN: N-amidino-aminoethanoic acid) taurine (TRN: 2-aminoethanesulphonic acid) and pyridoxal [PDL: 3-hydroxy-5-(hydroxymethyl)-2-methyl-pyridine-4-carbaldehyde] have been examined by pH-metric titration technique in their binary complex formation with copper(II) and uranyl(VI) ions. The work has further been extended to investigating the ternary complex formation involving 2.2'-bipyridine. 1,10-phenanthroline or nitrilotriacetic acid as a primary and TRN and PDL as secondary ligands. All the experiments were carried out at 250C and at an ionic strength of 0.1M (NaCl04) in aqueous or 50% (v/v) aqueous-ethanol medium according to the suitability of the experimental conditions. Stabilities of ternary complexes as compared to those of the corresponding binary complexes of the secondary ligands have also been discussed. (author)

  7. μ-Oxido-bis[chlorido(4,4′-di-tert-butyl-2,2′-bipyridine-κ2N,N′)dioxidomolybdenum(VI)] 0.2-hydrate

    OpenAIRE

    Gomes, Ana C.; José A. Fernandes; Gamelas, Carla A.; Isabel S. Gonçalves; Almeida Paz, Filipe A.

    2011-01-01

    The title hydrate, [Mo2Cl2O5(C18H24N2)2]·0.2H2O, has been isolated as the oxidation product of [Mo(η3-C3H5)Cl(CO)2(di-t-Bu-bipy)] (where di-t-Bu-bipy is 4,4′-di-tert-butyl-2,2′-bipyridine). A μ-oxide ligand bridges two similar MoCl(di-t-Bu-bipy)O2 units, having the terminal oxide ligands mutually cis, and the chloride and μ-oxide trans to each other. In the binuclear complex, the coordination geometries of the metal atoms can be describe...

  8. (2,2′-Bipyridine-κ2 N,N′)[2-tert-butyl­anilinato(2−)]dichloridooxido­molybdenum(VI) dichloro­methane hemisolvate

    OpenAIRE

    Alastair J. Nielson; Waters, Joyce M.

    2010-01-01

    The MoVI atom in the title structure, [Mo(C10H13N)Cl2O(C10H8N2)]·0.5CH2Cl2, has a distorted octa­hedral coord­ination sphere with cis-orientated oxide and imide ligands, trans-chloride ligands and the 2,2′-bipyridine (bipy) ligand N atoms lying trans to the oxide and imide ligands. An imide-ligand tert-butyl-methyl-group H atom makes a close approach with the oxide ligand (distance = 2.53 Å) and the imide-ligand N atom (distance = 2.41 Å). Another imide-ligand tert-butyl-methyl-group H atom m...

  9. Tuning of Supramolecular Architectures of l-Valine-Containing Dicyanoplatinum(II) 2,2'-Bipyridine Complexes by Metal-Metal, π-π Stacking, and Hydrogen-Bonding Interactions.

    Science.gov (United States)

    Fu, Heidi Li-Ki; Po, Charlotte; He, Hexiang; Leung, Sammual Yu-Lut; Wong, Kam Sing; Yam, Vivian Wing-Wah

    2016-08-01

    A series of newly synthesized dicyanoplatinum(II) 2,2'-bipyridine complexes exhibits self-assembly properties in solution after the incorporation of the l-valine amino units appended with various hydrophobic motifs. These l-valine-derived substituents were found to have critical control over the aggregation behaviors of the complexes in the solution state. On one hand, one of the complexes was found to exhibit interesting circularly polarized luminescence (CPL) signals at low temperature due to the formation of chiral spherical aggregates in the temperature-dependent studies. On the other hand, systematic transformation from less uniform aggregates to well-defined fibrous and rod-like structures via Pt⋅⋅⋅Pt and π-π stacking interactions has also been observed in the mixed-solvent studies. These changes were monitored by UV/Vis absorption, emission, circular dichroism (CD), and CPL spectroscopies, and morphologies were studied by electron microscopy. PMID:27412571

  10. Bis[4-amino-N-(pyrimidin-2-yl-κNbenzenesulfonamidato-κN](4,4′-dimethyl-2,2′-bipyridine-κ2N,N′cadmium dimethylformamide disolvate

    Directory of Open Access Journals (Sweden)

    G. M. Golzar Hossain

    2012-03-01

    Full Text Available In the title compound, [Cd(C10H9N4O2S2(C12H12N2]·2C3H7NO, the CdII ion lies on a twofold rotation axis, is six-coordinated by N atoms, and displays a trigonal–prismatic geometry arising from the two sulfadiazinate ligands and one 4,4′-dimethyl-2,2′-bipyridine ligand. Both ligands are bidentate and coordinate via their N atoms. The O and carbonyl C atoms of the dimethylformamide molecule show disorder and were modelled with two different orientations and with site occupancies of 0.584 (10:0.416 (10. The geometry around the sulfadiazine S atom is distorted tetrahedral. The crystal structure involves N—H...O hydrogen bonds which link molecules into a three-dimensional network. Weak C—H...O hydrogen bonds are also observed.

  11. Photoprocess of molecules encapsulated in porous solids X: Photosensitization of zeolite-Y encapsulated tris(2,2'-bipyridine-nickel-(II)ion by phenosafranine adsorbed onto the external surface of the nanoporous host

    Indian Academy of Sciences (India)

    Karuppannan Senthil Kumar; Sudha T; Paramasivam Natarajan

    2014-07-01

    Tris-(2,2'-bipyridine)-nickel-(II) complex ion encapsulated by zeolite-Y host has been synthesized by ship-in-a-bottle method. Photosensitization of nickel(II) complex (Ni(bpy)$^{2+}_{3}$) in the zeolite host by surface adsorbed phenosafranine dye was investigated by time-resolved fluorescence and absorption spectral measurements. Formation of nickel (II)-complex in the super cage of the host was ascertained by XRD, FTIR, solidstate NMR, diffuse reflectance UV-visible absorption spectroscopic techniques and ICP-OES measurements. Phenosafranine dye adsorbed on the external surface of zeolite-Y shows a decrease in fluorescence intensity with increased loading of the nickel(II) complex in zeolite-Y. Time-resolved emission studies show two excited state lifetimes for the photoexcited phenosafranine dye. Average fluorescence lifetimes of the dye in this case do not change with increase in the loading of the nickel(II) complex. However, relative contribution of short lifetime component increases when the amount of encapsulated nickel(II) complex is increased. The zeolite-Y host containing only bipyridyl ligand shows a marked decrease in fluorescence intensity. Fluorescence lifetimes of the dye however do not change with increased loading of bipyridyl while relative contribution of short lifetime component increases with an increase in the loading of bipyridyl in the host. This observation is interpreted to be due to electron transfer from the excited state of phenosafranine dye to the bipyridine. Picosecond pump-probe investigations confirm that the photoinduced electron transfer occurs from the surfaceadsorbed phenosafranine in the excited state to the nickel(II) complex within zeolite-Y cavity and also to the Ni(bpy)$^{2+}_{3}$ complex in contact with the phenosafranine dye co-adsorbed on the external surface of the host.

  12. Adsorption of gases and vapors on nanoporous Ni2(4,4'-Bipyridine)3(NO3)4 metal-organic framework materials templated with methanol and ethanol: structural effects in adsorption kinetics.

    Science.gov (United States)

    Fletcher, Ashleigh J; Cussen, Edmund J; Bradshaw, Darren; Rosseinsky, Matthew J; Thomas, K Mark

    2004-08-11

    Desolvation of Ni(2)(4,4'-bipyridine)(3)(NO(3))(4).2CH(3)OH and Ni(2)(4,4'-bipyridine)(3)(NO(3))(4).2C(2)H(5)OH give flexible metal-organic porous structures M and E, respectively, which have the same stoichiometry, but subtly different structures. This study combines measurements of the thermodynamics and kinetics of carbon dioxide, methanol, and ethanol sorption on adsorbents M and E over a range of temperatures with adsorbent structural characterization at different adsorbate (guest) loadings. The adsorption kinetics for methanol and ethanol adsorption on porous structure E obey a linear driving force (LDF) mass transfer model for adsorption at low surface coverage. The corresponding adsorption kinetics for porous structure M follow a double exponential (DE) model, which is consistent with two different barriers for diffusion through the windows and along the pores in the structure. The former is a high-energy barrier due to the opening of the windows in the structure, required to allow adsorption to occur, while the latter is a lower-energy barrier for diffusion in the pore cavities. X-ray diffraction studies at various methanol and ethanol loadings showed that the host porous structures E and M underwent different scissoring motions, leading to an increase in unit cell volume with the space group remaining unchanged during adsorption. The results are discussed in terms of reversible adsorbate/adsorbent (host/guest) structural changes and the adsorption mechanism involving hydrogen-bonding interactions with specific surface sites for methanol and ethanol adsorption in relation to pore size and extent of filling. This paper contains the first evidence for individual kinetic barriers to diffusion through windows and pore cavities in flexible porous coordination polymer frameworks. PMID:15291578

  13. Reactivity of thiazolidine-2-thione towards CuI/CuII: Synthesis and structures of [3-(2-thiazolin-2-yl)thiazolidine-2-thione]copper(I) bromide and [bis(2,2′-bipyridine)nitratocopper(II)] nitrate

    Indian Academy of Sciences (India)

    Tarlok S Lobana; Anu Rani; Amanpreet K Jassal; Jerry P Jasinski

    2015-01-01

    Thiazolidine-2-thione (L1,NC3H5S2) reacted with copper(I) bromide in CH3CN under aerobic conditions and transformed through C-S bond cleavage into 3-(2-thiazolin-2-yl)thiazolidine-2-thione (L2, C3H4S2N-C3H4SN). This thio-ligand L2 with CuI ion yielded a three coordinate complex, [3-(2-Thiazolin-2-yl)thiazolidine-2-thione]copper(I)bromide 1a which crystallized in the triclinic system with the space group P1 as reported earlier. Treatment of 1a with bis(diphenylphosphino)methane (dppm) in dichloromethane also formed [3-(2-thiazolin-2-yl)thiazolidine-2-thione]copper(I) bromide 1b but it crystallized into the triclinic system with a new space group, P-1: 296(2) K, a, 7.3890(19); b, 8.473(2); c, 9.491(2) Å; , 70.273(5); , 67.170(5); , 84.949(5)°; R, 6.79%. Reactions of copper(II) nitrate with thiazolidine-2-thione followed by the addition of 2,2′-bipyridine or with 2,2′-bipyridine first followed by the addition of thiazolidine-2-thione, gave blue crystals in both the cases. The x-ray crystallography revealed stoichiometry of the complex formed as: [Cu(2-N,N′-bipy)2(1-ONO2)](NO3) 2, which crystallized in monoclinic crystal system with space group, P21/n(14). Crystal data: 173(2) K, a, 11.318(1), b, 12.160(1), c, 14.967(1) Å; = 98.01(1)°, R, 3.99%; 296(2) K, a, 11.340(5), b, 12.249(5), c, 15.065(6) Å; = 98.04(2)◦, R, 4.09%.

  14. Poly[(μ2-4,4′-bipyridine-κ2N:N′(μ2-2,2-dimethylcyclopentane-1,3-dicarboxylato-κ4O1,O1′:O3,O3′cadmium

    Directory of Open Access Journals (Sweden)

    Xian-Fa Zhang

    2011-11-01

    Full Text Available In the title polymeric compound, [Cd(C9H12O4(C10H8N2]n, the CdII atom is located on a twofold rotation axis and is coordinated by two 4,4′-bipyridine ligands and two 2,2-dimethylcyclopentane-1,3-dicarboxylate ions. The carboxylate ion and the N-heterocycle both function as bridges to link adjacent CdII atoms to result in the formation of a layer structure parallel to (010. The mid-point of the central C—C bond of the 4,4′-bipyridine ligand is located on an inversion center. In the crystal, the carboxylate ion is disordered over a twofold rotation axis in respect of its methyl group and the cyclopentane ring.

  15. Adsorption dynamics of gases and vapors on the nanoporous metal organic framework material Ni2(4,4'-bipyridine)3(NO3)4: guest modification of host sorption behavior.

    Science.gov (United States)

    Fletcher, A J; Cussen, E J; Prior, T J; Rosseinsky, M J; Kepert, C J; Thomas, K M

    2001-10-17

    This study combines measurements of the thermodynamics and kinetics of guest sorption with powder X-ray diffraction measurements of the nanoporous metal organic framework adsorbent (host) at different adsorptive (guest) loadings. The adsorption characteristics of nitrogen, argon, carbon dioxide, nitrous oxide and ethanol and methanol vapors on Ni2(4,4'-bipyridine)3(NO3)4 were studied over a range of temperatures as a function of pressure. Isotherm steps were observed for both carbon dioxide and nitrous oxide adsorption at approximately 10-20% of the total pore volume and at approximately 70% of total pore volume for methanol adsorption. The adsorption kinetics obey a linear driving force (LDF) mass transfer model for adsorption at low surface coverage. At high surface coverage, both methanol and ethanol adsorption follow a combined barrier resistance/diffusion model. The rates of adsorption in the region of both the carbon dioxide and methanol isotherm steps were significantly slower than those observed either before or after the step. X-ray diffraction studies at various methanol loadings showed that the host structure disordered initially but underwent a structural change in the region of the isotherm step. These isotherm steps are ascribed to discrete structural changes in the host adsorbent that are induced by adsorption on different sites. Isotherm steps were not observed for ethanol adsorption, which followed a Langmuir isotherm. Previous X-ray crystallography studies have shown that all the sites are equivalent for ethanol adsorption on Ni2(4,4'-bipyridine)3(NO3)4, with the host structure undergoing a scissoring motion and the space group remaining unchanged during adsorption. The activation energies and preexponential factors for methanol and ethanol adsorption were calculated for each pressure increment at which the linear driving force model was obeyed. There was a good correlation between activation energy and ln(preexponential factor), indicating a

  16. Synthesis, spectral and single crystal X-ray structural studies on bis(2,2’-bipyridinesulphidoM(II (M = Cu or Zn and diaqua 2,2’-bipyridine zinc(IIsulphate dihydrate

    Directory of Open Access Journals (Sweden)

    ARUMUGAM MANOHAR

    2010-08-01

    Full Text Available Reaction of bis(diethanoldithiocarbamatocopper(II, [Cu(deadtc2] and bis(di-n-propyldithiocarbamatozinc(II, [Zn(dnpdtc2] complexes with 2,2’-bipyridine (2,2’-bipy (1:1 ratio in ethanol was investigated. Simple mixing of the reactants in 1:1 ratio resulted in five-coordinated [Cu(2,2’--bipy2S]•CH3CH2OSO3H (1 and [Zn(2,2’-bipy2S]•CH3CH2OSO3H·2H2O (2. Refluxing the reactants and cooling the contents result in the formation of [Zn(2,2’-bipy(H2O2]SO4 (3 and [Cu(2,2’-bipy(H2O2]SO4 (4. Complexes 1 and 2 are monomeric with trigonal bipyramidal geometry. A distorted octahedral environment was observed in complexes 3 and 4. The crystal structure of 4 has already been reported in the literature. Crystal structures of 1, 2 and 3 are reported in this paper. The M–S distances in 1 and 2 are 2.318(1 Å and 2.323 Å, respectively. The N–M–S angles are larger than the N–M–N angles due to the steric requirements.

  17. μ-Oxido-bis[chlorido(4,4′-di-tert-butyl-2,2′-bipyridine-κ2N,N′dioxidomolybdenum(VI] 0.2-hydrate

    Directory of Open Access Journals (Sweden)

    Ana C. Gomes

    2011-12-01

    Full Text Available The title hydrate, [Mo2Cl2O5(C18H24N22]·0.2H2O, has been isolated as the oxidation product of [Mo(η3-C3H5Cl(CO2(di-t-Bu-bipy] (where di-t-Bu-bipy is 4,4′-di-tert-butyl-2,2′-bipyridine. A μ-oxide ligand bridges two similar MoCl(di-t-Bu-bipyO2 units, having the terminal oxide ligands mutually cis, and the chloride and μ-oxide trans to each other. In the binuclear complex, the coordination geometries of the metal atoms can be described as highly distorted octahedra. Individual complexes co-crystallize with a partially occupied water molecule of crystallization (occupancy factor = 0.20; H atoms not located, with the crystal packing being mediated by the need to effectively fill the available space. A number of weak C—H...O and C—H...Cl interactions are present.

  18. Bis (4,4′-dimethyl-2,2′-bipyridine) ruthenium (Ⅱ) Complexes Containing 2-Arylimidazo- [4,5-f ] [ 1,10 ] phenanthroline: Syntheses, Characterization and Third-order Nonlinear Optical Properties

    Institute of Scientific and Technical Information of China (English)

    CHAO,Hui(巢晖); LI,Rrn-Hua(李润华); HUANG,Qi-Wen(黄绮雯); JI,Liang-Nian(计亮年)

    2002-01-01

    Four novel mononuclear ruthenium(Ⅱ) complexes [ Ru(dmb)2L]2+ [dmp = 4,4′-dimethyl-2,2′-bipyridine, L = imidazo-[4,5-f][1,10]phenanthroline(IP), 2-phenylimidazo-[4,5-f][1,10]phenanthroline(PIP),2-(4′-hydroxyphenyl)imidazo-[4,5-f][1, 10]phenanthroline(HOP), 2-(4′-dimethylaminophenyl) imidazo-[4, 5-f] [1, 10] phenanthroline(DMNP)]were synthesized and characterized by ES-MS,1H NMR,UVvis and electrochemistry.The nonlinear optical properties of the ruthenium(Ⅱ) complexes were investigated by Z-scan techniques with 12 ns laser pulse at 540nm,and all of them exhibitboth nonlinear optical (NLO)absorption and self-defocusing effect. The corresponding effective NLO susceptibility |x3|of the complexes is in the range of 2.68×10-12 -4.57×10-12esu.

  19. catena-Poly[[(diaquacalcium-bis(μ-2-fluorobenzoato-1′:1κ3O:O,O′;1:1′′κ3O,O′:O] 2,2′-bipyridine hemisolvate

    Directory of Open Access Journals (Sweden)

    Bi-Song Zhang

    2012-01-01

    Full Text Available In the title compound, {[Ca(C7H4FO22(H2O2]·0.5C10H8N2}n, the CaII atom is coordinated by eigth O atoms from four 2-fluorobenzoate ligands and two water molecules, resulting in a distorted CaO8 square-antiprismatic coordination environment. The 2-fluorobenzoate ligand bridges two symmetry-related CaII atoms, giving rise to a chain structure extending along [100]. The distances between the Ca atom and its two symmetry-related counterparts are 4.054 (2 and 4.106 (2 Å. The polymeric chains are connected by classical O—H...N hydrogen bonds into a layer structure parallel to (010. The layers are connected by non-classical C—H...F hydrogen bonds into a three-dimensional supramolecular structure. O—H...O and C—H...O interactions also occur. The uncoordinated 2,2′-bipyridine molecule is located on a centre of symmetry at the mid-point of the bond between the two heterocycles. One of the two benzene rings is disordered over two sites with occupancy factors of 0.60 and 0.40.

  20. Influence of the Torsion Angle in 3,3'-Dimethyl-2,2'-bipyridine on the Intermediate Valence of Yb in (C5Me5)2 Yb(3,3'-Me2-bipy)

    Energy Technology Data Exchange (ETDEWEB)

    Nocton, Gr& #233; gory; Booth, Corwin H.; Maron, Laurent; Andersen, Richard A.

    2014-06-26

    The synthesis and X-ray crystal structures of Cp-2*Yb(3,3'-Me(2)bipy) and [Cp-2 Yb(3,3'-Me(2)bipy)][Cp-2 YbCl1.6I0.4]center dot CH2Cl2 are described. In both complexes, the NCCN torsion angles are approximately 40 degrees. The temperature-independent value of n(f) of 0.17 shows that the valence of ytterbium in the neutral adduct is multiconfigurational, in reasonable agreement with a CASSCF calculation that yields a n(f) value of 0.27; that is, the two configurations in the wave function are f(13)(pi(1))(1) and f(14)(pi(1))(0) in a ratio of 0.27:0.73, respectively, and the open-shell singlet lies 0.28 eV below the triplet state (n(f) accounts for f-hole occupancy; that is, n(f) = 1 when the configuration is f(13) and n(f) = 0 when the configuration is f(14)). A correlation is outlined between the value of nf and the individual ytterbocene and bipyridine fragments such that, as the reduction potentials of the ytterbocene cation and the free x,x'-R-2-bipy ligands approach each other, the value of nf and therefore the f(13):f(14) ratio reaches a maximum; conversely, the ratio is minimized as the disparity increases.

  1. Synthesis, Structure and Properties of a Novel Infinite Triple Helices Coordination Polymer { [Co(4, 4′-bipyridine) (4, 4′-azobispyridine)2(NCS)2]·H2O }n%新颖无限三股螺旋钴配位聚合物{[Co(4,4′-bipyridine)(4,4′-azobispyridine)2(NCS)2]·H2O}n的合成、结构和性质的研究

    Institute of Scientific and Technical Information of China (English)

    李宝龙; 李宝宗; 徐正; 陈久桐

    2003-01-01

    The novel complex { [ Co (bipy) (azpy) 2 (NCS) 2 ] @ H2O } n (where bipy = 4, 4′-bipyridine, azpy = 4, 4′-azobisp-yridine) has been synthesized and characterized by elemental analyses, IR, UV, thermal analyses, and vari-able-temperature magnetic susceptibility. The crystal (C32H26CoN12OS2, Mr = 717.70) belongs to the orthorhombic,space group Pnna, a =2. 21312(16)nm, b = 1.40403(10)nm, c = 1. 14237(8)nm, V=3. 5497(4)nm3, Z =4,Dc = 1. 343g @ cm-3, μ=0. 645mm-1, F(000) = 1476, and final R1 =0. 0691, wR2 =0. 1129 for 231 parametersand 1674 observed reflections [ I > 2.00 σ(I) ]. The Co (Ⅱ) atom is, in a distorted octahedral geometry, coordi-nated by six nitrogen atoms from two bridging bipy, two monodentate azpy, and two thiocyanate groups. Thebridging ligand bipy links Co (Ⅱ) atoms to form the infinite "rod" with terminal coordination azpy ligand acting assidearms. Unprecedented three parallel interpenetrating two-dimensional (4, 4) networks and novel infinite triplehelices are formed via hydrogen-bonding interactions. CCDC: 155588.

  2. Optical and relaxometric properties of monometallic (Eu(III), Tb(III), Gd(III)) and heterobimetallic (Re(I)/Gd(III)) systems based on a functionalized bipyridine-containing acyclic ligand.

    Science.gov (United States)

    Leygue, Nadine; Boulay, Alexandre; Galaup, Chantal; Benoist, Eric; Laurent, Sophie; Vander Elst, Luce; Mestre-Voegtlé, Béatrice; Picard, Claude

    2016-05-17

    A series of lanthanide complexes of [LnL(H2O)](2-) composition where Ln = Eu(III), Tb(III) or Gd(III) has been studied for determining their photophysical and relaxometric properties in aqueous solution. The bifunctional ligand L (H5BPMNTA) is an acyclic chelator based on a central functionalized 2,2'-bipyridine core and two iminodiacetate coordinating arms. The mono-aqua Eu(III) and Tb(III) complexes display attractive spectroscopic properties with an excitation wavelength at 316 nm, similar excited state lifetimes and overall quantum yields (in the ranges 0.5-0.6 ms and 10-13%, respectively) in Tris buffer (pH 7.4). The proton longitudinal relaxivity, r1, of the Gd(III) complex is 4.4 mM(-1) s(-1) at 20 MHz and 310 K, which is comparable to that of the clinically used Gd-DTPA (Magnevist®). Interestingly, the water exchange rate between the coordination site and the bulk solvent is very fast (Kex = 2.6 × 10(8) s(-1) at 310 K). The ability of the complex to bind non-covalently to human serum albumin (HSA) was also examined by relaxometric measurements. We also report the synthesis and properties of a bimetallic complex based on Gd-BPMNTA and Re(I)(bpy)(CO)3 components. In this system, the Re core exhibits interesting photophysical properties (λem = 588 nm, Φ = 1.4%) and the Gd-BPMNTA core displays improved relaxivity (r1 = 6.6 mM(-1) s(-1) at 20 MHz and 310 K), due to an increase of the rotational correlation time. Besides these appealing optical and relaxometric properties, the presence of a reactive function on the structure proposes this potential dual imaging probe for conjugation to biomolecules or nanomaterials. PMID:27109253

  3. Self-assembly of multinuclear coordination species with chiral bipyridine ligands: silver complexes of 5,6-CHIRAGEN(o,m,p-xylidene) ligands and equilibrium behaviour in solution.

    Science.gov (United States)

    Mamula, O; Monlien, F J; Porquet, A; Hopfgartner, G; Merbach, A E; von Zelewsky, A

    2001-01-19

    The complexation reactions between Ag- and a series of enantiopure ligands belonging to the CHIRAGEN (from CHIRAlity GENerator) family (L1, L2, L3, based on (-)-5,6-pinene bipyridine) have been studied in solution. It has been shown that the length of the bridge plays a fundamental role in the self-assembly processes leading to different compounds: mononuclear complexes (with L3), mixtures of polynuclear complexes (with L2) and circular helicates (with L 1). Although the absolute configuration of the chiral centres in all three ligands is the same, the metal-centred chirality of L3 (delta) is inverted with respect to that in the other two complexes with L1 and L2 (delta). The metal configuration is thus opposite in the mononuclear complex with respect to the polynuclear species. Detailed thermodynamic studies were carried out for the Ag+ and L1 ligand system by 1H and 109Ag NMR spectroscopy (as a function of concentration, temperature and pressure). At low temperature and high pressure, the [Ag6L1(6)]6+ hexanuclear circular helicate forms a tetranuclear circular helicate [Ag4L1(4)]4+: 2[Ag6L1(6)]6+ 3 [Ag4L1(4)]4+. The thermodynamics parameters, obtained by temperature and pressure variation, have the following values: K298 = (8.7 +/- 0.7) x 10(-5) mol x kg(-1), deltaHo = -15.65 +/- 0.8 kJ x mol(-1), deltaSo = -130.2 +/- 3 J x mol(-1) x K(-1) and deltaVo(256 K)= -160 +/- 12 cm3 x mol(-1). The reaction volume calculated according to Connolly's method indicates that the calculated structure of [Ag4L1(4)]4+ is plausible. Both the signs and large magnitudes of deltaSo and deltaVo are counterintuitive, yet can be understood by modelling methods. PMID:11271539

  4. Sonochemical synthesis and characterization of a nano-sized Manganese (II) coordination polymer, [{Mn(NCS)2(4,4´-bipy)(H2O)2}(4,4´-bipy)]n; with 4,4'-Bipyridine (4,4'-bipy) ligand

    OpenAIRE

    N. Mosallanejad

    2014-01-01

    A novel nano – sized  manganese (II) coordination polymer, [{Mn(NCS)2(L)(H2O)2}(L)]n  , (1) (L- = 4,4'-Bipyridine), have been synthesized by a sonochemical process and characterized by scanning electron microscopy (SEM), X-ray diffraction (XRD), IR spectroscopy and elemental analysis.  Direct calcination of the single crystals and nano-sized compound 1 at 400 0C under air atmosphere yields mixture of K2Mn2 (SO4)3, MnOS and Mn3O4 nanoparticles. Results show that the size and morphology of the ...

  5. catena-Poly[[[(2,2′-bipyridine-κ2 N,N′)manganese(II)]-μ-(2,5-dichloro-3,6-dioxocyclo­hexa-1,4-diene-1,4-diolato)-κ4 O 1,O 6:O 3,O 4] ethanol disolvate

    OpenAIRE

    Yuji Nishimura; Akiko Himegi; Akira Fuyuhiro; Shinya Hayami; Satoshi Kawata

    2013-01-01

    The asymmetric unit of the title coordination polymer, {[Mn(C6Cl2O4)(C10H8N2)]·2C2H5OH}n, consists of one MnII ion, one 2,2′-bipyridine (bpy) ligand, one chloranilate (CA2−) ligand and two ethanol solvent molecules. The MnII ion is octahedrally coordinated by two N atoms of one bpy ligand and four O atoms of two chloranilate ions. The chloranilate ion serves as a bridging ligand between the MnII ions, leading to an infinite zigzag chain along [101]. π–π stacki...

  6. Homoleptic Iron(II) Complexes with the Ionogenic Ligand 6,6'-Bis(1H-tetrazol-5-yl)-2,2'-bipyridine: Spin Crossover Behavior in a Singular 2D Spin Crossover Coordination Polymer.

    Science.gov (United States)

    Seredyuk, Maksym; Piñeiro-López, Lucía; Muñoz, M Carmen; Martínez-Casado, Francisco J; Molnár, Gábor; Rodriguez-Velamazán, José Alberto; Bousseksou, Azzedine; Real, José Antonio

    2015-08-01

    Deprotonation of the ionogenic tetradentate ligand 6,6'-bis(1H-tetrazol-5-yl)-2,2'-bipyridine [H2bipy(ttr)2] in the presence of Fe(II) in solution has afforded an anionic mononuclear complex and a neutral two-dimensional coordination polymer formulated as, respectively, NEt3H{Fe[bipy(ttr)2][Hbipy(ttr)2]}·3MeOH (1) and {Fe[bipy(ttr)2]}n (2). The anions [Hbipy(ttr)2](-) and [bipy(ttr)2](2-) embrace the Fe(II) centers defining discrete molecular units 1 with the Fe(II) ion lying in a distorted bisdisphenoid dodecahedron, a rare example of octacoordination in the coordination environment of this cation. The magnetic behavior of 1 shows that the Fe(II) is high-spin, and its Mössbauer spectrum is characterized by a relatively large average quadrupole splitting, ΔEQ = 3.42 mm s(-1). Compound 2 defines a strongly distorted octahedral environment for Fe(II) in which one [bipy(ttr)2](-) anion coordinates the equatorial positions of the Fe(II) center, while the axial positions are occupied by peripheral N-tetrazole atoms of two adjacent {Fe[bipy(ttr)2]}(0) moieties thereby generating an infinite double-layer sheet. Compound 2 undergoes an almost complete spin crossover transition between the high-spin and low-spin states centered at about 221 K characterized by an average variation of enthalpy and entropy ΔH(av) = 8.27 kJ mol(-1), ΔS(av) = 37.5 J K(-1) mol(-1), obtained from calorimetric DSC measurements. Photomagnetic measurements of 2 at 10 K show an almost complete light-induced spin state trapping (LIESST) effect which denotes occurrence of antiferromagnetic coupling between the excited high-spin species and TLIESST = 52 K. The crystal structure of 2 has been investigated in detail at various temperatures and discussed. PMID:26172431

  7. Crystal structures of tetramethylammonium (2,2′-bipyridinetetracyanidoferrate(III trihydrate and poly[[(2,2′-bipyridine-κ2N,N′di-μ2-cyanido-dicyanido(μ-ethylenediamine(ethylenediamine-κ2N,N′cadmium(IIiron(II] monohydrate

    Directory of Open Access Journals (Sweden)

    Songwuit Chanthee

    2016-05-01

    Full Text Available The crystal structures of the building block tetramethylammonium (2,2′-bipyridine-κ2N,N′tetracyanidoferrate(III trihydrate, [N(CH34][Fe(CN4(C10H8N2]·3H2O, (I, and a new two-dimensional cyanide-bridged bimetallic coordination polymer, poly[[(2,2′-bipyridine-κ2N,N′di-μ2-cyanido-dicyanido(μ-ethylenediamine-κ2N:N′(ethylenediamine-κ2N,N′cadmium(IIiron(II] monohydrate], [CdFe(CN4(C10H8N2(C2H8N22]·H2O, (II, are reported. In the crystal of (I, pairs of [Fe(2,2′-bipy(CN4]− units (2,2′-bipy is 2,2′-bipyridine are linked together through π–π stacking between the pyridyl rings of the 2,2′-bipy ligands to form a graphite-like structure parallel to the ab plane. The three independent water molecules are hydrogen-bonded alternately with each other, forming a ladder chain structure with R44(8 and R66(12 graph-set ring motifs, while the disordered [N(CH34]+ cations lie above and below the water chains, and the packing is stabilized by weak C—H...O hydrogen bonds. The water chains are further linked with adjacent sheets into a three-dimensional network via O—H...O hydrogen bonds involving the lattice water molecules and the N atoms of terminal cyanide groups of the [Fe(2,2′-bipy(CN4]− building blocks, forming an R44(12 ring motif. Compound (II features a two-dimensional {[Fe(2,2′-bipy(CN4Cd(en2]}n layer structure (en is ethylenediamine extending parallel to (010 and constructed from {[Fe(2,2′-bipy(CN4Cd(en]}n chains interlinked by bridging en ligands at the Cd atoms. Classical O—H...N and N—H...O hydrogen bonds involving the lattice water molecule and N atoms of terminal cyanide groups and the N—H groups of the en ligands are observed within the layers. The layers are further connected via π–π stacking interactions between adjacent pyridine rings of the 2,2′-bipy ligands, completing a three-dimensional supramolecular structure.

  8. The role of acid in the formation of hydrogen-bonded networks featuring 4,4'-dicarboxy-2,2'-bipyridine (H2dcbp): Synthesis, structural and magnetic characterisation of {[Cu(H2dcbp)Cl2].H2O}2 and [Cu(H2dcbp)(NO3)2(H2O)

    OpenAIRE

    Tynan, Eithne; Jensen, Paul; Lees, Anthea C.; Moubaraki, Boujemaa; Murray, Keith S.; Kruger, Paul E.

    2005-01-01

    Reported herein are the synthesis, structural and magnetic characterisation of two hydrogen-bonded networks featuring the 4,4?-dicarboxy-2,2?-bipyridine (H2dcbp) ligand: {[Cu(H2dcbp)(Cl)2]·H2O}2 1 and [Cu(H2dcbp)(NO3)2(H2O)] 2. Compounds 1 and 2 result from the reaction of CuCl2 and Cu(NO3)2, respectively, with H2dcbp under hydrothermal conditions in the presence of either HCl or HNO3. The acid ensures that H2dcbp remains protonated and provides the anions required for charge balance irrespec...

  9. Triaqua-1κO,2κ2O-bis(2,2′-bipyridine-1κ2N,N′;2κ2N,N′-chlorido-1κCl-μ-terephthalato-1:2κ2O1:O4-dicopper(II nitrate monohydrate

    Directory of Open Access Journals (Sweden)

    Yang Liu

    2012-06-01

    Full Text Available In the binuclear title compound, [Cu2(C8H4O4Cl(C10H8N22(H2O3]NO3·H2O, the two crystallographically independent CuII ions have similar coordination environments. One of the CuII ions has a square-pyramidal arrangement, which is defined by a water molecule occupying the apical position, with the equatorial ligators consisting of two N atoms from a 2,2′-bipyridine molecule, one carboxylate O atom from a terephthalate ligand and one O atom from a water molecule. The other CuII ion has a similar coordination environment, except that the apical position is occupied by a chloride ligand instead of a water molecule. An O—H...O and O—H...Cl hydrogen-bonded three-dimensional network is formed between the components.

  10. Sonochemical synthesis and characterization of a nano-sized Manganese (II coordination polymer, [{Mn(NCS2(4,4´-bipy(H2O2}(4,4´-bipy]n; with 4,4'-Bipyridine (4,4'-bipy ligand

    Directory of Open Access Journals (Sweden)

    N. Mosallanejad

    2014-05-01

    Full Text Available A novel nano – sized  manganese (II coordination polymer, [{Mn(NCS2(L(H2O2}(L]n  , (1 (L- = 4,4'-Bipyridine, have been synthesized by a sonochemical process and characterized by scanning electron microscopy (SEM, X-ray diffraction (XRD, IR spectroscopy and elemental analysis.  Direct calcination of the single crystals and nano-sized compound 1 at 400 0C under air atmosphere yields mixture of K2Mn2 (SO43, MnOS and Mn3O4 nanoparticles. Results show that the size and morphology of the K2Mn2 (SO43, MnOS, Mn3O4 nanoparticles depend on the particles size of compound 1. Decrease in the particles size of compound 1 leads to decrease in the particles size of the K2Mn2 (SO43, MnOS and Mn3O4.

  11. [μ-2-(4-Hydroxyphenylacetato]-κ3O:O,O′;κ3O,O′:O′-bis{aqua(4,4′-bipyridine-κNbis[2-(4-hydroxyphenylacetato-κ2O,O′]holmium(III} monohydrate

    Directory of Open Access Journals (Sweden)

    Jia-Lu Liu

    2011-02-01

    Full Text Available In the title dinuclear complex, [Ho2(C8H7O36(C10H8N22(H2O2]·H2O, each of the two independent HoIII ions is coordinated by eight O atoms from four 4-hydroxyphenylacetate (HPAA ligands and a water molecule, and one N atom from a 4,4′-bipyridine (bipy ligand in a distorted tricapped trigonal–prismatic geometry. The HPAA ligands are coordinated in bis-chelate, bridging and bridging tridentate modes. In the crystal, O—H...O and O—H...N hydrogen bonds link the molecules into a three-dimensional network.

  12. catena-Poly[[{diaqua[2-(4-hydroxyphenylacetato-κ2O,O′]cerium(III}-bis[μ-2-(4-hydroxyphenylacetato]-κ3O,O′:O;κ3O:O,O′] 4,4′-bipyridine disolvate monohydrate

    Directory of Open Access Journals (Sweden)

    Jia-Lu Liu

    2010-12-01

    Full Text Available In the polymeric title complex, {[Ce(C8H7O33(H2O2]·2C10H8N2·H2O}n, the CeIII ion is coordinated by ten O atoms from four 2-(4-hydroxyphenylacetate (HPAA ligands and two water molecules. One HPAA ligand coordinates just to one CeIII ion, whereas the remaining two bridge two CeIII ions. The 4,4′-bipyridine molecule and one water molecule are not coordinated to Ce. In the crystal, O—H...O and O—H...N hydrogen bonds link molecules into a three-dimensional network.

  13. Structure of a dinuclear cadmium complex with 2,2'-bi-pyridine, monodentate nitrate and 3-carb-oxy-6-methyl-pyridine-2-carboxyl-ate ligands: intra-molecular carbon-yl(lone pair)⋯π(ring) and nitrate(π)⋯π(ring) inter-actions.

    Science.gov (United States)

    Granifo, Juan; Suarez, Sebastián; Baggio, Ricardo

    2015-08-01

    The centrosymmetric dinuclear complex bis-(μ-3-carb-oxy-6-methyl-pyridine-2-carboxyl-ato)-κ(3) N,O (2):O (2);κ(3) O (2):N,O (2)-bis-[(2,2'-bi-pyridine-κ(2) N,N')(nitrato-κO)cadmium] methanol monosolvate, [Cd2(C8H6NO4)2(NO3)2(C10H8N2)2]·CH3OH, was isolated as colourless crystals from the reaction of Cd(NO3)2·4H2O, 6-methyl-pyridine-2,3-di-carb-oxy-lic acid (mepydcH2) and 2,2'-bi-pyridine in methanol. The asymmetric unit consists of a Cd(II) cation bound to a μ-κ(3) N,O (2):O (2)-mepydcH(-) anion, an N,N'-bidentate 2,2'-bi-pyridine group and an O-mono-dentate nitrate anion, and is completed with a methanol solvent mol-ecule at half-occupancy. The Cd complex unit is linked to its centrosymmetric image through a bridging mepydcH(-) carboxyl-ate O atom to complete the dinuclear complex mol-ecule. Despite a significant variation in the coordination angles, indicating a considerable departure from octa-hedral coordination geometry about the Cd(II) 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 inter-stitial columnar voids that are filled by the methanol solvent mol-ecules. These in turn inter-act with the complex mol-ecules 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-κ(3) coordination mode found in the title compound. PMID:26396748

  14. (2,2′-Bipyridine-4,4′-dicarboxylic acid-κ2N,N′chlorido(2,2′:6′,2′′-terpyridyl-κ3N,N′,N′′ruthenium(II perchlorate ethanol monosolvate monohydrate

    Directory of Open Access Journals (Sweden)

    Anne Nielsen

    2012-01-01

    Full Text Available In the title compound, [RuCl(C15H11N3(C12H8N2O4]ClO4·C2H5OH·H2O, the geometry of the ClN5 coordination set around the RuII atom is close to octahedral, but distorted on account of the limited bite angles of the polypyridyl ligands. The complexes are linked by O—H...O hydrogen bonds between the carboxyl groups and the crystal lattice water molecules into chains along [110]. Face-to-face stacking interactions are formed between terpyridine ligands, with interplanar separations of 3.66 (1 and 3.42 (1 Å, and between bipyridine-4,4′-dicarboxylic acid ligands, with interplanar separations of 3.65 (1 and 3.72 (1 Å. Three O atoms of the perchlorate ion are each disordered equally over two positions. The hydroxy group of the ethanol molecule is also disordered over two sites with refined occupancies of 0.794 (9 and 0.206 (9.

  15. Synthesis and crystal structures of new complexes of Np(V) glycolate with 2,2'-bipyridine, [NpO2(C10H8N2)(OOC2H2OH)].1.5H2O and [NpO2(C10H8N2)(OOC2H2OH)].2.5H2O

    International Nuclear Information System (INIS)

    Single crystals were prepared, and the structures of two complexes of Np(V) glycolate with 2,2'-bipyridine of the compositions [NpO2(C10H8N2)(OOC2H2OH)].1.5H2O (I) and [NpO2(C10H8N2)(OOC2H2OH)]2.5H2O (II) were studied. The structures of the compounds are based on neptunyl-glycolate chains in which the glycolate anion manifests its complexation ability in different manner. In structure I, the bidentate-bridging anion links the adjacent NpO2- cations through the oxygen atoms of the carboxylate group. The neptunyl-glycolate chains of I exhibits the mutual coordination of the NpO2- cations acting toward each other simultaneously as ligands and coordinating centers. In compound II, the glycolate anion is bidentately coordinated to one neptunium atom to form a planar five-membered metallocycle [NpOCCO]. The O atom external with respect to the metallocycle is in the coordination environment of the adjacent neptunyl. The nitrogen-containing molecular ligand Bipy is included into the coordination environment of Np. The coordination polyhedron of the Np atoms in both structures is a pentagonal bipyramid in which the average Np-N bond length is 2.666 Aa (I) and 2.596 Aa (II). (orig.)

  16. Hindered rotation in a novel 1,2,4-triazinyl phenanthroline (T-Phen) ligand leading to improved separation of Am3+ and Eu3+ vis-a-vis 1,2,4-triazinyl bipyridine (T-Bipy): synthesis and computational validation of the experimental results

    International Nuclear Information System (INIS)

    A novel nitrogen donor ligand having more pre-organized structure, 1,2,4-triazinyl phenanthroline (T-phen), was synthesized and evaluated for lanthanide - actinide separation. The extraction and selectivity for Am3+ over Eu3+ was found to be improved with T-phen as compared to the analogous 1,2,4-triazinyl bipyridine bipy, which was explained by analyzing their conformational energies and energy differences between the frontier orbitals (highest occupied molecular orbital (HOMO) and lowest unoccupied molecular (LUMO) with the help of ab initio molecular orbital calculations. Higher covalence in Am3+ complexes compared to the Eu3+ complexes were indicated by more shared electrons between Am3+ and bonded 'N' atoms, shorter 'Am-N' bonds and higher overlap between the orbitals of Am3+ and ligands in the frontier orbitals complexes in case of both the ligands. The separation factor values with T-phen and T-bipy are given at varying pH values. The results suggest more efficient separation with T-phen as compared to T-bipy which is attributed to hindered rotation of the former ligand

  17. catena-Poly[[[(2,2′-bipyridine-κ2N,N′manganese(II]-μ-(2,5-dichloro-3,6-dioxocyclohexa-1,4-diene-1,4-diolato-κ4O1,O6:O3,O4] ethanol disolvate

    Directory of Open Access Journals (Sweden)

    Yuji Nishimura

    2013-02-01

    Full Text Available The asymmetric unit of the title coordination polymer, {[Mn(C6Cl2O4(C10H8N2]·2C2H5OH}n, consists of one MnII ion, one 2,2′-bipyridine (bpy ligand, one chloranilate (CA2− ligand and two ethanol solvent molecules. The MnII ion is octahedrally coordinated by two N atoms of one bpy ligand and four O atoms of two chloranilate ions. The chloranilate ion serves as a bridging ligand between the MnII ions, leading to an infinite zigzag chain along [101]. π–π stacking interactions [centroid–centroid distance = 4.098 (2 Å] is observed between the pyridine rings of adjacent chains. The ethanol molecules act as accepters as well as donors for O—H...O hydrogen bonds, and form a hydrogen-bonded chain along the a axis. The H atoms of the hydroxy groups of the two independent ethanol molecules are each disordered over two sites with equal occupancies.

  18. Mixed ligand complexes of Cu(II)/Zn(II) ions containing (m-)/(p-) carboxylato phenyl azo pentane 2,4-dione and 2,2‧-bipyridine/1,10 phenanthroline: Synthesis, characterization, DNA binding, nuclease and topoisomerase I inhibitory activity

    Science.gov (United States)

    Hasan, Md. Amin; Kumari, Niraj; Singh, Kanhaiya; Singh, Kiran; Mishra, Lallan

    2016-01-01

    Metal complexes of type [Cu(L1H)2(bpy)] (1), [Zn(L1H)2(bpy)] (2), [Cu(L2H)2(bpy)] (3) and [Cu(L2H)2(Phen)] (4) (L1H2 = 3-[N‧-(1-acetyl-2-oxo-propylidene)-hydrazino]-benzoic acid, L2H2 = 4-[N‧-(1-acetyl-2-oxo-propylidene)-hydrazino]-benzoic acid, bpy = 2,2‧-bipyridine, Phen = 1,10 phenanthroline) are synthesized and characterized using spectroscopic techniques (FT-IR, 1H NMR, 13C NMR, electronic absorption and emission) and elemental analysis data. The assembly of the complexes involving intramolecular H-bonding is displayed using corresponding crystal structure. Binding of the complexes separately with Calf Thymus DNA is monitored using UV-vis spectral titrations. The displacement of ethidium bromide (EB) bound to DNA by the complexes, in phosphate buffer solution (pH ∼ 7.2) is monitored using fluorescence spectral titrations. Nuclease activity of the complexes follow the order 4 > 3 > 1 > 2. The gel electrophoretic mobility assay measurement in presence of minor groove binder 4‧,6-diamidino-2-phenylindole (DAPI), suggests that complexes preferably bind with the minor groove of DNA. Topoisomerase I inhibitory activity of the complexes 3 and 4 inhibit topoisomerase I activity with IC50 values of 112 and 87 μM respectively.

  19. Synthesis and Characterization of Chiral Mercury(II) and Cadmium(II) Complexes with 3,3'-Bipyridine-5,5',6,6'-tetramethyl-2,2'-dimethoxy-1,1'-biphenyl

    Institute of Scientific and Technical Information of China (English)

    FANG Yu; XUAN Wei-Min; ZHU Cheng-Feng; YUAN Guo-Zan; CUI Yong

    2011-01-01

    Two homochiral mercury (1) and cadmium (2) complexes derived from chiral twisted biphenyl pyridine ligand (3,3'-bipyridine-5,5',6,6'-tetramethyl-2,2'-dimethoxy-1,1'-biphenyl) have been synthesized and characterized by IR, microanalysis, TGA, UV-Vis, powder and single-crystal X-ray crystallography. Both 1 and 2 crystallize in orthorhombic space group P21212 with Z = 2. For 1, a = 14.2038(16), b = 14.3630(17), c = 7.0257(8), V = 1433.3(3)3, Mr = 878.91, Dc = 2.037 g/cm3, μ = 7.549 mm-1, F(000) = 824, the final GOF = 1.017, R = 0.0296 and wR = 0.0645 for 2925 observed reflections with I 2σ(I). For 2, a = 14.212(3), b = 14.392(3), c = 7.0498(14), V = 1442.0(5)3, Mr = 790.72, Dc = 1.821 g/cm3, μ = 2.924 mm–1, F(000) = 760, the final GOF = 1.075, R = 0.0340 and wR = 0.0834 for 3144 observed reflections with I 2σ(I). The crystal structures of 1 and 2 are isostructural and each adopts a two-dimensional supramolecular network which contains the C–H···π interactions.

  20. DNA hybridization biosensor using chitosan-carbon nanotubes composite film as an immobilization platform and [Cu(bpy)(MBZ){sub 2}(H{sub 2}O)] (bpy = 2,2'-bipyridine, MBZ = p-methylbenzoate) as a novel redox indicator

    Energy Technology Data Exchange (ETDEWEB)

    Wang Qingxiang, E-mail: axiang236@126.co [Department of Chemistry and Environment Science, Zhangzhou Normal University, Zhangzhou 363000 (China) and Fujian Province University Key Laboratory of Analytical Science, Zhangzhou Normal University, Zhangzhou 363000 (China); Shi Juanlan; Ni Jiancong; Gao Fei; Gao Feng [Department of Chemistry and Environment Science, Zhangzhou Normal University, Zhangzhou 363000 (China); Weng Wen [Department of Chemistry and Environment Science, Zhangzhou Normal University, Zhangzhou 363000 (China); Fujian Province University Key Laboratory of Analytical Science, Zhangzhou Normal University, Zhangzhou 363000 (China); Jiao Kui, E-mail: kjiao@qust.edu.c [College of Chemistry and Molecular Engineering, Qingdao University and Science and Technology, Qingdao 266042 (China)

    2011-04-15

    Research highlights: Chitosan-carbon nanotubes composite was used as a platform for DNA immobilization. Discrimination of a synthetic copper complex to ds- and ss-DNA was obtained. Hybridization detection was performed using the copper complex as an indicator. Good specificity and high sensitivity were achieved on the constructed DNA biosensor. - Abstract: In this paper, a new DNA hybridization detection strategy was developed based on the immobilization of capture probe DNA on a chitosan (CS)-carbon nanotubes (CNTs) composite modified glassy carbon electrode (CS-CNTs/GCE) and the use of a copper complex, [Cu(bpy)(MBZ){sub 2}(H{sub 2}O)] (bpy = 2,2'-bipyridine, MBZ = p-methylbenzoate), as a new redox hybridization indicator. The electrochemical characterization experiments showed that the nanocomposite film of CS-CNTs could effectively immobilize the capture probe DNA and greatly improve the electron-transfer reactions of the electroactive molecules. Electrochemical and fluorescent spectroscopic analysis revealed that the polypyridyl copper complex of [Cu(bpy)(MBZ){sub 2}(H{sub 2}O)] bound to DNA via a typical intercalation mode. Surface studies further showed that the copper complex can discriminate between double-stranded and single-stranded DNA that immobilized on the surface of CS-CNTs/GCE. When being utilized as a redox indicator for the detection of hybridization for short DNA species related to phosphinothricin acetyltransferase (PAT), the indicator showed good specificity for recognizing the complementary, three-base mismatched and non-complementary DNA. Under the optimized conditions, the oxidation peak currents of the copper complex enhanced linearly with increases in the concentration of the complementary sequence in the range from 5.0 x 10{sup -10} to 1.0 x 10{sup -8} M. A detection limit of 5.0 x 10{sup -10} M was also obtained based on the constructed DNA biosensor.

  1. 6,6 '-bis (5,5,8,8-tetramethyl-5,6,7,8-tetra-hydro-benzo 1,2,4 triazine-3-yl) 2,2 ' bipyridine, an effective extracting agent for the separation of americium(III) and curium(III) from the lanthanides

    International Nuclear Information System (INIS)

    The extraction of americium(III), curium(III), and the lanthanides(III) from nitric acid by 6,6'- bis (5,5,8,8-tetramethyl-5,6,7,8-tetra-hydro-benzo[1,2,4]triazine-3-yl)-[2,2'] bipyridine (CyMe4-BTBP) has been studied. Since the extraction kinetics were slow, N,N'-dimethyl-N,N'-di-octyl-2-(2-hexyl-oxy-ethyl)malonamide (DMDOHEMA) was added as a phase transfer reagent. With a mixture of 0.01 M CyMe4-BTBP + 0.25 M DMDOHEMA in n -octanol, extraction equilibrium was reached within 5 min of mixing. At a nitric acid concentration of 1 M, an americium(III) distribution ratio of approx. 10 was achieved. Americium(III)/lanthanide(III) separation factors between 50 (dysprosium) and 1500 (lanthanum) were obtained. Whereas americium(III) and curium(III) were extracted as di-solvates, the stoichiometries of the lanthanide(III) complexes were not identified unambiguously, owing to the presence of DMDOHEMA. In the absence of DMDOHEMA, both americium(III) and europium(III) were extracted as di-solvates. Back-extraction with 0.1 M nitric acid was thermodynamically possible but rather slow. Using a buffered glycolate solution of pH=4, an americium(III) distribution ratio of 0.01 was obtained within 5 min of mixing. There was no evidence of degradation of the extractant, for example, the extraction performance of CyMe4-BTBP during hydrolysis with 1 M nitric acid did not change over a two month contact. (authors)

  2. An octanuclear molybdenum(VI) complex containing coordinatively bound 4,4'-di-tert-butyl-2,2'-bipyridine, [Mo8O22(OH)4(di-tBu-bipy)4]: synthesis, structure, and catalytic epoxidation of bio-derived olefins.

    Science.gov (United States)

    Amarante, Tatiana R; Neves, Patrícia; Tomé, Cátia; Abrantes, Marta; Valente, Anabela A; Paz, Filipe A Almeida; Pillinger, Martyn; Gonçalves, Isabel S

    2012-03-19

    The reaction of [MoO(2)Cl(2)(di-tBu-bipy)] (1) (di-tBu-bipy = 4,4'-di-tert-butyl-2,2'-bipyridine) with water at 100-120 °C in a Teflon-lined stainless steel autoclave, in an open reflux system, or in a microwave synthesis system gave the octanuclear complex [Mo(8)O(22)(OH)(4)(di-tBu-bipy)(4)] (2) as a microcrystalline powder in good yields. Single crystals of 2 suitable for X-ray diffraction were obtained by the reaction of MoO(3) and di-tBu-bipy in water at 160 °C for 3 days. The molecular structure of 2 comprises a purely inorganic core, Mo(4)O(8)(μ(3)-OH)(2)(μ(2)-O)(2), attached to two peripheral oxo-bridged binuclear units, Mo(2)O(4)(μ(2)-O)(2)(OH)(di-tBu-bipy)(2). The inorganic core is composed of a unique assembly of four {MoO(5)} distorted square pyramids connected to each other via edge-sharing. Overall, the octanuclear complex adopts a highly distorted form strongly resembling an "S"-shaped molecular unit. Complex 2 was applied in the catalytic epoxidation of the biorenewable olefins DL-limonene (Lim) and methyl oleate (Ole), using tert-butylhydroperoxide (TBHP) as an oxygen donor, under mild reaction conditions (55 °C, air). The reactions of Lim and Ole gave the respective epoxide monomers in fairly high selectivities at high conversions (89% 1,2-epoxy-p-menth-8-ene selectivity at 96% Lim conversion; 99% methyl 9,10-epoxystearate selectivity at 94% Ole conversion, reached within 24 h reaction). Iodometric titrations revealed no measurable "non-productive" decomposition of TBHP. PMID:22372402

  3. Involvement of a binuclear species with the Re-C(O)O-Re moiety in CO2 reduction catalyzed by tricarbonyl rhenium(I) complexes with diimine ligands: strikingly slow formation of the Re-Re and Re-C(O)O-Re species from Re(dmb)(CO)3S (dmb = 4,4'-dimethyl-2,2'-bipyridine, S = solvent).

    Science.gov (United States)

    Hayashi, Yukiko; Kita, Shouichi; Brunschwig, Bruce S; Fujita, Etsuko

    2003-10-01

    Excited-state properties of fac-[Re(dmb)(CO)(3)(CH(3)CN)]PF(6), [Re(dmb)(CO)(3)](2) (where dmb = 4,4'-dimethyl-2,2'-bipyridine), and other tricarbonyl rhenium(I) complexes were investigated by transient FTIR and UV-vis spectroscopy in CH(3)CN or THF. The one-electron reduced monomer, Re(dmb)(CO)(3)S (S = CH(3)CN or THF), can be prepared either by reductive quenching of the excited states of fac-[Re(dmb)(CO)(3)(CH(3)CN)]PF(6) or by homolysis of [Re(dmb)(CO)(3)](2). In the reduced monomer's ground state, the odd electron resides on the dmb ligand rather than on the metal center. Re(dmb)(CO)(3)S dimerizes slowly in THF, k(d) = 40 +/- 5 M(-1) s(-1). This rate constant is much smaller than those of other organometallic radicals which are typically 10(9) M(-1) s(-1). The slower rate suggests that the equilibrium between the ligand-centered and metal-centered radicals is very unfavorable (K approximately 10(-4)). The reaction of Re(dmb)(CO)(3)S with CO(2) is slow and competes with the dimerization. Photolysis of [Re(dmb)(CO)(3)](2) in the presence of CO(2) produces CO with a 25-50% yield based on [Re]. A CO(2) bridged dimer, (CO)(3)(dmb)Re-CO(O)-Re(dmb)(CO)(3) is identified as an intermediate. Both [Re(dmb)(CO)(3)](2)(OCO(2)) and Re(dmb)(CO)(3)(OC(O)OH) are detected as oxidation products; however, the previously reported formato-rhenium species is not detected. PMID:14505419

  4. Selective Zn2+ sensing using a modified bipyridine complex

    Energy Technology Data Exchange (ETDEWEB)

    Akula, Mahesh; El-Khoury, Patrick Z.; Nag, Amit; Bhattacharya, Anupam

    2014-06-01

    A novel fluorescent Zn2+ sensor, 4-(pyridin-2-yl)-3H-pyrrolo[2, 3-c]quinoline (PPQ), has been designed, synthesized and characterized by various spectroscopic and analytical techniques. PPQ exhibits superior detection of Zn2+ in the presence of various cations tested, including Cd2+ and Hg2+, via wavelength shifted fluorescence intensity enhancement. The emission wavelength at 500 nm, ensures probable noninterference from cellular components while performing biological applications.

  5. Platinum chloride complexes containing 6-[9,9-di(2-ethylhexyl)-7-R-9H-fluoren-2-yl]-2,2'-bipyridine ligand (R = NO2, CHO, benzothiazol-2-yl, n-Bu, carbazol-9-yl, NPh2): tunable photophysics and reverse saturable absorption.

    Science.gov (United States)

    Li, Zhongjing; Badaeva, Ekaterina; Ugrinov, Angel; Kilina, Svetlana; Sun, Wenfang

    2013-07-01

    Six new platinum(II) chloride complexes 1-6 containing a 6-[9,9-di(2-ethylhexyl)-7-R-9H-fluoren-2-yl]-2,2'-bipyridine (R = NO2, CHO, benzothiazol-2-yl (BTZ), n-Bu, carbazol-9-yl (CBZ), NPh2) ligand were synthesized and characterized. The influence of the electron-donating or electron-withdrawing substituent at the 7-position of the fluorenyl component on the photophysics of these complexes was systematically investigated by spectroscopic methods and simulated by time-dependent density functional theory (TDDFT). Electron-withdrawing or -donating substituents exert distinct effects on the photophysics of the complexes. All complexes feature a low-energy, broad (1)MLCT (metal-to-ligand charge transfer)/(1)ILCT (intraligand charge transfer)/(1)π,π* absorption band (tail) above ca. 430 nm and a major absorption band(s) between 320 and 430 nm, which admix (1)MLCT, (1)π,π*, (1)ILCT, and/or (1)LLCT (ligand-to-ligand charge transfer) characters. The contributions of different configurations to the major absorption band(s) vary depending on the nature of the substituent. Strong electron-donating or -withdrawing substituents (NPh2 and NO2) and the aromatic substituent BTZ cause a pronounced red-shift of the absorption spectra of 1, 3, and 6. All complexes are emissive at room temperature and at 77 K. The emitting excited state is dominated by (3)π,π* character in 1-3, with some contributions from (3)MLCT in 1 and 2, while the emission is predominantly from the (3)MLCT state for 4 and 5 but with some (3)π,π* character. For 6, the emitting state is (3)ILCT in nature. With the increased electron-donating ability of the substituent, the (3)π,π* character diminishes while charge transfer character increases. All complexes exhibit broad and strong triplet excited-state absorption (TA) from the near-UV to the near-IR spectral region. The TA band maxima are red-shifted for complexes 1-3 (which possess the electron-withdrawing substituents) compared to those of 4-6 (which

  6. Synthesis, Superoxide Dismutase Mimetic and Anticancer Activities of Metal Complexes of 2,2-Dimethylpentanedioic Acid(2dmepdaH2 and 3,3-Dimethylpentanedioic acid(3dmepdaH2: X-Ray Crystal Structures of [Cu(3dmepda(bipy]2⋅6H2O and [Cu(2dmepda(bipy(EtOH]2⋅4EtOH(bipy=2,2′Bipyridine

    Directory of Open Access Journals (Sweden)

    Carol Deegan

    2005-03-01

    Full Text Available 2,2-dimethylpentanedioic acid (2dmepdaH2 and 3,3-dimethylpentanedioic acid (3dmepdaH2 reacted with copper(II acetate to give [Cu(2dmepda(H2O3]2 (1 and [Cu(3dmepda(H2O3]2 (2. Reaction of (1 and (2 with 1,10-phenanthroline and 2,2′-bipyridine yielded [Cu(2dmepda(phen(H2O]20.5phen (3, [Cu(2dmepda(bipy(H2O]2 (4, [Cu(2dmepda(bipy(EtOH]2⋅2EtOH (4A, [Cu(3dmepda(phen(H2O]2 (5, and [Cu(3dmepda(bipy(H2O]2⋅ (6. The structures of (4A and (6 each consists of a [Cu(bipy(dicarboxylate(solvent]2 dimer. The superoxide dismutase (SOD mimetic activity of the novel copper complexes and their manganese analogues was investigated. The dimethyl sulphoxide(DMSO soluble complexes (1–(4 and (6 were assessed for their cancer chemotherapeutic potential towards hepatocellular carcinoma and kidney adenocarcinoma cell lines. The 1,10-phenanthroline containing complex [Cu(2dmepda(phen(H2O]20.5phen (3 was the most potent with activity that compares well to that of cisplatin.

  7. Effects of Br substituent on catalytic performance of Ru-bda (H2bda = 2,2′-bipyridine-6,6′-dicarboxylic acid) catalysts for water oxidation%溴的吸电子效应对Ru-bda(H2bda =2,2′-联吡啶-6,6′-二羧基)型催化剂催化水氧化的性能影响

    Institute of Scientific and Technical Information of China (English)

    刘昭; 高岩; 于泽; 张敏; 刘建辉

    2015-01-01

    表明催化剂2和3与催化剂1的反应机理有所不同.由于催化剂1发生二级反应即在催化水氧化过程中发生双分子间的自由基耦合反应,而催化剂2和3的反应级数均小于2,说明核心配体上的Br取代基的吸电子效应导致催化剂2和3的反应机理发生改变,在水氧化反应过程中部分催化剂2和3分子发生了单分子反应,即水分子亲核进攻机理.当轴向配体由4-甲基吡啶替换为异喹啉时,对比催化剂4和5的催化水氧化活性和动力学研究,也可以得到类似的结果.但与催化剂2和3相比,催化剂5的反应级数降低不明显,说明催化体系中只有一部分分子发生一级反应,大部分分子发生二级反应.这说明在以化合物5为催化剂的水氧化体系中,除了核心配体上Br的吸电子效应对催化剂机理产生影响之外,轴向配体的异喹啉的π-π堆积效应也有重要影响(异喹啉的π-π堆积效应能够促进单核催化剂发生二级反应),并且后者产生的影响占  主导位置,从而导致催化剂5的反应级数降低的不明显.%A series of new Ru-bda catalysts with Br modification on the equatorial ligand, [Ru(Ln)(picoline)2] (H2L1 = 4-Br-2,2′-bipyridine-6,6′-dicarboxylic acid (4-Br-bda),2;H2L2 = 4,4′-diBr-bda,3) and [Ru(L1)(isoquinoline)2]5, were synthesized for catalytic water oxidation. Compared with the un-substituted catalysts, the catalysts modified with Br displayed a marked change in the catalytic activities and reaction orders. The results confirm that the electronic effect of Br has a large effect on the kinetics and leads to the change in reaction orders.

  8. 4,4′-Di-tert-butyl-2,2′-bipyridine

    Directory of Open Access Journals (Sweden)

    Tatiana R. Amarante

    2009-08-01

    Full Text Available In the title compound, C18H24N2, the molecular unit adopts a trans conformation around the central C—C bond [N—C—C—N torsion angle of 179.2 (3°], with the two aromatic rings almost coplanar [dihedral angle of only 0.70 (4°]. The crystal packing is driven by co-operative contacts involving weak C—H...N and C—H...π interactions, and also the need to fill effectively the available space.

  9. New Ruthenium Complexes Based on Tetradentate Bipyridine Ligands for Catalytic Hydrogenation of Esters.

    Science.gov (United States)

    Wang, Fangyuan; Tan, Xuefeng; Lv, Hui; Zhang, Xumu

    2016-08-01

    New bipyridinemethanamine-containing tetradentate ligands and their corresponding ruthenium complexes have been synthesized. The synthesized complexes performed well in the hydrogenation of a variety of esters with high efficiency (TON up to 9700) giving alcohols in good yields. PMID:27385062

  10. Catalytic asymmetric allylation of aliphatic aldehydes by chiral bipyridine N,N'-dioxides

    Czech Academy of Sciences Publication Activity Database

    Hrdina, R.; Boyd, T.; Valterová, Irena; Hodačová, Jana; Kotora, Martin

    -, č. 20 (2008), s. 3141-3144. ISSN 0936-5214 Grant ostatní: GA MŠk(CZ) LC06070 Institutional research plan: CEZ:AV0Z40550506 Keywords : allylations * aldehydes * Lewis base * asymmetric catalysis * solvent effect Subject RIV: CC - Organic Chemistry Impact factor: 2.659, year: 2008

  11. Synthesis and Coordination Behavior of a Bipyridine Platinum(II) Complex with Thioglucose

    OpenAIRE

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

    2013-01-01

    This document is the Accepted Manuscript version of a Published Work that appeared in final form in Inorganic Chemistry, © American Chemical Society after peer review and technical editing by the publisher. To access the final edited and published work see http://dx.doi.org/10.1021/ic400287g

  12. Bridging function mediated intermetallic coupling in diruthenium-bis(bipyridine) complexes

    Indian Academy of Sciences (India)

    Soma Chakraborty; Biplab Mondal; Biprajit Sarkar; Goutam Kumar Lahiri

    2002-08-01

    The interactions of potentially dinucleating bridging functionalities (I-VI) with the ruthenium-bis(bypyridine) precursor [RuII(bpy)2(EtOH)2]2+ have been explored. The bridging functions I, II and VI directly result in the expected dinuclear complexes of the type [(bpy)2RuII{L}RuII(bpy)2]+ (1, 2, 7 and 8) ( = 0, = 4 and = -2, = 2). The bridging ligand III undergoes N-N or N-C bond cleavage reaction on coordination to the RuII(bpy)2 core which eventually yields a mononuclear complex of the type [(bpy)2RuII(L)]+, 3, where L = -OC6H3(R)C(R′)=N-H. However, the electrogenerated mononuclear ruthenium(III) congener, 3+ in acetonitrile dimerises to [(bpy)2RuIII {-OC6H3(R)C(R′)=N-N=(R′)C(R)C6H3O-}RuIII(bpy)2]4+ (4). In the presence of a slight amount of water content in the acetonitrile solvent the dimeric species (4) reduces back to the starting ruthenium(II) monomer (3). The preformed bridging ligand IV undergoes multiple transformations on coordination to the Ru(bpy)2 core, such as hydrolysis of the imine groups of IV followed by intermolecular head-to-tail oxidative coupling of the resultant amino phenol moieties, which in turn results in a new class of dimeric complex of the type [(bpy)2RuII {-OC6H4-N=C6H3(=NH)O-}RuII(bpy)2]2+ (5). In 5, the bridging ligand comprises of two , chelating binding sites each formally in the semiquinone level and there is a -benzoquinonediimine bridge between the metal centres. In complex 6, the preformed bridging ligand, 3,6-bis(3,5-dimethylpyrazol-1-yl)-1,2-dihydro-1,2,4,5- tetrazine, H2L (V) undergoes oxidative dehydrogenation to aromatic tetrazine based bridging unit, 3,6-bis(3,5-dimethylpyrazol-1-yl)-1,2,4,5-tetrazine, L. The detailed spectroelectrochemical aspects of the complexes have been studied in order to understand the role of the bridging units towards the intermetallic electronic coupling in the dinuclear complexes.

  13. Tetraaquatetrakis(4,4′-bipyridine dioxide-κOterbium(III octacyanidomolybdate(V

    Directory of Open Access Journals (Sweden)

    Su-Yan Qian

    2011-07-01

    Full Text Available In the title compound, [Tb(C10H8N2O24(H2O4][Mo(CN8], both metal atoms are eight-coordinated. The TbIII atom displays a dodecahedral geometry, while the MoV ion exhibits a distorted square-antiprismatic geometry. The Tb atoms are located on a special position of site symmetry overline{4}, whereas the Mo atoms are located on a twofold rotation axis. The cations are linked by O—H...O hydrogen bonds.

  14. Tetraaquatetrakis(4,4′-bipyridine dioxide-κOterbium(III octacyanidotungstate(V

    Directory of Open Access Journals (Sweden)

    Ying-Ying Chen

    2012-03-01

    Full Text Available In the title compound, [Tb(C10H8N2O24(H2O4][W(CN8], both metal atoms are eight-coordinated. The TbIII ion displays a dodecahedral geometry, while the Wv ion exhibits a distorted square-antiprismatic geometry. The Tb atoms are located on a special position of site symmetry -4, whereas the W atoms are located on a twofold rotation axis. The cations are linked by O—H...O hydrogen bonds. The title compound is isotypic with the corresponding and previously described Mo compound [Qian & Yuan (2011. Acta Cryst. E67, m845].

  15. Vitamin C derivatives as new coreactants for tris(2,2'-bipyridine)ruthenium(II) electrochemiluminescence

    International Nuclear Information System (INIS)

    Highlights: → Ru(bpy)32+ electrochemiluminescence of vitamin C derivatives have been investigated. → Ascorbyl phosphate and ascorbyl palmitate show intense electrochemiluminescence. → Ascorbyl 2-phosphate was detected with high sensitivity. → This study provides a new way to detect vitamin C derivatives. - Abstract: Vitamin C derivatives (VCDs) have been widely used as the alternative and stable sources of vitamin C, and accordingly exhibit many new applications, such as anti-tumor and central nervous system drug delivery. In this study, their Ru(bpy)32+ electrochemiluminescence (ECL) properties have been investigated for the first time using well-known ascorbyl phosphate and ascorbyl palmitate as representative VCDs. Ascorbyl phosphate and ascorbyl palmitate are VCDs with different substituted positions. Both of them increase Ru(bpy)32+ ECL, indicating that other VCDs may also enhance Ru(bpy)32+ ECL signal. The calibration plot for ascorbyl phosphate is linear from 3 x 10-6 to 1.0 x 10-3 M with a detection limit of 1.4 x 10-6 M at a signal-to-noise ratio of 3. The relative standard deviation is 3.6% for six replicate measurements of 0.01 mM ascorbyl 2-phosphate solution. The proposed method is about one order of magnitude more sensitive than electrochemical and UV-vis methods for the determination of ascorbyl phosphate, and is used successfully for the determination of ascorbyl phosphate in whitening and moisturising body wash.

  16. Bipyridine (2,2′-dipyridyl) potentiates Escherichia coli lethality induced by nitrogen mustard mechlorethamine

    Energy Technology Data Exchange (ETDEWEB)

    De Alencar, T.A.M.; Wilmart-Gonçalves, T.C.; Vidal, L.S.; Fortunato, R.S.; Leitão, A.C. [Laboratório de Radiobiologia Molecular (Brazil); Lage, C., E-mail: claudia_lage_dna@yahoo.com.br [Laboratório de Radiações em Biologia (Brazil)

    2014-07-15

    Highlights: • Reduction of Fe{sup 2+} ensues a respiratory burst to reduce the oxidized iron pool. • Through Harber–Weiss recycling, superoxide electrons can reduce oxidized iron. • Redox imbalance sensitized repair proficient Escherichia coli to mustard lethal crosslinks. • A stronger synergism impacted survival of a superoxide dismutase-deficient strain. • Anti-cancer cocktails added of an iron chelator may impact hypoxia and genotoxicity. - Abstract: Alkylating agents are used in anti-tumor chemotherapy because they bind covalently to DNA and generate adducts that may lead to cell death. Bifunctional (HN2) and monofunctional (HN1) nitrogen are two such agents, and HN2 was the first drug successfully employed in anti-leukemia chemotherapy. Currently, HN2 is used either alone or combined with other drugs to treat Hodgkin's disease. It is well known that several crosslinking agents require metabolic activation via reactive oxygen species (ROS) to exert their lethal effects. The objective of this work was therefore to determine whether the abovementioned mustards would also require metabolic activation to exert lethal action against Escherichia coli. For this purpose, we measured survival following exposure to HN2 in E. coli strains that were deficient in nucleotide excision repair (uvrA NER mutant), base excision repair (xthA nfo nth fpg BER mutant) or superoxide dismutase (sodAB mutant) activity. We also performed the same experiments in cells pretreated with an iron chelator (2,2′-dipyridyl, DIP). The NER and BER mutants were only sensitive to HN2 treatment (survival rates similar to those of the wild-type were achieved with 5-fold lower HN2 doses). However, wild-type and sodAB strains were not sensitive to treatment with HN2. In all tested strains, survival dropped by 2.5-fold following pretreatment with DIP compared to treatment with HN2 alone. Furthermore, DIP treatment increased ROS generation in both wild type and sodAB-deficient strains. Based on these data and on the survival of the SOD-deficient strain, we suggest that the increased production of ROS caused by Fe{sup 2+} chelation may potentiate the lethal effects of HN2 but not HN1. This potentiation may arise as a consequence of enhancement in the number of or modification of the type of lesions formed. No sensitization was observed for the non-crosslinkable HN2 analog, HN1.

  17. Graphene Nanoplatelets Outperforming Platinum as the Electrocatalyst in Co-Bipyridine-Mediated Dye-Sensitized Solar Cells

    Czech Academy of Sciences Publication Activity Database

    Kavan, Ladislav; Yum, J. H.; Grätzel, M.

    2011-01-01

    Roč. 11, č. 12 (2011), s. 5501-5506. ISSN 1530-6984 R&D Projects: GA MŠk LC510; GA AV ČR IAA400400804; GA AV ČR KAN200100801 Institutional research plan: CEZ:AV0Z40400503 Keywords : graphene * dye sensitized solar cell * cobalt redox shuttle Subject RIV: CG - Electrochemistry Impact factor: 13.198, year: 2011

  18. Study of solid extractants based on malonamides, diglycolamides, and bipyridines for the partitioning of minor actinides from high active wastes

    Science.gov (United States)

    Šul'Aková, J.; John, J.; Šebesta, F.

    2006-01-01

    In this work, the performance of the solid extractants with polyacrylonitrile (PAN) binding matrix was studied for the separation of lanthanides and actinides from nitric acid solutions. As extractants, incorporated into the PAN matrix, the N,N‧-dimethyl-N,N‧-dibutyltetradecylmalonamide (DMDBTDMA), N,N‧-dimethyl-N,N‧-dioctyl-hexy-loxyethylmalonamide (DMDOHEMA), N,N,N‧,N‧-tetraoctyldiglycolamide (TODGA), 6,6‧-bis-(5,6-dipentyl-[1,2,4]triazin-3-yl[2,2‧]bipyridinyl (C5BTBP) were used. Weight distribution coefficients Dg of europium and several actinides have been determined for all the composite materials. The kinetics of europium uptake, practical dynamic extraction capacities, and extraction isotherms were also determined. The results obtained revealed that the solid extractants studied are prospective for the partitioning of lanthanides and actinides from liquid radioactive wastes.

  19. Characterization of electrochemiluminescence of tris(2,2'-bipyridine)ruthenium(II) with glyphosate as coreactant in aqueous solution

    Energy Technology Data Exchange (ETDEWEB)

    Jin, Jiye, E-mail: jin@shinshu-u.ac.j [Department of Chemistry, Faculty of Science, Shinshu University, 3-1-1 Asahi, Matsumoto, Nagano 390-8621 (Japan); Takahashi, Fumiki; Kaneko, Tsutomu; Nakamura, Toshio [Department of Chemistry, Faculty of Science, Shinshu University, 3-1-1 Asahi, Matsumoto, Nagano 390-8621 (Japan)

    2010-08-01

    Glyphosate, a phosphorus-containing amino acid type herbicide was used as a coreactant for studying of electrochemiluminescence (ECL) reaction of tris(2,2'-bipyridyl)ruthenium(II) [Ru(bpy){sub 3}{sup 2+}] in an aqueous solution. In a phosphate buffer solution of pH 8, glyphosate itself was known to be electrochemically inactive at glassy carbon electrode, however, it participated in a homogeneous chemical reaction with the electrogenerated Ru(bpy){sub 3}{sup 3+}, and resulted in producing Ru(bpy){sub 3}{sup 2+} species at the electrode surface. Kinetic and mechanistic information for the catalysis of glyphosate oxidation were evaluated by the steady-state voltammetric measurement with an ultramicroelectrode. The simulated cyclic voltammogram based on this mechanism was in good agreement with that obtained experimentally. ECL reaction of Ru(bpy){sub 3}{sup 2+}/glyphosate system was found to be strongly dependent on the media pH. In a pH region of 5-9, an ECL wave appeared at ca. +1.1 V vs. Ag/AgCl, which was caused by the generation of *Ru(bpy){sub 3}{sup 2+} via a Ru(bpy){sub 3}{sup 3+}-mediated oxidation of glyphosate. When pH >10, a second ECL wave was observed at ca. +1.35 V vs. Ag/AgCl, which was believed to be associated with a reaction between Ru(bpy){sub 3}{sup 3+} and the species from direct oxidation of GLYP at a GC electrode surface.

  20. Host–guest complexes of mixed glycol-bipyridine cryptands: prediction of ion selectivity by quantum chemical calculations, part V

    OpenAIRE

    Svetlana Begel; Ralph Puchta; Rudi van Eldik

    2013-01-01

    The selectivity of the cryptands [2.2.bpy] and [2.bpy.bpy] for the endohedral complexation of alkali, alkaline-earth and earth metal ions was predicted on the basis of the DFT (B3LYP/LANL2DZp) calculated structures and complex-formation energies. The cavity size in both cryptands lay between that for [2.2.2] and [bpy.bpy.bpy], such that the complexation of K+, Sr2+ and Tl3+ is most favorable. While the [2.2.bpy] is moderately larger, preferring Rb+ complexation and demonstrating equal priorit...

  1. Design, Synthesis and Properties of Bipyridine-capped Oligothiophenes for Directed Energy and Electron Transfer in Molecular Electronic Applications

    OpenAIRE

    Nurkkala, Lasse

    2007-01-01

    The earliest landmark in computer technology was construction of the Electronic Numerial Integrator and Computer, ENIAC. Computational switching was performed with vacuum tubes and relays, rather large in size, making this computer rather unwieldy. The next milestone came with the integration of transistors into computers as the switching component. Since then, transistors have been miniaturised dramatically, resulting in the amount of components integrated on a computer chip increasing logar...

  2. Characterization of electrochemiluminescence of tris(2,2'-bipyridine)ruthenium(II) with glyphosate as coreactant in aqueous solution

    International Nuclear Information System (INIS)

    Glyphosate, a phosphorus-containing amino acid type herbicide was used as a coreactant for studying of electrochemiluminescence (ECL) reaction of tris(2,2'-bipyridyl)ruthenium(II) [Ru(bpy)32+] in an aqueous solution. In a phosphate buffer solution of pH 8, glyphosate itself was known to be electrochemically inactive at glassy carbon electrode, however, it participated in a homogeneous chemical reaction with the electrogenerated Ru(bpy)33+, and resulted in producing Ru(bpy)32+ species at the electrode surface. Kinetic and mechanistic information for the catalysis of glyphosate oxidation were evaluated by the steady-state voltammetric measurement with an ultramicroelectrode. The simulated cyclic voltammogram based on this mechanism was in good agreement with that obtained experimentally. ECL reaction of Ru(bpy)32+/glyphosate system was found to be strongly dependent on the media pH. In a pH region of 5-9, an ECL wave appeared at ca. +1.1 V vs. Ag/AgCl, which was caused by the generation of *Ru(bpy)32+ via a Ru(bpy)33+-mediated oxidation of glyphosate. When pH >10, a second ECL wave was observed at ca. +1.35 V vs. Ag/AgCl, which was believed to be associated with a reaction between Ru(bpy)33+ and the species from direct oxidation of GLYP at a GC electrode surface.

  3. Osmium tetroxide, 2,2’-bipyridine: Electroactive marker for probing accessibility of tryptophan residues in proteins

    Czech Academy of Sciences Publication Activity Database

    Fojta, Miroslav; Billová, Sabina; Havran, Luděk; Pivoňková, Hana; Černocká, Hana; Horáková Brázdilová, Petra; Paleček, Emil

    2008-01-01

    Roč. 80, č. 12 (2008), s. 4598-4605. ISSN 0003-2700 R&D Projects: GA MŠk(CZ) LC06035; GA AV ČR(CZ) IAA4004402; GA AV ČR(CZ) 1QS500040581; GA AV ČR(CZ) KAN400310651 Institutional research plan: CEZ:AV0Z50040507; CEZ:AV0Z50040702 Keywords : osmium tetroxide * chemical modification * tryptophan Subject RIV: BO - Biophysics Impact factor: 5.712, year: 2008

  4. Vitamin C derivatives as new coreactants for tris(2,2'-bipyridine)ruthenium(II) electrochemiluminescence

    Energy Technology Data Exchange (ETDEWEB)

    Yuan Yali; Li Haijuan; Han Shuang; Hu Lianzhe [State Key Laboratory of Electroanalytical Chemistry, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, Changchun, Jilin 130022 (China); Graduate University of the Chinese Academy of Sciences, Beijing 100864 (China); Parveen, Saima [State Key Laboratory of Electroanalytical Chemistry, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, Changchun, Jilin 130022 (China); Graduate University of the Chinese Academy of Sciences, Beijing 100864 (China); Department of Chemistry, Baghdad-ul-Jadeed Campus, The Islamia University of Bahawalpur, Bahawalpur (Pakistan); Xu Guobao, E-mail: guobaoxu@ciac.jl.cn [State Key Laboratory of Electroanalytical Chemistry, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, Changchun, Jilin 130022 (China)

    2011-09-09

    Highlights: {yields} Ru(bpy){sub 3}{sup 2+} electrochemiluminescence of vitamin C derivatives have been investigated. {yields} Ascorbyl phosphate and ascorbyl palmitate show intense electrochemiluminescence. {yields} Ascorbyl 2-phosphate was detected with high sensitivity. {yields} This study provides a new way to detect vitamin C derivatives. - Abstract: Vitamin C derivatives (VCDs) have been widely used as the alternative and stable sources of vitamin C, and accordingly exhibit many new applications, such as anti-tumor and central nervous system drug delivery. In this study, their Ru(bpy){sub 3}{sup 2+} electrochemiluminescence (ECL) properties have been investigated for the first time using well-known ascorbyl phosphate and ascorbyl palmitate as representative VCDs. Ascorbyl phosphate and ascorbyl palmitate are VCDs with different substituted positions. Both of them increase Ru(bpy){sub 3}{sup 2+} ECL, indicating that other VCDs may also enhance Ru(bpy){sub 3}{sup 2+} ECL signal. The calibration plot for ascorbyl phosphate is linear from 3 x 10{sup -6} to 1.0 x 10{sup -3} M with a detection limit of 1.4 x 10{sup -6} M at a signal-to-noise ratio of 3. The relative standard deviation is 3.6% for six replicate measurements of 0.01 mM ascorbyl 2-phosphate solution. The proposed method is about one order of magnitude more sensitive than electrochemical and UV-vis methods for the determination of ascorbyl phosphate, and is used successfully for the determination of ascorbyl phosphate in whitening and moisturising body wash.

  5. cis-Aquabis(2,2′-bipyridine-κ2N,N′fluoridochromium(III bis(perchlorate dihydrate

    Directory of Open Access Journals (Sweden)

    Torben Birk

    2010-02-01

    Full Text Available The title mixed aqua–fluoride complex, [CrF(C10H8N22(H2O](ClO42·2H2O, has been synthesized by aquation of the corresponding difluoride complex using lanthanide(III ions as F− acceptors. The complex crystallizes with a CrIII ion at the center of a distorted octahedral coordination polyhedron with a cis arrangement of ligands. The crystal packing shows a hydrogen-bonding pattern involving water molecules, the coordinated F atom and the perchlorate anions

  6. Aquabis(3′-hydroxy-2,2′-bipyridine-3-olato-κ2N,N′)zinc(II)

    OpenAIRE

    Chao Hou; Shi Guo Zhang

    2008-01-01

    In the title complex, [Zn(C10H7N2O2)2(H2O)], the ZnII ion and water O atom are located on a crystallographic twofold rotation axis and the metal atom assumes a distorted trigonal-bipyramidal ZnN4O coordination geometry. An intramolecular O—H...O hydrogen bond occurs within the ligand and intermolecular O—H...O hydrogen bonds involving the water molecule result in a sheet structure in the crystal structure. In addition, a short C—O...π contact between the O atom of the d...

  7. Aqua­bis(3′-hydr­oxy-2,2′-bipyridine-3-olato-κ2 N,N′)zinc(II)

    OpenAIRE

    Zhang, Shi Guo; Hou, Chao

    2008-01-01

    In the title complex, [Zn(C10H7N2O2)2(H2O)], the ZnII ion and water O atom are located on a crystallographic twofold rotation axis and the metal atom assumes a distorted trigonal-bipyramidal ZnN4O coordination geometry. An intra­molecular O—H⋯O hydrogen bond occurs within the ligand and inter­molecular O—H⋯O hydrogen bonds involving the water mol­ecule result in a sheet structure in the crystal structure. In addition, a short C—O⋯π contact between the O atom of the deprotonated hydroxyl group...

  8. 1,1′-Bicyclohexyl-1,1′-diyl 2,2′-bipyridine-3,3′-dicarboxylate

    Directory of Open Access Journals (Sweden)

    Hoong-Kun Fun

    2012-06-01

    Full Text Available The title compound, C24H26N2O4, lies about a crystallographic twofold rotation axis. The cyclohexane rings adopts a chair conformation. The two pyridine rings form a dihedral angle of 41.02 (4°. In the crystal, molecules are linked via C—H...O and C—H...N hydrogen bonds into a layer parallel to the bc plane.

  9. Selective oxidation of benzyl alcohol with tert-butylhydroperoxide catalysed via Mn (II) 2, 2-bipyridine complexes immobilized over the mesoporous hexagonal molecular sieves (HMS)

    Indian Academy of Sciences (India)

    Vahid Mahdavi; Mahdieh Mardani

    2012-09-01

    A series ofMn(II)bipy complexes with different loading of Mn2+ supported on HMS was prepared. These samples were characterized by Brunauer-Emmett-Teller (BET), X-ray diffraction (XRD), Thermogravimetric and Differential Scanning Calorimetry (TG-DSC), Ultraviolet and Visible spectra (UV-Vis) and Fourier transforms Infrared (FT-IR). The catalytic activity of the supportedMn(II)bipy complexes, [Mn(bipy)2]2+/HMS was evaluated in the oxidation of benzyl alcohol in the liquid phase using tert-butylhydroperoxide (TBHP) as an oxidant. The effects of Mn2+ loading and various solvents on the conversion and selectivity were studied. A second order function for the variation in catalytic activity with respect to the loading of Mn2+ ions in different catalyst samples was observed. The activity of the [Mn(bipy)2]2+/HMS catalyst differs with the type of the solvent and in this case, acetonitrile gives the best conversion results. The kinetic of benzyl alcohol oxidation was investigated at temperatures of 27, 46, 60, 75 and 90°C using [Mn(bipy)2]2+/HMS and excess TBHP. The order of reaction with respect to benzyl alcohol was determined to be pseudo-first order. The value of the apparent activation energy was also determined.

  10. Electrogenerated chemiluminescence reaction of tris(2,2'-bipyridine)ruthenium(II) with 2,5-dimethylthiophene as co-reactant in aqueous solution

    International Nuclear Information System (INIS)

    A novel effective co-reactant for electrogenerated chemiluminescence (ECL) of Ru(bpy)32+ has been found. α-Position-dialkylated thiophene derivatives such as 2,5-dimethylthiophene (DMT) could be used as a co-reactant for Ru(bpy)32+ ECL. The reaction mechanism of the Ru(bpy)32+/DMT system was proposed on the basis of the identification of the reaction product, the relationship between the molecular structure and the chemiluminescent intensity, and the electrochemical study. The obtained reaction mechanism was similar to that of the Ru(bpy)32+/aliphatic tertiary amine system. Based on these results, the preliminary studies of the Ru(bpy)32+ ECL detection system using DMT as a co-reactant were performed. Under the optimal ECL conditions, the plot of ECL intensity versus the concentration of Ru(bpy)32+ was linear over the concentration range 1.0 x 10-8 to 1.5 x 10-7 M (determination coefficient = 0.9996)

  11. Synthesis, structures, spectroscopy and antimicrobial properties of complexes of copper(II) with salicylaldehyde N-substituted thiosemicarbazones and 2,2'-bipyridine or 1,10-phenanthroline.

    Science.gov (United States)

    Lobana, Tarlok S; Indoria, Shikha; Jassal, Amanpreet Kaur; Kaur, Harpreet; Arora, Daljit S; Jasinski, Jerry P

    2014-04-01

    Among the biometals (Cu, Co, Ni-cofactors in many enzymes), copper derivatives of O, N, S-donor salicylaldehyde thiosemicarbazones have received considerable attention owing to their potential biological applications. Eight new complexes of salicylaldehyde-N-substituted thiosemicarbazones [5-MeO-2-HO-C₆H₄-C(2)(H)N(3)-N(2)H-C(1)(S)-N(1)HR; R = Me, H2L(1); Et, H₂L(1), Ph, H₂L(3), H, H₂L(4)] with copper(II), namely, [Cu(κ(3)-O,N,S-L)( κ(2)-N,N-L')] {(L)(2-) = (L(1))(2-), L' = bipy, 1, phen, 2; (L)(2-) = (L(2))(2-), L' = bipy, 3, phen, 4; (L)(2-) = (L(3))(2-), L' = bipy, 5, phen, 6; (L)(2-) = (L(4))(2-), L' = bipy, 7, phen, 8} have been isolated. Complexes have slightly distorted square pyramidal geometry around the metal center (τ parameter = 0.243-0.357) and display weak to intense fluorescence in the region, 375-475 nm. These copper complexes have shown significant growth inhibitory activity (antimicrobial activity) against Staphylococcus aureus (MTCC740), methicillin resistant Staphylococcus aureus (MRSA), Klebsiella pneumoniae 1 (MTCC109), Shigella flexneri (MTCC1457), Pseudomonas aeruginosa (MTCC741) and Candida albicans (MTCC227). The activity against MRSA is an interesting observation as the commercially available gentamycin is found to be inactive against this bacterial strain. Specifically complex 5 formed by 5-methoxysalicylaldehyde-N-phenylthiosemicatbazone has shown novel antimicrobial activity against various bacteria and yeast investigated. PMID:24583354

  12. Self-assembly of metalloporphyrins: first TPP-bipy coordination polymer with CoII (TPP=meso-tetraphenylporphyrin and bipy=4,4´-bipyridine)

    OpenAIRE

    Fidalgo Marijuan, Arkaitz; Barandika Argoitia, Miren Gotzone; Bazán Blau, Begoña del Pilar; Urtiaga Greaves, Miren Karmele; Arriortua Marcaida, María Isabel

    2015-01-01

    Póster presentado en: 11th International Symposium on Applied Bioinorganic Chemistry. 2-5 Diciembre 2011. Barcelona, España (ISABC 2011) Supramolecular entities based on self-assembly of metalloporphyrins are paradigmatic examples of the great efficiency of the nanodevices used by natural systems in photosynthesis, oxygen transport, electron transfer and catalysis. Obtaining supramolecular entities may be approached by different strategies of synthetic design. One of them consists on t...

  13. Reversible and pH dependent photophysical properties of mixed-ligand Ru(II) complexes containing 2,20-bipyridine and nitrosobarbiturate: Experimental and theoretical approach

    Czech Academy of Sciences Publication Activity Database

    Dixit, N.; Záliš, Stanislav; Maiti, B.; Mishra, L.

    2013-01-01

    Roč. 404, AUG 2013 (2013), s. 123-130. ISSN 0020-1693 Institutional support: RVO:61388955 Keywords : Mixed-ligand Ru(II) complex * spectroscopy * X-ray diffraction Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 2.041, year: 2013

  14. Molecular wiring of olivine LiFePO4 by ruthenium(II)-bipyridine complexes and by their assemblies with single-walled carbon nanotubes

    Czech Academy of Sciences Publication Activity Database

    Kavan, Ladislav; Exnar, I.; Zakeeruddin, S. M.; Graetzel, M.

    2008-01-01

    Roč. 112, č. 23 (2008), s. 8708-8714. ISSN 1932-7447 R&D Projects: GA MŠk LC510; GA MŠk 1P05OC069; GA AV ČR IAA400400804; GA AV ČR KAN200100801 Institutional research plan: CEZ:AV0Z40400503 Keywords : molecular wiring * LiFePO4 * carbon nanotube Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 3.396, year: 2008

  15. Interaction with biomacromolecules and antiproliferative activities of Mn(II), Ni(II), Zn(II) complexes of demethylcantharate and 2,2'-bipyridine

    Science.gov (United States)

    Zhang, Fan; Lin, Qiu-Yue; Hu, Wan-Li; Song, Wen-Ji; Shen, Shu-Ting; Gui, Pan

    2013-06-01

    Three new transition metal complexes [Mn2(DCA)2(bipy)2]·5H2O (1), [M2(DCA)2(bipy)2(H2O)]·10H2O(M = Ni(II)(2);Zn(II)(3)), (DCA = demethylcantharate, 7-oxabicyclo[2,2,1]heptane-2,3-dicarboxylate, C8H8O5) were synthesized and characterized by elemental analysis, molar conductance, infrared spectra and X-ray diffraction techniques. Each metal ion was six-coordinated in complexes. Complex 1 has a Mn2O2 center. Complexes 2 and 3 have asymmetric binuclear structure. Great amount of intermolecular hydrogen-bonding and π-π* stacking interactions were formed in these complex structures. The DNA-binding properties of complexes were investigated by electronic absorption spectra and viscosity measurements. The DNA binding constants Kb/(L mol-1) were 1.71 × 104 (1), 2.62 × 104 (2) and 1.59 × 104 (3) at 298 K. The complexes could quench the intrinsic fluorescence of bovine serum albumin (BSA) strongly through static quenching. The protein binding constants Ka/(L mol-1) were 7.27 × 104 (1), 4.55 × 104 (2) and 7.87 × 104 L mol-1 (3) and binding site was one. The complexes bind more tightly with DNA and BSA than with ligands. Complexes 1 and 3 had stronger inhibition ratios than Na2(DCA) against human hepatoma cells (SMMC-7721) lines and human gastric cancer cells (MGC80-3) lines in vitro. Complex 3 showed the strongest antiproliferative activity against SMMC-7721 (IC50 = 29.46 ± 2.12 μmol L-1) and MGC80-3 (IC50 = 27.02 ± 2.38 μmol L-1), which shows potential in anti-cancer drug development.

  16. Bipyridine- and phenanthroline-based metal-organic frameworks for highly efficient and tandem catalytic organic transformations via directed C-H activation

    Energy Technology Data Exchange (ETDEWEB)

    Manna, Kuntal [Univ. of Chicago, Chicago, IL (United States); Zhang, Teng [Univ. of Chicago, Chicago, IL (United States); Greene, Francis X. [Univ. of Chicago, Chicago, IL (United States); Lin, Wenbin [Univ. of Chicago, Chicago, IL (United States)

    2015-02-16

    We report here the synthesis of a series of robust and porous bipyridyl- and phenanthryl-based metal–organic frameworks (MOFs) of UiO topology (BPV-MOF, mBPV-MOF, and mPT-MOF) and their postsynthetic metalation to afford highly active single-site solid catalysts. While BPV-MOF was constructed from only bipyridyl-functionalized dicarboxylate linker, both mBPV- and mPT-MOF were built with a mixture of bipyridyl- or phenanthryl-functionalized and unfunctionalized dicarboxylate linkers. The postsynthetic metalation of these MOFs with [Ir(COD)(OMe)]2 provided Ir-functionalized MOFs (BPV-MOF-Ir, mBPV-MOF-Ir, and mPT-MOF-Ir), which are highly active catalysts for tandem hydrosilylation of aryl ketones and aldehydes followed by dehydrogenative ortho-silylation of benzylicsilyl ethers as well as C–H borylation of arenes using B₂pin₂. Both mBPV-MOF-Ir and mPT-MOF-Ir catalysts displayed superior activities compared to BPV-MOF-Ir due to the presence of larger open channels in the mixed-linker MOFs. Impressively, mBPV-MOF-Ir exhibited high TONs of up to 17000 for C–H borylation reactions and was recycled more than 15 times. The mPT-MOF-Ir system is also active in catalyzing tandem dehydrosilylation/dehydrogenative cyclization of N-methylbenzyl amines to azasilolanes in the absence of a hydrogen acceptor. Importantly, MOF-Ir catalysts are significantly more active (up to 95 times) and stable than their homogeneous counterparts for all three reactions, strongly supporting the beneficial effects of active site isolation within MOFs. This work illustrates the ability to increase MOF open channel sizes by using the mixed linker approach and shows the enormous potential of developing highly active and robust single-site solid catalysts based on MOFs containing nitrogen-donor ligands for important organic transformations.

  17. Synthesis, 2D NMR, electrochemistry and luminescence of ruthenium (II) complexes with 2,2-bipyridine and 5-(ω-bromoalkylamido)-1, 10-phenanthroline

    International Nuclear Information System (INIS)

    The efficient synthesis of 5-(5-bromovaleramido)-1, 10-phenanthroline, 5-(6-bromohexanamido)-1,10-phenanthroline, and 5-(11-bromoundecanamido)-1, 10-phenanthroline are described, which reacted with cis-Ru(bpy)2Cl2.2H2O and sodium hexafluorophosphate to form Ru(bpy)2[phen-NHCO(CH2)nBr](PF6)2 (n=4, 5 or 10; phen=1,10-phenanthroline). The intricate 1H NMR spectra at low field of these complexes were completely assigned in virtue of 1H-1H COSY technique. Cyclic voltammetry was used to study electrochemical behaviours of these complexes, and their luminescent properties were investigated with fluorescent spectra. (author)

  18. Derivatisation of peptides with osmium tetroxide, 2,2´-bipyridine: capillary electrophoretic and MALDI-TOF mass spectrometric study

    Czech Academy of Sciences Publication Activity Database

    Šedo, O.; Billová, Sabina; Peńa-Méndez, E. M.; Paleček, Emil; Havel, J.

    2004-01-01

    Roč. 515, č. 2 (2004), s. 261-269. ISSN 0003-2670 R&D Projects: GA ČR GA305/03/1100; GA ČR GA204/03/0566 Institutional research plan: CEZ:AV0Z5004920 Keywords : peptide derivatisation * osmium tetroxide * CZE Subject RIV: BO - Biophysics Impact factor: 2.588, year: 2004

  19. cis-Aquabis(2,2'-bipyridine2N,N')-fluoridochromium(III) bis(perchlorate) dihydrate

    DEFF Research Database (Denmark)

    Birk, Torben; Bendix, Jesper

    2010-01-01

    The title mixed aqua-fluoride complex, [CrF(C(10)H(8)N(2))(2)(H(2)O)](ClO(4))(2)·2H(2)O, has been synthesized by aqua-tion of the corresponding difluoride complex using lanthan-ide(III) ions as F(-) acceptors. The complex crystallizes with a Cr(III) ion at the center of a distorted octa......-hedral coordination polyhedron with a cis arrangement of ligands. The crystal packing shows a hydrogen-bonding pattern involving water mol-ecules, the coordinated F atom and the perchlorate anions....

  20. Crystal structure of poly[[μ3-4,4′-(4,4′-bipyridine-2,6-diyl)dibenzoato]{μ2-4-[6-(4-carboxyphenyl)-4,4′-bipyridin-4′-ium-2-yl]benzoato}manganese(II)] hemi­hydrate

    OpenAIRE

    Li, Yaping; Sun, Dajun; Ming, Julia; Han, Liying; Su, Guanfang

    2014-01-01

    The title compound, {[Mn(C24H14N2O4)(C24H16N2O4)]·0.5H2O} n , was obtained by the reaction of manganese nitrate with the ligand 4,4′-(4,4′-bi­pyridine-2,6-di­yl) di­benzoic acid under hydro­thermal conditions. The water O atom is located on a twofold rotation axis. The Mn2+ ion is hepta­coordinated by six O atoms and one N atom from the ligands. In this structure, the ligands adopts two different forms, one completely deprotonated and one with a protonated N atom (pyridinium) and a carboxylic...

  1. (2,2 '-Bipyridine-4,4 '-dicarboxylic acid-kappa N-2,N ')chlorido(2,2 ':6 ',2 ''-terpyridyl-kappa N-3,N ',N '')ruthenium(II) perchlorate ethanol monosolvate monohydrate

    DEFF Research Database (Denmark)

    Nielsen, A.; McKenzie, C. J.; Bond, A. D.

    2012-01-01

    In the title compound, [RuCl(C15H11N3)(C12H8N2O4)]ClO4 center dot C2H5OH center dot H2O, the geometry of the ClN5 coordination set around the Ru-II atom is close to octahedral, but distorted on account of the limited bite angles of the polypyridyl ligands. The complexes are linked by O-H center d...

  2. Periphery-palladated carbosilane dendrimers : Synthesis and reactivity of model organopalladium(II) and (IV) complexes : Crystal structure of [PdMe(C6H4(OCH2Ph)-4)(bpy)] (bpy=2,2'-bipyridine

    OpenAIRE

    van Koten, G; Hovestad, N.J.; Hoare, J.L.; Jastrzebski, J.T.B.H.; Canty, A.J.; Smeets, W.J.J.; Spek, A.L.

    1999-01-01

    A carbosilane dendrimer with 12 peripheral iodoarene groups, [Si{(CH2)3Si((CH2)3SiMe2(C6H4CH2OC6H4I-4))3}4] (G1-ArI, 9), and the corresponding G0 model compound [Si{(CH2)3SiMe2(C6H4CH2OC6H4I-4)}4] (G0-ArI, 8) have been prepared from [Si{(CH2)3Si((CH2)3SiMe2(C6H4CH2Br))3}4] (G1-Br, 7) and the corresponding G0 model compound [Si{(CH2)3SiMe2(C6H4CH2Br)}4] (G0-Br, 6). These dendritic species react with [Pd2(dba)3·dba/tmeda] (dba = dibenzylideneacetone, tmeda = N,N,N',N'-tetramethylethylenediamine...

  3. Anharmonicity Effects in IR Spectra of [Re(X)(CO)(3)(alpha-diimine)] (alpha-diimine=2,2 '-bipyridine or pyridylimidazo[1,5-a]pyridine; X = Cl or NCS) Complexes in Ground and Excited Electronic States

    Czech Academy of Sciences Publication Activity Database

    Kvapilová, Hana; Vlček Jr., Antonín; Barone, V.; Biczysko, M.; Záliš, Stanislav

    2015-01-01

    Roč. 119, č. 40 (2015), s. 10137-10146. ISSN 1089-5639 R&D Projects: GA MŠk LD14129 Institutional support: RVO:61388955 Keywords : RESOLVED INFRARED-SPECTROSCOPY * TRANSITION-METAL-COMPLEXES * LARGE MOLECULAR- SYSTEMS Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 2.693, year: 2014

  4. Theoretical studies on the geometrical and electronic structures of supramolecule bis(2,2‧-bipyridine)-5-amino-1,10-phenanthroline ruthenium(II)/functionalized SWCNT dyads

    Science.gov (United States)

    Ahmadnezhad, M.; Darvish Ganji, M.; Rezvani, M.

    2015-11-01

    Functionalization of carbon nanotube (CNT) with multiple redox and photo active entities is one of the extensive processes due to its importance in building molecular or supramolecular electronic devices, solar energy storage and conversion systems. Thus, to have better understanding about structural aspects and correct electronic structure of these large systems, the quantum studies have gained increased popularity. In present study, we have investigated the structural and electronic properties of functionalized CNTs (fCNTs) with [Ru(bpy)2(5-NH2-1,10-phen)]+2, (Ru-bpy-phen)+2, supramolecule based on DFT calculations. Main attention has been applied to obtain stable configuration, binding energies and effect of functionalization on electronic behavior of the selected supramolcule. We also evaluate the effect of nanotube's diameter and chirality on electronic properties of considered supramolecule. Calculated binding energies show that interaction between the (Ru-bpy-phen)+2 and the host CNTs depends on the tube diameter while the chirality doesn't affect significantly on the binding nature of respected complex. We have also investigated the influence of non-local dispersion interactions (vdW) and temperature on the stability and electronic structure of the considered system. Results obtained from the ab initio MD simulations showed that increasing the temperature can affect the distance between C and N atoms in the linkage position. The charge analysis indicates the existence of remarkable charge transfer between (Ru-bpy-phen)+2 as donor and fCNTs as acceptor moieties in the isolated molecule. In the presence of vdW forces and at higher temperature, the charge transfer was decreased but the direction of transferred charge remains unchanged.

  5. 1,1'-Diethyl-4,4'-bipyridine-1,1'-diium bis(1,1,3,3-tetracyano-2- ethoxypropenide) : multiple C-H⋯N hydrogen bonds form a complex sheet structure

    OpenAIRE

    Setifi, Z.; Lehchili, F.; Setifi, F.; Beghidja, A.; Ng, S W; Glidewell, C.

    2014-01-01

    The authors acknowledge the Algerian ATRST (Agence The´matique de Recherche en Sciences et Technologie; PNR project) and the Ministry of Higher Education of Malaysia (grant No. UM.C/HIR-MOHE/SC/03) for financial support.

  6. Influence of diluent alkyl substitution on the extraction of Am(III) and Eu(III) by a 6,6'-bis(1,2,4-triazin-3-yl)-2,2'-bipyridine ligand dissolved in alkylated cyclohexanone diluents

    International Nuclear Information System (INIS)

    Several alkylated cyclohexanones were investigated as potential diluents for the selective extraction of Am(III) from Eu(III) from nitric acid solutions by the CyMe4-BTBP ligand. No significant extraction of either of the metal ions was observed for these diluents themselves. In the extractions from 1 M HNO3, 3-methylcyclohexanone and 4-methylcyclohexanone gave comparable results to cyclohexanone whereas in the extractions from 4 M HNO3, 2-methylcyclohexanone, 3-methylcyclohexanone and 4-methylcyclohexanone all gave superior results. For the monomethylated diluents, DAm and SFAm/Eu decreased in the order of alkyl substitution 2 > 4 ∝ 3. However, alkyl substitution of cyclohexanone significantly slows down the extraction kinetics compared to cyclohexanone, and the position of alkyl substitution was found to play an important role in the solvents properties. 3-Methylcyclohexanone was identified as the most promising of the diluents. (orig.)

  7. MOF Formation vs. Reversible High Ligand Uptake in Anhydrous Halides: Two Opposing Aspects of 3[La2Cl6(4,4'-bipy)5]•4(4,4'-bipy)

    OpenAIRE

    Höller, Christoph J.; Matthes, Philipp; Beckmann, Jens; Mueller-Buschbaum, Klaus

    2009-01-01

    Abstract Construction of the framework structure 3?[La2Cl6(4,4?-bipy)5]?4(4,4?-bipy) (1), bipy = 4,4'-bipyridine, C10H8N2, is achieved by reaction of the anhydrous halide LaCl3 with molten 4,4'-bipyridine. Five equivalents of bipyridine are used for the framework construction linking LaCl3 units to give an extended, three-dimensional MOF. Furthermore four additional equivalents of bipyridine per LaCl3 unit are incorporated within the crystalline MOF, which is thereby completely fi...

  8. Fermi level alignment in molecular nanojunctions and its relation to charge transfer

    DEFF Research Database (Denmark)

    Stadler, Robert; Jacobsen, Karsten Wedel

    2006-01-01

    by orders of magnitude. We present a quantitative analysis of the relation between this level alignment (which can be estimated from charging free molecules) and charge transfer for bipyridine and biphenyl dithiolate (BPDT) molecules attached to gold leads based on density functional theory...... energetically higher end of the gap in the transmission function for bipyridine and at its lower end for BPDT....

  9. Métodos sintéticos para preparação de 2,2'-bipiridinas substituídas

    Directory of Open Access Journals (Sweden)

    Donnici Claudio Luis

    2002-01-01

    Full Text Available The 2,2'-bipyridine has been entitled as the most widely used ligand. Nowadays there is a large variety of known molecules comprising at least two 2,2'-bipyridine units and the number of applications in many areas such as catalysis, new materials, optoeletronics and electrochemistry have increased very much in the past decades. Nevertheless, there is no article that gives an overview of the main synthetic methods for obtaining the substituted 2,2'-bipyridines, generally non available. This article presents a synthetic discussion about the three different methods (coupling reaction, ciclo-functionalization and functionalization of the heteroaromatic rings of 2,2'-bipyridine for preparing these heterocyclic compounds and also provides a practical and fundamental guide, for obtaining more than eighty different symmetric and unsymmetrical substituted 2,2'-bipyridines, shown in a table with the corresponding references.

  10. Coupling of the 4f Electrons in Lanthanide Molecules

    Energy Technology Data Exchange (ETDEWEB)

    Kazhdan, Daniel

    2008-09-12

    (C5Me5)2LnOTf where Ln = La, Ce, Sm, Gd, and Yb have been synthesized and these derivatives are good starting materials for the synthesis of (C5Me5)2LnX derivatives. (C5Me5)2Ln(2,2'-bipyridine), where Ln = La, Ce, Sm, and Gd, along with several methylated bipyridine analogues have been synthesized and their magnetic moments have been measured as a function of temperature. In lanthanum, cerium, and gadolinium complexes the bipyridine ligand ligand is unequivocally the radical anion, and the observed magnetic moment is the result of intramolecular coupling of the unpaired electron on the lanthanide fragment with the unpaired electron on the bipyridine along with the intermolecular coupling between radicals. Comparison with the magnetic moments of the known compounds (C5Me5)2Sm(2,2'-bipyridine) and (C5Me5)2Yb(2,2'-bipyridine) leads to an understanding of the role of the Sm(II)/Sm(III) and Yb(II)/Yb(III) couple in the magnetic properties of (C5Me5)2Sm(2,2'-bipyridine) and (C5Me5)2Yb(2,2'-bipyridine). In addition, crystal structures of (C5Me5)2Ln(2,2'-bipyridine) and [(C5Me5)2Ln(2,2'-bipyridine)][BPh4](Ln= Ce and Gd), where the lanthanide is unequivocally in the +3 oxidation state, give the crystallographic characteristics of bipyridine as an anion and as a neutral ligand in the same coordination environment, respectively. Substituted bipyridine ligands coordinated to (C5Me5)2Yb are studied to further understand how the magnetic coupling in (C5Me5)2Yb(2,2'-bipyridine) changes with substitutions. In the cases of (C5Me5)2Yb(5,5'-dimethyl-2,2'-bipyridine) and (C5Me5)2Yb(6-methyl-2,2'-bipyridine), the valence, as measured by XANES, changes as a function of temperature. In general, the magnetism in complexes of the type (C5Me5)2Yb(bipy.-), where bipyo represents 2,2'-bipyridine and substituted 2,2'-bipyridine ligands, is described by a multiconfiguration model, in which the ground state is an open-shell singlet

  11. Bis(2,2′-bipyridine-1κ2N,N′;3κ2N,N′-hexa-μ-methacrylato-1:2κ6O:O′;2:3κ6O:O′-(nitrato-2κ2O,O′-1,3-dicobalt(II-2-terbium(III

    Directory of Open Access Journals (Sweden)

    Bin Wu

    2010-09-01

    Full Text Available In the title trinuclear cobalt–terbium complex, [Co2Tb(C4H5O26(NO3(C10H8N22], the central TbIII and each of the CoII ions are bridged by three carboxylate groups of the methacrylate anions. The TbIII cation is coordinated by six O atoms from six methacrylate anions and two O atoms from a chelating nitrate anion in a distorted square-antiprismatic geometry. Each CoII ion is coordinated by three O atoms from three methylacrylate anions and two N atoms of a 2,2′-bypiridine ligand in a distorted square-pyramidal geometry. In the crystal structure, π–π stacking between the pyridine rings [centroid–centroid distances = 3.682 (8 and 3.760 (8 Å] is observed and weak intermolecular C—H...O hydrogen bonding is also present.

  12. Hydrothermal syntheses, crystal structures and magnetic properties of two inorganic-organic hybrid materials: [{Cu(phen)}2(VVO2)2VIVO2(H2O)(PO4)2] and [V4O7(2,2'-bpy)2(HPO4)2] (phen=1,10-phenathroline, bpy=bipyridine)

    International Nuclear Information System (INIS)

    Two two-dimensional inorganic-organic hybrid materials formulated as [{Cu(phen)}2(VVO2)2VIVO2(H2O)(PO4)2] 1 and [V4O7(2,2'-bpy)2(HPO4)2] 2 have been hydrothermally synthesized and characterized by single-crystal X-ray diffraction. Both crystallize in the triclinic space group P1-bar (no. 2), with cell parameters a=8.118(3), b=9.272(3), c=10.348(5) A, α=96.71(1), β=100.97(1), γ=104.66(1) deg. , V=728.5(5) A3, Z=1 for 1 and a=8.402(4), b=9.270(5), c=9.676(7) A, α=97.10(1), β=110.29(1), γ=98.92(1) deg. , V=685.4(7) A3, Z=1 for 2. The structure of 1 is analogous to that of [{Cu(phen)}2(VVO2)3(OH)(PO4)2] (1') and consists of [{Cu(phen)}2VIVO6(H2O)]∞ chains that are bridged by {(VO2)(PO4)}2 4-membered rings via oxygen atoms into a two-dimensional network. Compounds 1 and 1' are isostructural but the oxidization states of vanadium atoms in them are not fully same. Thus, 1 and 1' are relatively rare examples of all V(V) and V(V)/V(IV) mixed valence analogues in the solid state. Compound 2 is also relatively uncommon and features 2,2'-bipy ligands directly coordinated to vanadium atoms. The structure of 2 is constructed by 4-, 6- and 8-membered rings and is topologically relevant to [V3O7(phen)]. The temperature-dependent magnetic susceptibility of 1 shows alternating ferro- and antiferromagnetic interactions

  13. Synthesis and Coordination Chemistry of Ligands for Supramolecular Chemistry and Sensing Applications

    OpenAIRE

    Clayton, Hayley J.

    2008-01-01

    A series of multidentate N-donor ligands have been synthesised all containing pyridyl and pyridyl/thiazole units and their coordination behaviour is described. The ligands are classified into four types; i) terpyridine containing pyridyl/thiazole ligands (L1-3); ii) pyridyl/thiazole ligands containing a 3,3′-disubstituted bipyridine core. (L4-8); iii) 2,2′-bipyridine containing a crown ether moiety (L9-11); and iv) a 2,2′- bipyridine derived ligand containing a urea functional ...

  14. Formtreue Macrocyclen mit 2,2´-Bipyridinen: Synthese, Selbstorganisation und Komplexierung

    OpenAIRE

    Henze, Oliver

    2010-01-01

    Summary The report describes the syntheses of pyridines, 2,2ý-bipyridines and benzene derivatives and the connection of these units using the chemo- and regioselectivity in Pd° catalysed couplings. So the construction of rigid bipyridine building blocks for the generation of macrocycles with donor positions was achieved. The Sonogashira cross-coupling of these building blocks gave a macrocycle with a size of approx. 2.0 x 1.2 nm. The Macrocycle has two rotating bipyridine donor un...

  15. Exceptionally long-lived light-emitting electrochemical cells: multiple intra-cation π-stacking interactions in [Ir(C^N)2(N^N)][PF6] emitters

    OpenAIRE

    Buenzli, Andreas M.; Constable, Edwin C.; Housecroft, Catherine E.; Prescimone, Alessandro; Zampese, Jennifer A.; Longo, Giulia; Gil-Escrig, Lidon; Pertegas, Antonio; Orti, Enrique; Bolink, Henk J.

    2015-01-01

    A series of cyclometalated iridium(III) complexes [Ir(C^N)2(N^N)][PF6] (N^N = 2,2′-bipyridine (1), 6-phenyl-2,2′-bipyridine (2), 4,4′-di-tert-butyl-2,2′-bipyridine (3), 4,4′-di-tert-butyl-6-phenyl-2,2′-bipyridine (4); HC^N = 2-(3-phenyl)phenylpyridine (HPhppy) or 2-(3,5-diphenyl)phenylpyridine (HPh2ppy)) are reported. They have been synthesized using solvento precursors so as to avoid the use of chlorido-dimer intermediates, chloride ion contaminant being detrimental to the performance of [Ir...

  16. Sintesi, reattività, chiralità in complessi di Pt(II)

    OpenAIRE

    Sini, Alessandro

    2010-01-01

    My PhD thesis concerns basically the synthesis and reactivity of organometallic platinum(II) complexes with pyridine and bipyridine ligands. These complexes are very interesting due to their applications in many fields: catalysis, biology and farmacology, photophysic and photochemistry. Chirality of several complexes with 2-R-pyridines, S-(-)-nicotine and 1,2-bis(2-pyridil)benzene has been carefully taken into account. Concerning bipyridine complexes, reactivity with carbon monoxide and phosp...

  17. A density functional theory study of the electronic properties of Os(II) and Os(III) complexes immobilized on Au(111)

    DEFF Research Database (Denmark)

    O'Boyle, N.M.; Albrecht, Tim; Murgida, D.H.;

    2007-01-01

    We present a density functional theory (DFT) study of an osmium polypyridyl complex adsorbed on Au(111). The osmium polypyridyl complex [Os(bpy)(2)(P0P)Cl](n+) [bpy is 2,2'-bipyridine, P0P is 4,4'-bipyridine, n = 1 for osmium(II), and n = 2 for osmium(III)] is bound to the surface through the fre...

  18. Structure-Activity Relationships and Identification of Optmized CC-Chemokine Receptor CCR1, 5, and 8 Metal-Ion Chelators

    DEFF Research Database (Denmark)

    Chalikiopoulos, Alexander; Thiele, Stefanie; Malmgaard-Clausen, Mikkel;

    2013-01-01

    Chemokine receptors are involved in trafficking of leukocytes and represent targets for autoimmune conditions, inflammatory diseases, viral infections, and cancer. We recently published CCR1, CCR8, and CCR5 agonists and positive modulators based on a three metal-ion chelator series: 2,2'-bipyridine...... bipyridine (23). The structure-activity relationships contribute to small-molecule drug development, and the novel chelators constitute valuable tools for studies of structural mechanisms for chemokine receptor activation....

  19. Poly[bis(μ2-4,4′-bipyridinebis(3-nitrobenzoatocobalt(II

    Directory of Open Access Journals (Sweden)

    Pei-Hsuan Chiang

    2009-11-01

    Full Text Available The hydrothermal reaction of cobalt nitrate with 4,4′-bipyridine and 3-nitrobenzoic acid lead to the formation of the title complex, [Co(C7H4NO42(C10H8N22]n. In the crystal structure, the CoII atoms are coordinated by two terminal carboxylate anions and four 4,4′-bipyridine ligands within slightly distorted octahedra. The CoII atom and one of the two independent 4,4′-bipyridine ligands are located on a twofold rotation axis, while the second independent 4,4′-bipyridine molecule is located on a centre of inversion. One of the two rings of one 4,4′-bipyridine ligand is disordered over two orientations and was refined using a split model [occupancy ratio 0.68 (2:0.32 (2]. The CoII atoms are connected by the 4,4′-bipyridine ligands into layers, which are located parallel to the ab plane.

  20. Increasing the ordering temperatures in oxalate-based 3D chiral magnets: the series [Ir(ppy)2(bpy)][M(II)M(III)(ox)3] x 0.5 H2O (M(II)M(III) = MnCr, FeCr, CoCr, NiCr, ZnCr, MnFe, FeFe); bpy = 2,2'-bipyridine; ppy = 2-phenylpyridine; ox = oxalate dianion).

    Science.gov (United States)

    Clemente-León, Miguel; Coronado, Eugenio; Gómez-García, Carlos J; Soriano-Portillo, Alejandra

    2006-07-10

    The synthesis, structure, and physical properties of a novel series of oxalate-based bimetallic magnets obtained by using the Ir(ppy)2(bpy)]+ cation as a template of the bimetallic [M(II)M(III)(ox)3]- network are reported. The compounds can be formulated as [Ir(ppy)2(bpy)][M(II)Cr(III)(ox)3] x 0.5 H2O (M(II) = Ni, Mn, Co, Fe, and Zn) and [Ir(ppy)2(bpy)]-[M(II)Fe(III)(ox)3] x 0.5 H2O (M(II) = Fe, Mn) and crystallize in the chiral cubic space group P4(1)32 or P4(3)32. They show the well-known 3D chiral structure formed by M(II) and M(III) ions connected through oxalate anions with [Ir(ppy)2(bpy)]+ cations and water molecules in the holes left by the oxalate network. The M(II)Cr(III) compounds behave as soft ferromagnets with ordering temperatures up to 13 K, while the Mn(II)Fe(III) and Fe(II)Fe(III) compounds behave as a weak ferromagnet and a ferrimagnet, respectively, with ordering temperatures of 31 and 28 K. These values represent the highest ordering temperatures so far reported in the family of 3D chiral magnets based on bimetallic oxalate complexes. PMID:16813431

  1. Oligomeric complexes of some heteroaromatic ligands and aromatic diamines with rhodium and molybdenum tetracarboxylates: 13C and 15N CPMAS NMR and density functional theory studies.

    Science.gov (United States)

    Leniak, Arkadiusz; Kamieński, Bohdan; Jaźwiński, Jarosław

    2015-05-01

    Seven new oligomeric complexes of 4,4'-bipyridine; 3,3'-bipyridine; benzene-1,4-diamine; benzene-1,3-diamine; benzene-1,2-diamine; and benzidine with rhodium tetraacetate, as well as 4,4'-bipyridine with molybdenum tetraacetate, have been obtained and investigated by elemental analysis and solid-state nuclear magnetic resonance spectroscopy, (13)C and (15)N CPMAS NMR. The known complexes of pyrazine with rhodium tetrabenzoate, benzoquinone with rhodium tetrapivalate, 4,4'-bipyridine with molybdenum tetrakistrifluoroacetate and the 1 : 1 complex of 2,2'-bipyridine with rhodium tetraacetate exhibiting axial-equatorial ligation mode have been obtained as well for comparison purposes. Elemental analysis revealed 1 : 1 complex stoichiometry of all complexes. The (15)N CPMAS NMR spectra of all new complexes consist of one narrow signal, indicating regular uniform structures. Benzidine forms a heterogeneous material, probably containing linear oligomers and products of further reactions. The complexes were characterized by the parameter complexation shift Δδ (Δδ = δcomplex  - δligand). This parameter ranged from around -40 to -90 ppm in the case of heteroaromatic ligands, from around -12 to -22 ppm for diamines and from -16 to -31 ppm for the complexes of molybdenum tetracarboxylates with 4,4'-bipyridine. The experimental results have been supported by a density functional theory computation of (15)N NMR chemical shifts and complexation shifts at the non-relativistic Becke, three-parameter, Perdew-Wang 91/[6-311++G(2d,p), Stuttgart] and GGA-PBE/QZ4P levels of theory and at the relativistic scalar and spin-orbit zeroth order regular approximation/GGA-PBE/QZ4P level of theory. Nucleus-independent chemical shifts have been calculated for the selected compounds. PMID:25614975

  2. Organic-Disulfonate Ligand Manganese(Ⅱ) Coordination Compound%有机二磺酸锰配合物

    Institute of Scientific and Technical Information of China (English)

    宋玉梅; 庞洁

    2005-01-01

    The crystal structure of [Mn (BDA) (bpy)2(H2O)] (H2O)2 (1)(BDA =6,6' -dibromo-2,2' -dimethoxy- 1,1' -bi-naphthylene-4,4'-disulfonate, bpy=2,2'-bipyridine) composes of a manganese center which is surrounded by twonitrogen atoms from 2,2'-bipyridine and four oxygen atoms from three water and sulfonate group of BDA that alsoparticipate in H-bonding interactions to form 3D network as well as some uncoordinated water. CCDC: 277922.

  3. Metal ion controlled self-assembly of a chemically reengineered protein drug studied by small-angle X-ray scattering

    DEFF Research Database (Denmark)

    Jesper, Nygaard; Munch, Henrik K.; Thulstrup, Peter W.; Christensen, Niels Johan; Hoeg-Jensen, Thomas; Jensen, Knud J.; Arleth, Lise

    2012-01-01

    Precise control of the oligomeric state of proteins is of central importance for biological function and for the properties of biopharmaceutical drugs. Here, the self-assembly of 2,2′-bipyridine conjugated monomeric insulin analogues, induced through coordination to divalent metal ions, was studi...

  4. Gallium and Functionalized-Porphyrins Combine to Form Potential Lysosome-Specific Multimodal Bioprobes.

    Science.gov (United States)

    Pan, Jie; Harriss, Bethany I; Chan, Chi-Fai; Jiang, Lijun; Tsoi, Tik-Hung; Long, Nicholas J; Wong, Wing-Tak; Wong, Wai-Kwok; Wong, Ka-Leung

    2016-07-18

    A water-soluble bimetallic normal ("cold") and radiochemical ("hot") gallium-porphyrin-ruthenium-bipyridine complex (GaporRu-1) has been synthesized by microwave methodology in short reaction times with good (>85%) yields. (68)GaporRu-1 is demonstrated to be a potential multimodal and functional bioprobe for positron emission tomography (PET), lysosome specific optical imaging, and photodynamic therapy. PMID:27355871

  5. Cu(Ⅰ) and Cu(Ⅱ) helical complexes formed with oligobipyridine ligand

    Institute of Scientific and Technical Information of China (English)

    舒谋海; 付有君; 孙为银; 唐雯霞; 张文剑; 段春迎

    1999-01-01

    A new asymmetric oligobipyridine ligand, 1-(5’-methyl-2, 2’-bipyridin-5-yl)-2-(6’-methyl-2, 2’-bipyridin-6-yl)ethane (L), in which the bipyridine units are bridged by CH2CH2 at 5, 6’-position has been synthesized. The ligand L reacts with Cu(Ⅰ) and Cu(Ⅱ) ions giving double-stranded helical complexes [Cu2ⅠL2] (ClO4)2·Et2O (1) and [Cu2ⅡL2 (OH) (H2O)][ClO4]3(2), respectively. Complexes 1 and 2 were characterized by X-ray diffraction analyses, ES-MS, ESR and cyclic voltammetry, etc. Differing from the oligobipyridine ligands bridged by CH2CH2 at 6,6’-or 5,5’-position, the ligand L not only forms a double-stranded helicate with Cu(Ⅰ) ion, but also gives a double-stranded helicate with Cu(Ⅱ) ion. The results show that the linkage mode of the spacer group to the bipyridine units exerts a great impact on the formation of helix.

  6. Solvent effect on thermodynamics of Ag(I) coordination to tripodal polypyridine ligands

    DEFF Research Database (Denmark)

    Del Piero, Silvia; Melchior, Andrea; Menotti, Davide;

    2009-01-01

      An investigation on the thermodynamics of complex formation between Ag(I) ion and different tripodal ligands (tris[(2-pyridyl)methyl]amine) (TPA) and 6,6'-bis[bis(2-pyridylmethyl)aminomethyl]-2,2'-bipyridine (BTPA) has been carried out in the aprotic solvents dimethylsulfoxide (DMSO) and...

  7. Cluster-controlled dimerisation in supramolecular ruthenium photosensitizer-polyoxometalate systems.

    Science.gov (United States)

    Heussner, Kirsten; Peuntinger, Katrin; Rockstroh, Nils; Rau, Sven; Streb, Carsten

    2015-01-01

    A supramolecular reaction system is reported where a labile molecular metal oxide cluster enables the unprecedented dimerisation of ruthenium photosensitizers [Ru(L)2(tmbiH2)](2+) (L = 4,4'-di-tert-butyl-2,2'-bipyridine (1a) or 2,2'-bipyridine (1b); tmbiH2 = 5,5',6,6'-tetramethyl-2,2'-bibenzimidazole). In the presence of [Mo8O26](4-) clusters (2) the dimerisation is triggered by the in situ conversion of [Mo8O26](4-) to [Mo6O19](2-) which results in the release of hydroxide ions. Simultaneous deprotonation of the pH-sensitive tmbiH2-ligands starts the dimerisation, resulting in the formation of the dinuclear complex [(Ru(L)2)2(tmbi)](2+) (L = 4,4'-di-tert-butyl-2,2'-bipyridine (3) or 2,2'-bipyridine (4)). The dimerisation reaction can be suppressed when 2 is replaced by a stable polyoxomolybdate cluster, [Mo5O15(PhPO3)2](4-) (5) and the reaction between 1a and 5 leads to the formation of hydrogen-bonded supramolecular aggregates 6. The solution and solid-state interactions in these systems were investigated using a range of spectroscopic and crystallographic techniques and compounds 3, 4 and 6 were characterized using single-crystal XRD. PMID:25381808

  8. Photocatalytic hydrogen evolution with ruthenium polypyridine sensitizers: unveiling the key factors to improve efficiencies.

    Science.gov (United States)

    Deponti, Elisa; Natali, Mirco

    2016-05-31

    Photochemical hydrogen evolution studies aimed at evaluating new molecular catalysts have usually exploited Ru(bpy)3(2+) (where bpy = 2,2'-bipyridine) as the reference photosensitizer, thanks to its suitable optical and redox properties. In principle, an additional improvement of the photocatalytic performances can be achieved also by a careful adjustment of the photophysical and/or electrochemical characteristics of the ruthenium-based sensitizer. Herein we describe homogeneous molecular systems for photocatalytic hydrogen evolution composed of a series of ruthenium polypyridine complexes as the photosensitizers (), a cobaloxime catalyst, and ascorbic acid as the sacrificial electron donor. Suitable functionalizations of the 4,4' positions of bipyridine ligands have been addressed in order to modify the redox properties of the chromophores rather than their optical ones. A careful and detailed kinetic characterization of the relevant processes at the basis of hydrogen evolving photocatalysis has been addressed to rationalize the observed behavior. The results show that the ruthenium complex involving two 2,2'-bipyridines and one 4,4'-dimethyl-2,2'-bipyridine () may outperform the standard Ru(bpy)3(2+) (), combining the right balance of structural and redox properties, thus posing as an alternative benchmark photosensitizer for the study of new hydrogen evolving catalysts. PMID:27165725

  9. Synthesis, structure, and electrochemistry and magnetic properties of a novel 1D homochiral MnIII(5-Brsalen) coordination polymer with left-handed helical character

    Science.gov (United States)

    Dong, Dapeng; Yu, Naisen; Zhao, Haiyan; Liu, Dedi; Liu, Jia; Li, Zhenghua; Liu, Dongping

    2016-01-01

    A novel homochiral manganese (III) Mn(5-Brsalen) coordination polymer with left-handed helical character by spontaneous resolution on crystallization by using Mn(5-Brsalen) and 4,4-bipyridine, [MnIII(5-Brsalen)(4,4-bipy)]·ClO4·CH3OH (1) (4,4-bipy = 4,4-bipyridine) has been synthesized and structurally characterized by X-ray single-crystal diffraction, elemental analysis and infrared spectroscopy. In compound 1, each manganese(III) anion is six-coordinate octahedral being bonded to four atoms of 5-Brsalen ligand in an equatorial plane and two nitrogen atoms from a 4,4-bipyridine ligand in axial positions. The structure of compound 1 can be described a supramolecular 2D-like structure which was formed by the intermolecular π-stacking interactions between the neighboring chains of the aromatic rings of 4,4-bipyridine and 5-Brsalen molecules. UV-vis absorption spectrum, electrochemistry and magnetic properties of the compound 1 have also been studied.

  10. Synthesis of Dendritic-Linear Block Copolymers by Atom Transfer Radical Polymerization

    Institute of Scientific and Technical Information of China (English)

    2001-01-01

    The dendritic polyarylether 2-bromoisobutyrate as the macromolecular initiator for the controlled free radical polymerization of styrene was investigated. The polymerization was carried out with CuBr/2,2′-bipyridine catalyst at 110℃. It is found that the hybrid dendritic-linear block copolymers possess well-defined molecular weights and low polydispersities.

  11. Triggering Gel Formation and Luminescence through Donor-Acceptor Interactions in a C3 -Symmetric Tris(pyrene) System.

    Science.gov (United States)

    Lai, Thanh-Loan; Pop, Flavia; Melan, Caroline; Canevet, David; Sallé, Marc; Avarvari, Narcis

    2016-04-18

    Straightforward modulation of the gelation, absorption and luminescent properties of a tris(pyrene) organogelator containing a C3 -symmetric benzene-1,3,5-tricarboxamide central unit functionalized by three 3,3'-diamino-2,2'-bipyridine fragments is achieved through donor-acceptor interactions in the presence of tetracyanoquinodimethane. PMID:26864120

  12. Electrochemical detection of osmium-modified peptides and streptavidin-biotin complex

    Czech Academy of Sciences Publication Activity Database

    Billová, Sabina; Brázdová, Marie; Havran, Luděk; Kizek, René; Masařík, Michal; Paleček, Emil

    Brno : Masarykova univerzita, 2002. s. 62. ISBN 80-210-2777-0. [Pracovní setkání biochemiků a molekulárních biologů /6./. 07.02.2002, Brno] Institutional research plan: CEZ:AV0Z5004920 Keywords : OSO4 * 2,2-bipyridine * electrochemical detection Subject RIV: BO - Biophysics

  13. Re and Br X-ray Absorption Near-Edge Structure Study of the Ground and Excited States of [ReBr(CO)3(bpy)] Interpreted by DFT and TDDFT Calculations

    Czech Academy of Sciences Publication Activity Database

    Záliš, Stanislav; Milne, C. J.; Nahhas, A. E.; Blanco-Rodríguez, A. M.; van der Veen, R. M.; Vlček Jr., Antonín

    2013-01-01

    Roč. 52, č. 10 (2013), s. 5775-5785. ISSN 0020-1669 R&D Projects: GA MŠk LD11086 Institutional support: RVO:61388955 Keywords : carbonyl-bipyridine complexes * density functional theory * order regular approximation Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 4.794, year: 2013

  14. Chiral metal complexes. 4. Stereoselective deuterium exchange at the coordinated NH/sub 2/ group of L-alanine

    Energy Technology Data Exchange (ETDEWEB)

    Vagg, R.S. (Macquarie Univ., North Ryde, Australia); Williams, P.A.

    1983-01-19

    This communication details results of initial /sup 1/H NMR investigations on one of the simplest of these ternary compounds, namely ..delta..,..lambda..-((L-alaninato)bis(2,2-bipyridine)ruthenium(II)) perchlorate. Possible mechanisms of deuterium exchange for chiral ruthenium complexes are presented in this study.

  15. Study of the emission oxidative reactions of ruthenium (II) complex by cationic compounds in anionic micelles

    International Nuclear Information System (INIS)

    The oxidative quenching of the emission of the tetraanionic complex tris (4,4' dicarboxylate - 2,2' - bipyridine ruthenium (II) in aqueous solution, by both organic and inorganic compounds in presence of anionic detergents, above and below the critical micelle concentration is studied. The organic cations, the inorganic ion and detergents used are shown. (M.J.C.)

  16. Synthesis and structural characterization of 14-vertex germa-, stanna-, and plumba-carboranes.

    Science.gov (United States)

    Zheng, Fangrui; Xie, Zuowei

    2014-04-01

    This article reports the synthesis and structures of several 14-vertex germa-, stanna-, and plumba-carboranes of the MC2B11 system. The reaction of GeCl2·dioxane, SnCl2 or Pb(OAc)2 with [8,9-(CH2)3-8,9-C2B11H11][Na2] in THF gave, after recrystallization from bidentate ligands such as bipyridine, 4,4'-dimethyl-2,2'-bipyridine, phenantroline and 1,2-bis(diphenylphosphino)ethane (dppe), eight 14-vertex p-block metallacarboranes 2,3-(CH2)3-1-(2',2''-bipyridine)-1,2,3-GeC2B11H11 (1), 2,3-(CH2)3-1-(4',4''-dimethyl-bipyridine)-1,2,3-GeC2B11H11 (2), 2,3-(CH2)3-1-(1',10'-phenantroline)-1,2,3-GeC2B11H11 (3), 2,3-(CH2)3-1-(2',2''-bipyridine)-1,2,3-SnC2B11H11 (4), 2,3-(CH2)3-1-(4',4''-dimethyl-bipyridine)-1,2,3-SnC2B11H11 (5), 2,3-(CH2)3-1-(1',10'-phenantroline)-1,2,3-SnC2B11H11 (6), 2,3-(CH2)3-1-(dppe)-1,2,3-SnC2B11H11 (7) and 2,3-(CH2)3-1-(2',2''-bipyridine)-1,2,3-PbC2B11H11 (8) in high isolated yields. Single-crystal X-ray analyses reveal that they adopt a distorted-bicapped-hexagonal antiprism geometry, in which the p-block metal atom slips away from the above center of the C2B4 bonding face towards the boron side, leading to an η(4) bonding mode. The results suggest that [nido-8,9-(CH2)3-8,9-C2B11H11](2-) is a redox inactive species and a good π-ligand for transition metals and p-block elements. PMID:24162337

  17. Ruthenium(II)- bipyridyl with extended -system: Improved thermo-stable sensitizer for efficient and long-term durable dye sensitized solar cells

    Indian Academy of Sciences (India)

    M Chandrasekharam; G Rajkumar; Ch Srinivasa Rao; T Suresh; P Y Reddy; Y Soujanya

    2011-09-01

    A new extended thermo-stable high molar extinction coefficient bipyridyl ruthenium(II) complex "cis-Ru(4,4'-bis(3,5-di-tert-butylphenyl)-2,2'-bipyridine)(Ln)(NCS)2 H101", where Ln = 4,4'-dicarboxylic acid-2,2'-bipyridine; was synthesized and characterized by 1H-NMR, FT-IR and ESI-MASS spectroscopes. The H101 sensitized solar cell constructed with an active area of 0.54 cm2 in combination with an ionic liquid electrolyte exhibited broader photocurrent action spectrum with solar-to-electric energy conversion efficiency () of 5.89 (JSC = 12.14 mA/cm2, VOC = 690 V, fill factor = 0.699) under Air Mass (AM) 1.5 sunlight, while the reference `cis-Ru(4,4'-dinonyl-2,2'-bipyridine)(Ln)(NCS)2', Z907 sensitized solar cell exhibited -value of 5.17% (JSC = 11.93 mA/cm2, VOC = 650 V, fill factor = 0.666). TGA analysis of H101 showed extended thermal-stability and under continuous light exposure and aging at 55°C, the DSSC retained 85% of its initial -value, while under comparable conditions Z907 sensitized solar cell retained 88%. As compared to 4,4'-dinonyl-2,2'-bipyridine in Z907, the new ancillary bipyridyl ligand `4,4'-bis(3,5-di-tert-butylphenyl)-2,2'-bipyridine’ in H101 shifts the absorption bands remarkably towards blue. The Density Functional Theory (DFT) and Time-Dependent DFT excited state calculations of the new sensitizer show that the first three HOMOs have t2g character with sizeable mixing from the NCS ligands with -bonding orbitals of 4,4'-bis(3,5-di-tert-butylphenyl)-2,2'-bipyridine. The LUMO is a *-orbital localized on the 4,4-dicarboxylic acid-2,2'-bipyridine and higher un-occupied frontier orbitals have *-combinations with 4,4'-bis(3,5-di-tert-butylphenyl)-2,2'-bipyridine.

  18. Topological evolution and photoluminescent properties of a series of divalent zinc-based metal–organic frameworks tuned via ancillary ligating spacers

    International Nuclear Information System (INIS)

    The combination of divalent zinc ions, 4-(4-carboxybenzamido)benzoic acid and exo-bidendate bipyridine ligands gave rise to a series of new MOFs: [ZnL(bipy)]·DMF·H2O (1), [ZnL(bpe)]·1.5H2O (2), [ZnL(bpa)]·4H2O (3) and [ZnL(bpp)]·1.75H2O (4) (MOF=metal-organic framework, bipy=4,4′-bipyridine, bpe=trans-1,2-bis(4-pyridyl)ethylene, bpa=1,2-bis(4-pyridinyl)ethane, bpp=1,3-bis(4-pyridinyl)propane, H2L=4,4′-(carbonylimino)dibenzoic acid). Fine tune over the topology of the MOFs was achieved via systematically varying the geometric length of the second ligating bipyridine ligands. Single-crystal X-ray analysis reveals that complex 1 has a triply interpenetrated three-dimensional (3D) framework with elongated primitive cubic topology, whereas isostructural complexes 2 and 3 each possesses a 6-fold interpenetrated diamondiod 3D framework. Further expansion of the length of the bipyridine ligand to bpp leads to the formation of 4, which features an interesting entangled architecture of 2D→3D parallel polycatenation. In addition, the thermogravimetric analyses and solid-state photoluminescent properties of the selected complexes are investigated. - Graphical abstract: The incorporation of exo-bidendate bipyridine spacers into the Zn–H2L system has yielded a series of new MOFs exhibiting topological evolution from 3-fold interpenetration to 6-fold interpenetration and 2D→3D parallel polycatenation. Highlights: ► The effect of the pyridyl-based spacers on the formation of MOFs was explored. ► Fine tune over the topology of the MOFs was achieved. ► An interesting structure of 2D→3D parallel polycatenation is reported

  19. Nonsteroidal Anti-inflammatory-Organometallic Anticancer Compounds.

    Science.gov (United States)

    Păunescu, Emilia; McArthur, Sarah; Soudani, Mylène; Scopelliti, Rosario; Dyson, Paul J

    2016-02-15

    Compounds that combine metal-based drugs with covalently linked targeted organic agents have been shown, in some instances, to exhibit superior anticancer properties compared to the individual counterparts. Within this framework, we prepared a series of organometallic ruthenium(II)- and osmium(II)-p-cymene complexes modified with the nonsteroidal anti-inflammatory drugs (NSAIDs) indomethacin and diclofenac. The NSAIDs are attached to the organometallic moieties via monodentate (pyridine/phosphine) or bidentate (bipyridine) ligands, affording piano-stool Ru(II) and Os(II) arene complexes of general formula [M(η(6)-p-cymene)Cl2(N)], where N is a pyridine-based ligand, {2-(2-(1-(4-chlorobenzoyl)-5-methoxy-2-methyl-1H-indol-3-yl)acetoxy)ethyl-3-(pyridin-3-yl)propanoate} or {2-(2-(2-((2,6-dichlorophenyl)amino)phenyl)acetoxy)ethyl-3-(pyridin-3-yl)propanoate}, [M(η(6)-p-cymene)Cl2(P)], where P is a phosphine ligand, {2-(2-(1-(4-chlorobenzoyl)-5-methoxy-2-methyl-1H-indol-3-yl)acetoxy)ethyl-4-(diphenylphosphanyl)benzoate} or {2-(2-(2-((2,6-dichlorophenyl)amino)phenyl)acetoxy)ethyl-4-(diphenylphosphanyl)benzoate, and [M(η(6)-p-cymene)Cl(N,N')][Cl], where N,N' is a bipyridine-based ligand, (4'-methyl-[2,2'-bipyridin]-4-yl)methyl-2-(1-(4-chlorobenzoyl)-5-methoxy-2-methyl-1H-indol-3-yl)acetate), (4'-methyl-[2,2'-bipyridin]-4-yl)methyl-2-(2-((2,6-dichlorophenyl)amino)phenyl)acetate), (bis(2-(2-(1-(4-chlorobenzoyl)-5-methoxy-2-methyl-1H-indol-3-yl)acetoxy)ethyl)[2,2'-bipyridine]-5,5'-dicarboxylate), or (bis(2-(2-(2-((2,6-dichlorophenyl)amino)phenyl)acetoxy)ethyl)[2,2'-bipyridine]-5,5'-dicarboxylate). The antiproliferative properties of the complexes were assessed in human ovarian cancer cells (A2780 and A2780cisR, the latter being resistant to cisplatin) and nontumorigenic human embryonic kidney (HEK-293) cells. Some of the complexes are considerably more cytotoxic than the original drugs and also display significant cancer cell selectivity. PMID:26824462

  20. Organic-Ruthenium(II Polypyridyl Complex Based Sensitizer for Dye-Sensitized Solar Cell Applications

    Directory of Open Access Journals (Sweden)

    Lingamallu Giribabu

    2011-01-01

    Full Text Available A new high molar extinction coefficient organic-ruthenium(II polypyridyl complex sensitizer (RD-Cou that contains 2,2,6,6-tetramethyl-9-thiophene-2-yl-2,3,5,6,6a,11c-hexahydro1H,4H-11oxa-3a-aza-benzoanthracene-10-one as extended -conjugation of ancillary bipyridine ligand, 4,4-dicaboxy-2,26,2-bipyridine, and a thiocyanate ligand in its molecular structure has been synthesized and completely characterized by CHN, Mass, 1H-NMR, UV-Vis, and fluorescence spectroscopies as well as cyclic voltammetry. The new sensitizer was tested in dye-sensitized solar cells using a durable redox electrolyte and compared its performance to that of standard sensitizer Z-907.

  1. Synthesis and characterization of nanowire coils of organometallic coordination polymers for controlled cargo release.

    Science.gov (United States)

    Liang, Guodong; Ni, Huan; Bao, Suping; Zhu, Fangming; Gao, Haiyang; Wu, Qing

    2014-06-12

    Nanowire coils of organometallic coordination polymers have been synthesized for the first time by using the emulsion periphery polymerization technique. An amphiphilic triblock copolymer terminated with inclusion complex of β-cyclodextrin and 4,4'-bipyridine self-assembles into oil-in-water emulsion in a toluene/water mixture. Subsequent coordination of bipyridine with Ni(II) in periphery of emulsions results in the formation of coordination polymer nanowire coils. The nanowire coils are composed of nanowires with diameter of 2 nm. Nanowire coils exhibit enhanced thermal stability in contrast to their parent triblock copolymer. Interestingly, nanowire coils are capable of encapsulating organic cargoes. Encapsulated cargoes can be selectively extracted from nanowire coils without damaging nanowire coils. Nanowire coils are potential candidates for encapsulating and controlled release of organic cargoes. PMID:24842771

  2. High efficiency solid-state sensitized heterojunction photovoltaic device

    KAUST Repository

    Wang, Mingkui

    2010-06-01

    The high molar extinction coefficient heteroleptic ruthenium dye, NaRu(4,4′-bis(5-(hexylthio)thiophen-2-yl)-2,2′-bipyridine) (4-carboxylic acid-4′-carboxylate-2,2′-bipyridine) (NCS) 2, exhibits certified 5% electric power conversion efficiency at AM 1.5 solar irradiation (100 mW cm-2) in a solid-state dye-sensitized solar cell using 2,2′,7,7′-tetrakis-(N,N-di-pmethoxyphenylamine)-9, 9′-spirobifluorene (spiro-MeOTAD) as the organic hole-transporting material. This demonstration elucidates a class of photovoltaic devices with potential for low-cost power generation. © 2010 Elsevier Ltd. All rights reserved.

  3. Supramolecular effects in dendritic systems containing photoactive groups

    Directory of Open Access Journals (Sweden)

    GIANLUCA CAMILLO AZZELLINI

    2000-03-01

    Full Text Available In this article are described dendritic structures containing photoactive groups at the surface or in the core. The observed supramolecular effects can be attributed to the nature of the photoactive group and their location in the dendritic architecture. The peripheric azobenzene groups in these dendrimeric compounds can be regarded as single residues that retain the spectroscopic and photochemical properties of free azobenzene moiety. The E and Z forms of higher generation dendrimer, functionalized with azobenzene groups, show different host ability towards eosin dye, suggesting the possibility of using such dendrimer in photocontrolled host-guest systems. The photophysical properties of many dendritic-bipyridine ruthenium complexes have been investigated. Particularly in aerated medium more intense emission and a longer excited-state lifetime are observed as compared to the parent unsubstituted bipyridine ruthenium complexes. These differences can be attributed to a shielding effect towards dioxygen quenching originated by the dendritic branches.

  4. C-Methylcalix[4]resorcinarene–1,4-bis(pyridin-3-yl-2,3-diaza-1,3-butadiene (1/2

    Directory of Open Access Journals (Sweden)

    Konstantin A. Udachin

    2012-02-01

    Full Text Available In the title compound, 2C12H10N4·C32H32O8, the calixarene adopts a rctt conformation with dihedral angles of 138.40 (1 and 9.10 (1° between the opposite rings. The dihedral angles between the rings of the pyridine derivative are 8.80 (1 and 9.20 (1°. In the crystal, adjacent C-methylcalix[4]resorcinarene molecules are connected into columns parallel to [010] by O—H...O hydrogen bonds. O—H...N hydrogen bonds between the axial phenoxyl groups and bipyridine molecules link the columns into sheets parallel to (011, which are connected by O—H...N hydrogen bonds. Further O—H...N hydrogen bonds link the bipyridine and C-methylcalix[4]resorcinarene molecules, giving rise to a three-dimensional network.

  5. A Noble-Metal-Free Nickel(II) Polypyridyl Catalyst for Visible-Light-Driven Hydrogen Production from Water.

    Science.gov (United States)

    Yuan, Yong-Jun; Lu, Hong-Wei; Tu, Ji-Ren; Fang, Yong; Yu, Zhen-Tao; Fan, Xiao-Xing; Zou, Zhi-Gang

    2015-10-01

    The complex [Ni(bpy)3](2+) (bpy=2,2'-bipyridine) is an active catalyst for visible-light-driven H2 production from water when employed with [Ir(dfppy)2 (Hdcbpy)] [dfppy=2-(3,4-difluorophenyl)pyridine, Hdcbpy=4-carboxy-2,2'-bipyridine-4'-carboxylate] as the photosensitizer and triethanolamine as the sacrificial electron donor. The highest turnover number of 520 with respect to the nickel(II) catalyst is obtained in a 8:2 acetonitrile/water solution at pH 9. The H2 -evolution system is more stable after the addition of an extra free bpy ligand, owing to faster catalyst regeneration. The photocatalytic results demonstrate that the nickel(II) polypyridyl catalyst can act as a more effective catalyst than the commonly utilized [Co(bpy)3 ](2+). This study may offer a new paradigm for constructing simple and noble-metal-free catalysts for photocatalytic hydrogen production. PMID:26264140

  6. Formation of molecular glasses of (N-acylalaninato)europium(III) complexes and the luminescence properties

    International Nuclear Information System (INIS)

    Tris(N-octanoyl-DL-alaninato)europium(III) (Eu(oct-ala)3) was newly prepared and it was found that the complex takes a stable glassy state by an evaporation of methanol from the solution, whereas tris(octanoato)europium(III) (Eu(octnt)3, i.e. europium soap) does not easily take a purely vitrified state. The luminescence intensity was larger and the spectrum was simpler in the glassy state than those in the devitrified state. It is characteristic that an addition of 2,2'-bipyridine (bpy) or 4,4'-dinonyl-2,2'-bipyridine (dnbpy) to Eu(oct-ala)3 increases the luminescence intensity both in solutions and in solids and that Eu(octnt)3 becomes to take a stable glassy state by an addition of bpy

  7. Synthesis and crystal structure of Pb(Bipy)2B12H12

    International Nuclear Information System (INIS)

    Lead complex with B12H122- anion and 2,2' bipyridine-lead(2) dodecahydro-closo-dodecaborate di(2,2' bipyridine) is synthesized and characterized by IF, UV and NMR spectrography methods. According to roentgen-structural analysis the crystals belong to monoclinic syngony, sp.gr. C2/m,a=17.872(4), b=18.672(5), c=9.228(7)A, β=109.11(4), V=2910(2)A3, Z=4. The structure consists of Pb2(Bipy)4(B12H12)2 dimeric units. The Pb-B distances are within the limits of 3.313-3.514A. 11 refs.; 2 figs.; 2 tabs

  8. Peptide Nucleic Acid with a Lysine Side Chain at the β-Position: Synthesis and Application for DNA Cleavage.

    Science.gov (United States)

    Sugiyama, Toru; Kuwata, Keiko; Imamura, Yasutada; Demizu, Yosuke; Kurihara, Masaaki; Takano, Masashi; Kittaka, Atsushi

    2016-01-01

    This paper reports the synthesis of new β-Lys peptide nucleic acid (PNA) monomers and their incorporation into a 10-residue PNA sequence. PNA containing β-Lys PNA units formed a stable hybrid duplex with DNA. However, incorporation of β-Lys PNA units caused destabilization of PNA-DNA duplexes to some extent. Electrostatic attractions between β-PNA and DNA could reduce this destabilization effect. Subsequently, bipyridine-conjugated β-Lys PNA was prepared and exhibited sequence selective cleavage of DNA. Based on the structures of the cleavage products and molecular modeling, we reasoned that bipyridine moiety locates within the minor groove of the PNA-DNA duplexes. The lysine side chain of β-PNA is a versatile handle for attaching various functional molecules. PMID:27373637

  9. Development of high efficiency 100% aqueous cobalt electrolyte dye-sensitised solar cells.

    Science.gov (United States)

    Ellis, Hanna; Jiang, Roger; Ye, Sofie; Hagfeldt, Anders; Boschloo, Gerrit

    2016-03-28

    In this study we report the application of three cobalt redox shuttles in 100% aqueous electrolyte dye-sensitised solar cells (DSCs). By using chloride as a counter-ion for cobalt bipyridine, cobalt phenanthroline and cobalt bipyridine pyrazole, the redox shuttles were made water soluble; no surfactant or further treatment was necessary. A simple system of merely the redox shuttles and 1-methylbenzimidazole (MBI) in water as an electrolyte in combination with an organic dye and a mesoporous PEDOT counter electrode was optimised. The optimisation resulted in an average efficiency of 5.5% (record efficiency of 5.7%) at 1 sun. The results of this study present promising routes for further improvements of aqueous cobalt electrolyte DSCs. PMID:26931779

  10. 配位聚合物[Mn(4,4'-bpy)1.5(H2O)3](CIO4)·(4,4'-bpy)(L)·H2O的水热合成和晶体结构%Hydrothermal Synthesis and Crystal Structure of Coordination Polymer [Mn(4,4'-bpy)1.5(H2O)3] (ClO4)· (4,4'-bpy)(L)· H2O

    Institute of Scientific and Technical Information of China (English)

    黄妙龄

    2007-01-01

    The title compound, [Mn(4,4'-bpy)1.5(H2O)3](C1O4)·(4,4'-bpy)(L)· H2O(1), where L=2,4,6-trimethylbenzoic acid, was synthesized and its crystal structure was determined by X-ray diffraction analysis. The crystal is of triclinic, space group P(-1) with a=2.929 9(6) nm, b=1.0364(2) nm, c=8.222 0(1) nm, α=105.300(2)°, β=97.495(2)°,0.135 2. The Mn atoms are octahedrally coordinated by three N atoms of three 4,4'-bipyridine ligands and three O atoms of water. The complex shows a one-dimensional chain structure bridged by water and 4,4'-bipyridine molecules. CCDC: 615707.

  11. Substitution of Carbazole Modified Fluorenes as π-Extension in Ru(II) Complex-Influence on Performance of Dye-Sensitized Solar Cells

    OpenAIRE

    Malapaka Chandrasekharam; Ganugula Rajkumar; Thogoti Suresh; Chikkam Srinivasa Rao; Paidi Yella Reddy; Jun-Ho Yum; Mohammad Khaja Nazeeruddin; Michael Graetzel

    2011-01-01

    A new high molar extinction coefficient ruthenium(II) bipyridyl complex “cis-Ru(4, 4  -bis(9,9-dibutyl-7-(3,6-di-tert-butyl-9H-carbazol-9-yl)-9H-fluoren-2-yl)-2, 2  -bipyridine)(2, 2  -bipyridine-4, 4  -dicarboxylic acid)(NCS)2, BPFC” has been synthesized and characterized by FT-IR, 1 H -NMR, and ESI-MASS spectroscopes. The sensitizer showed molar extinction coefficient of 1 8 . 5 × 1 0 3  M−1cm−1, larger as compared to the reference N719, which showed 1 4 . 4 × 1 0 3  M−1cm−1. The test c...

  12. Photophysics of Singlet and Triplet Intraligand Excited States in [ReCl(CO)(3)(1-(2-pyridyl)-imidazo[1,5-alpha]pyridine)] Complexes

    Czech Academy of Sciences Publication Activity Database

    Blanco-Rodríguez, A. M.; Kvapilová, Hana; Sýkora, Jan; Towrie, M.; Nervi, C.; Volpi, G.; Záliš, Stanislav; Vlček Jr., Antonín

    2014-01-01

    Roč. 136, č. 16 (2014), s. 5963-5973. ISSN 0002-7863 R&D Projects: GA ČR GBP208/12/G016; GA MŠk LD11086 Institutional support: RVO:61388955 Keywords : CARBONYL-BIPYRIDINE COMPLEXES * RESOLVED INFRARED-SPECTROSCOPY * CHARGE-TRANSFER STATES Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 12.113, year: 2014

  13. Oxidation of Alcohols Catalyzed by Ruthenium Complexes with Iodosylbenzene as Oxidant

    Institute of Scientific and Technical Information of China (English)

    Zi Qiang LEI; Qiao Xiang KANG; Xiang Zhen BAI; Zhi Wang YANG; Qing Hua ZHANG

    2005-01-01

    Five ruthenium complexes such as Phen-Ru-Phen, Phen-Ru-Bipy, Phen-Ru-Quin,Quin-Ru-Quin and Bipy-Ru-Quin (where Phen=1, 10-phenanthroline, Quin=8-hydroxyquinoline,Bipy=2, 2′-bipyridine) were synthesized and used as catalysts for the oxidation of benzylic and primary aliphatic alcohols with iodosylbenzene as oxidant. The oxidations were carried out at room temperature, affording the corresponding aldehydes and ketones with high selectivity.

  14. Deactivation of signal amplification by reversible exchange catalysis, progress towards in vivo application.

    Science.gov (United States)

    Mewis, Ryan E; Fekete, Marianna; Green, Gary G R; Whitwood, Adrian C; Duckett, Simon B

    2015-06-18

    The catalyst which is used in the signal amplification by reversible exchange (SABRE) process facilitates substrate hyperpolarisation while acting to speed up the rate of relaxation. Consequently, the lifetime over which the hyperpolarised contrast agent is visible is drastically reduced. We show that the addition of a chelating ligand, such as bipyridine, rapidly deactivates the SABRE catalyst thereby lengthening the agent's relaxation times and improving the potential of SABRE for diagnostic MRI. PMID:25989727

  15. Pattern-Based Sensing of Sulfated Glycosaminoglycans with a Dynamic Mixture of Iron Complexes

    OpenAIRE

    Müller-Graff, Peter-Korbinian; Szelke, Helga; Severin, Kay; Krämer, Roland

    2010-01-01

    A dynamic mixture of iron complexes was used as a colorimetric sensor for sulfated glycosaminoglycans. The sensing ensemble was prepared by mixing [FeCl2(H2O)4] with dipicolylamine, the functionalized bipyridyl ligand N-(6-aminohexyl)-4'-methyl-2,2'-bipyridine-4-carboxamide, and the dye Evans Blue. Upon addition of the analytes, characteristic changes in the UV-Vis spectrum of the solutions were observed. The spectral changes allowed indentifying different sulfated glucosaminoglycans (unfr...

  16. Dithiocarbamate Anchoring in Molecular Wire Junctions: A First Principles Study

    OpenAIRE

    Li, Zhenyu; Kosov, D. S.

    2007-01-01

    Recent experimental realization [J. Am. Chem. Soc., 127 (2005) 7328] of various dithiocarbamate self assembly on gold surface opens the possibility for use of dithiocarbamate linkers to anchor molecular wires to gold electrodes. In this paper, we explore this hypothesis computationally. We computed the electron transport properties of 4,4'-bipyridine (BP), 4,4'-bipyridinium-1,1'-bis(carbodithioate) (BPBC), 4-(4'-pyridyl)-peridium-1-carbodithioate (BPC) molecule junctions based on the density ...

  17. Promoting the activity of LiFePO4 (olivine) cathode of Li-ion battery by supramolecular complexes with single walled carbon nanotubes

    Czech Academy of Sciences Publication Activity Database

    Kavan, Ladislav; Exnar, I.; Graetzel, M.

    Boca Raton : CRC Press, 2009, s. 58-61. ISBN 978-1-4398-1784-1 R&D Projects: GA MŠk LC510; GA AV ČR IAA400400804; GA AV ČR KAN200100801 Institutional research plan: CEZ:AV0Z40400503 Keywords : olivine cathode * Li-ion battery * carbon nanotubes * Ru-bipyridine complexes Subject RIV: CG - Electrochemistry

  18. Aufbau und Untersuchung multivalenter metallosupramolekularer Wirtsysteme

    OpenAIRE

    Linder, Igor

    2015-01-01

    The present thesis describes the construction of differently shaped di- to hexavalent crown ethers by coordination-driven self-assembly and their investigations according (pseudo¬-) rotaxane formation and kinetics of the dynamic ligand exchange. First, bipyridine and terpyridine ligand moieties as well as crown ether host moieties were synthesized. Then a toolbox of crown ether-substituted bi- and terpyridines was created by connecting the host and ligand moieties by Sonogashira reactio...

  19. Examining Rhodium Catalyst complexes for Use with Conducting Polymers Designed for Fuel Cells in Preparing Biosensors

    Energy Technology Data Exchange (ETDEWEB)

    Carpio, M.M.; Kerr, J.B.

    2005-01-01

    Biosensing devices are important because they can detect, record, and transmit information regarding the presence of, or physiological changes in, different chemical or biological materials in the environment. The goal of this research is to prepare a biosensing device that is effective, quick, and low cost. This is done by examining which chemicals will work best when placed in a biosensor. The first study involved experimenting on a rhodium catalyst complexed with ligands such as bipyridine and imidazole. The rhodium catalyst is important because it is reduced from RhIII to RhI, forms a hydride by reaction with water and releases the hydride to react with nicotinamide adenine dinucleotide (NAD+) to selectively produce 1,4-NADH, the reduced form of NAD+. The second study looked at different types of ketones and enzymes for the enzyme-substrate reaction converting a ketone into an alcohol. Preliminary results showed that the rhodium complexed with bipyridine was able to carry out all the reactions, while the rhodium complexed with imidazole was not able to produce and release hydrides. In addition, the most effective ketone to use is benzylacetone with the enzyme alcohol dehydrogenase from baker’s yeast. Future work includes experimenting with bis-imidazole, which mimics the structure of bipyridine to see if it has the capability to reduce and if the reduction rate is comparable to the bipyridine complex. Once all testing is completed, the fastest catalysts will be combined with polymer membranes designed for fuel cells to prepare biosensing devices that can be used in a variety of applications including ones in the medical and environmental fields.

  20. Structural archetypes in nickel(II) hybrid vanadates. Towards a directed hydrothermal synthesis

    International Nuclear Information System (INIS)

    In the present work, we relate the modifications of the initial synthesis parameters (pH value, stoichiometry and concentration) with the different structural archetypes obtained in the {Ni/Bpy/VO} and {Ni/Bpe/VO} systems (4,4'-bipyridine (Bpy), 1,2-di(4-pyridyl) ethylene (Bpe)). The vanadium coordination is partially controlled by the hydrothermal synthesis conditions, and the final crystal structures depend on the synergetic interaction between the metal-organic subnets and the vanadium oxide subunits.

  1. PFO-BPy Solubilizers for SWNTs: Modelling of Polymers from Oligomers

    OpenAIRE

    Glanzmann, Livia N.; Mowbray, Duncan J.; Rubio, Angel

    2014-01-01

    Due to their exeptional physical properties, single walled carbon nanotubes (SWNTs) embedded in organic polymers (polymer-SWNT hybrid systems) are promising materials for organic photovoltaic (OPV) devices. Already at the SWNT sorting and debundling step, polymers such as the copolymer of 9,9-dioctylfluorenyl-2,7-diyl and bipyridine (PFO-BPy) are used as solubilizers. However, to model polymer-SWNT hybrid systems, we must first determine the smallest oligomer needed to sufficiently describe t...

  2. Lanthanide modification of CdSe/ZnS core/shell quantum dots

    DEFF Research Database (Denmark)

    Dethlefsen, Johannes Rytter; Mikhailovsky, Alexander A.; Burks, Peter T.;

    2012-01-01

    Lanthanide-modified CdSe quantum dots (CdSe(Ln) QDs) have been prepared by heating a solution of Cd(oleate)(2), SeO2, and Ln(bipy)(S2CNEt2)(3) (bipy = 2,2'-bipyridine) to 180-190 degrees C for 10-15 min. The elemental compositions of the resulting CdSe(Ln) cores and CdSe(Ln)/ZnS core/shell QDs show...

  3. 1D ferrimagnetism in homometallic chains

    OpenAIRE

    Coronado Miralles, Eugenio; Gómez García, Carlos José; Borrás Almenar, Juan José

    1990-01-01

    The magnetic properties of the cobalt zigzag chain Co(bpy)(NCS)2 (bpy=2,2′‐bipyridine) are discussed on the basis of an Ising‐chain model that takes into account alternating Landé factors. It is emphasized, for the first time, that a homometallic chain containing only one type of site can give rise to a 1D ferrimagneticlike behavior. ,

  4. PREPARATION OF PHOTOFUNCTIONAL POLYMER THIN FILMS BY LANGMUIR-BLODGETT TECHNIQUE

    Institute of Scientific and Technical Information of China (English)

    Tokuji Miyashita; Tatsuo Taniguchi; Yoshihito Fukasawa

    1999-01-01

    Polymer LB films containing photofuntional groups were prepared by the copolymerization of N-dodecylacrylamide (DDA), which has an excellent property to form a stable monolayer and LB multilayers with photofunctional monomers. Tris(2, 2'-bipyridine) ruthenium complex, Ru(bpy)32+, one of the most wellknown redox-active sensitizer, was incorporated into the DDA copolymer. The photogalvanic effect based on the photoinduced electron transfer using the ruthenium complex in the polymer LB monolayer was discussed.

  5. Photoinduced oxidation of a water-soluble manganese(III) porphyrin

    OpenAIRE

    Maliyackel, Anthony C.; Otvos, John W.; Spreer, Larry O.; Calvin, Melvin

    1986-01-01

    The photoinduced oxidation of tetra(N-methyl-4-pyridyl)porphyrinmanganese(III) has been achieved in homogeneous solution. The manganese porphyrin was used as an electron donor in a three-component system with tris-(2,2′-bipyridine)ruthenium(II) as the photosensitizer and chloropentaamminecobalt(III) as the electron acceptor. The photooxidized manganese porphyrin is unstable in aqueous solution, reverting to the starting manganese(III) porphyrin. The oxidation of manganese(III) porphyrin and t...

  6. Sledování interakce poškozené DNA s komplexy osmia při použití eliminační voltametrie s lineárním scanem

    Czech Academy of Sciences Publication Activity Database

    Navrátil, Tomáš; Josypčuk, Bohdan

    Praha : Česká společnost chemická, 2003 - (Barek, J.; Navrátil, T.; Novotný, L.), s. 37-41 ISBN 80-86238-29-6. [Moderní elektrochemické metody /23./. Praha (CZ), 20.05.2003-22.05.2003] Grant ostatní: GIT(AR) 101/02/U111/CZ Institutional research plan: CEZ:AV0Z4040901 Keywords : DNA * voltammetry * Os(bipyridine) Subject RIV: CG - Electrochemistry

  7. Synthesis of asymmetric supramolecular compounds using a Ni(0) catalysed homo-coupling approach

    NARCIS (Netherlands)

    Cassidy, Lynda; Horn, Sabine; Cleary, Laura; Halpin, Yvonne; Browne, Wesley R.; Vos, Johannes G.

    2009-01-01

    The synthesis and characterisation of a series of dinuclear ruthenium and osmium polypyridyl metal complexes based on the bridging ligands [5-(5'-bipyridin-2',2 ''-yl)-3-(pyridin-2-yl)]-1,2,4-triazole (Hpytr-bipy), 2,2 ''-bis(pyridin-2 '' yl)-5,5 ''-bis(pyridin-3 ''-yl) (bipy-bipy) and 5,5'-bis(pyri

  8. Theoretical studies of -NH₂ and -NO₂ substituted dipyridines.

    Science.gov (United States)

    Liu, Hui; Wang, Fang; Wang, Gui-Xiang; Gong, Xue-Dong

    2012-10-01

    In this work, the experimental synthesized bipyridines 3,3'-Dinitro-2,2'-bipyridine (DNBPy), 3,3'-Dinitro-2,2'-bipyridine-1,1'-dioxide (DNBPyO), and (3-Nitro-2-pyridyl)(5-nitro-2-pyridyl) amine (NPyA), and a set of designed dipyridines that have similar frameworks but different linkages and substituents with NPyA were studied theoretically at the B3LYP/6-31G* level of density functional theory. The gas-phase heats of formation were predicted based on the isodesmic reactions and the condensed-phase heats of formation and heats of sublimation were estimated in the framework of the Politzer approach. The crystal densities have been computed from molecular packing. Results show that this method gives a good estimation of density in comparison with the available experimental data for DNBPy, DNBPyO, and NPyA. The predicted detonation velocities and pressures indicate that the performance of dipyridines linked with -O-, -NH-, or -CH₂- bridges have not been improved compared with that of the directly linked dipyridines, but all derivatives have better detonation properties than DNBPy, DNBPyO, and NPyA because of the presence of more nitro groups. An analysis of the bond dissociation energies (BDEs) or the impact sensitivity (h₅₀) suggests that introduction of different bridges but not substituents has little influence on thermal stability. The calculated h₅₀ may be more reliable than BDE for predicting stability. Four bridged bipyridines have quite good detonation performance and low sensitivity. PMID:22648786

  9. Chiral Cu(II-catalyzed enantioselective β-borylation of α,β-unsaturated nitriles in water

    Directory of Open Access Journals (Sweden)

    Lei Zhu

    2015-10-01

    Full Text Available The promising performance of copper(II complexes was demonstrated for asymmetric boron conjugate addition to α,β-unsaturated nitriles in water. The catalyst system, which consisted of Cu(OAc2 and a chiral 2,2′-bipyridine ligand, enabled β-borylation and chiral induction in water. Subsequent protonation, which was accelerated in aqueous medium, led to high activity of this asymmetric catalysis. Both solid and liquid substrates were suitable despite being insoluble in water.

  10. A three-dimensional accordion-like metal-organic framework: synthesis and unconventional oriented growth on a surface.

    Science.gov (United States)

    Haraguchi, Tomoyuki; Otsubo, Kazuya; Sakata, Osami; Kawaguchi, Shogo; Fujiwara, Akihiko; Kitagawa, Hiroshi

    2016-05-21

    We describe the synthesis and sorption properties of a new metal-organic framework (MOF), Fe(H2O)2(bpy)[Pt(CN)4]·H2O (bpy = 4,4'-bipyridine), with a three-dimensional accordion-like structure. Although crystalline oriented MOF thin films reported to date have been mainly limited to a layer-type structure, we succeeded in the fabrication of its crystalline oriented thin film. PMID:27063003

  11. Bis[4-amino-N-(pyrimidin-2-ylbenzenesulfonamidato](2,2′-bipyridinemanganese(II

    Directory of Open Access Journals (Sweden)

    Tian-Jing He

    2010-06-01

    Full Text Available The title compound, [Mn(C10H9N4O2S2(C10H8N2], contains a distorted octahedral [Mn(sdz2(bpy] (sdz is the sulfadiazine anion and bpy is 2,2′-bipyridine complex molecule. A three-dimensional network is generated by N—H...N, N—H...O and C—H...O hydrogen bonds from the sulfadiazine ligands.

  12. Nickel-Catalyzed Regiodivergent Opening of Epoxides with Aryl Halides: Co-Catalysis Controls Regioselectivity

    OpenAIRE

    Zhao, Yang; Weix, Daniel J.

    2013-01-01

    Epoxides are versatile intermediates in organic synthesis, but have rarely been employed in cross-coupling reactions. We report that bipyridine-ligated nickel can mediate the addition of functionalized aryl halides, a vinyl halide, and a vinyl triflate to epoxides under reducing conditions. For terminal epoxides, the regioselectivity of the reaction depends upon the co-catalyst employed. Iodide co-catalysis results in opening at the less hindered position via an iodohydrin intermediate. Titan...

  13. Amphiphilic nanocapsules entangled with organometallic coordination polymers for controlled cargo release.

    Science.gov (United States)

    Liang, Guodong; Ni, Huan; Bao, Suping; Zhu, Fangming; Gao, Haiyang; Wu, Qing; Tang, Ben Zhong

    2014-06-01

    A class of new amphiphilic nanocapsules entangled with organometallic coordination polymers has been developed for the first time. Poly(2-(N,N-dimethyl amino)ethyl methacrylate)-b-polystyrene capped with β-cyclodextrin (β-CD) (CD-PDMAEMA-b-PS) is first synthesized using sequent RAFT polymerization of styrene and 2-(N,N-dimethyl amino)ethyl methacrylate with xanthate modified β-CD as chain transfer agent. The end group of β-CD is allowed to include 4,4'-bipyridine through host-guest inclusion to yield PDMAEMA-b-PS terminated with an inclusion complex of β-CD and bipyridine (bpy-PDMAEMA-b-PS), which is then used as surfactant to prepare emulsion droplets in toluene/water mixture. Upon addition of Ni(II), bipyridine coordinates with Ni(II) to form coordination polymers in the periphery of emulsion droplets, affording amphiphilic capsules entangled with organometallic coordination polymers, as confirmed by GPC, (1)H NMR, SEM, TEM, DLS, and so on. The organometallic coordination polymer capsules are capable of encapsulating organic cargoes. Interestingly, encapsulated cargoes can be extracted from the capsules without damaging the capsules. Such capsules are potential candidates for encapsulating and controlled release of organic cargoes. PMID:24828951

  14. Cathodic electrogenerated chemiluminescence of Ru(bpy)32+ chelate at oxide-coated heavily doped silicon electrodes

    International Nuclear Information System (INIS)

    High amplitude cathodic pulse polarization of ultra thin oxide film-coated heavily doped silicon electrodes induces tunnel emission of hot electrons into aqueous electrolyte solution, which probably results in the generation of hydrated electrons in the vicinity of the electrode surface. The method allows the detection of tris (2,2'-bipyridine) ruthenium(II) chelate at subnanomolar concentration level. This paper shows that both n- and p-type heavily doped silicon electrodes can be used, illustrates the effect of oxide film thickness upon the silicon electrode on the intensity of ECL of tris (2,2'-bipyridine) ruthenium(II) and discusses the basic features of tris (2,2'-bipyridine) ruthenium(II) chelate-specific ECL at these electrodes. Thin oxide film-coated silicon electrodes provide a lower blank emission and a higher ECL intensity of the present ruthenium chelate than oxide-covered aluminium electrodes. This suggests that thin oxide film-coated silicon is a very promising working electrode material, especially in microanalytical systems made fully or partly of silicon

  15. Cu(N-N)2Cl2 and Cu(N-N-N)Cl2 and HgCl2 building blocks in the synthesis of coordination compounds-X-ray studies and magnetic properties

    International Nuclear Information System (INIS)

    A series of complexes containing Cu(N-N)2Cl2 (N-N=bis(pyrazol-1-yl)methane (bpzm), bis(3,5dimethylpyrazol-1-yl)methane (bdmpzm), 2,2-dipyridylamine (dpa), 5,6-diphenyl-3-(2-pyridyl)-1,2,4-trazine (dppt) and 2,2'-bipyridine (bipy)), Cu(N-N-N)Cl2 (N-N-N=2,2':6',2''-terpyridine (terpy)) and HgCl2 building blocks have been synthesized and structurally characterized. Increase in structural dimensionality is observed for [Cu(bpzm)2][HgCl4], [Cu(dpa)2][HgCl3]2 and [Cu(terpy)(μ-Cl)HgCl3] compounds. No coordination polymers have formed in the case of bis(3,5dimethylpyrazol-1-yl)methane, 5,6-diphenyl-3-(2-pyridyl)-1,2,4-trazine and 2,2'-bipyridine. The [Cu(bpzm)2][HgCl4] and [Cu(terpy)(μ-Cl)HgCl3] complexes have been studied by magnetic measurements. - Graphical abstract: N-N: bis(3,5dimethylpyrazol-1-yl)methane (bdmpzm), 2,2-dipyridylamine (dpa), 5,6-diphenyl-3-(2-pyridyl)-1,2,4-trazine (dppt) and 2,2'-bipyridine (bipy), 6',2''-terpyridine (terpy).

  16. Crystal structure of poly[[(2,2′-bipyridinemanganese(II]-di-μ-thiocyanato

    Directory of Open Access Journals (Sweden)

    Stefan Suckert

    2014-12-01

    Full Text Available In the crystal structure of the polymeric title compound, [Mn(NCS2(C10H8N2]n, the MnII cations are coordinated by one chelating 2,2′-bipyridine ligand and four thiocyanate anions (two N- and two S-coordinating, forming a distorted [MnN4S2] octahedron. The asymmetric unit consists of one manganese cation located on a twofold rotation axis and half of a 2,2′-bipyridine ligand, the other half being generated by the same twofold rotation axis, as well as one thiocyanate anion in a general position. The MnII cations are linked by two pairs of μ1,3-bridging thiocyanate ligands into chains along the c axis; because the N atoms of the 2,2′-bipyridine ligands, as well as the N and the S atoms of the thiocyanate anions, are each cis-coordinating, these chains show a zigzag arrangement.

  17. Synthesis and Crystal Structure of a 1-D Chain Coordination Complex {[Mn2(HCAM)3(H2bipy)]·5H2O}n

    Institute of Scientific and Technical Information of China (English)

    SUN Ya-Guang; RONG Shu-Ting; WU Yong-Li; YU Wan; WANG Chuan-Sheng; ZHANO Wan-Zhong; GAO En-Jun

    2009-01-01

    The 1-D chain coordination complex of {[Mn2(HCAM)3(H2bipy)]·5H2O}n (H3CAM = 4-hydroxypyridine-2,6-dicarboxylic acid, bipy = 4,4'-bipyridine) has been synthesized by the reaction of 4-hydroxypyridine-2,6-dicarboxylic acid, 4,4'-bipyridine and manganese carbonate under hydrothermal conditions, and its crystal structure was determined by X-ray diffraction method. The crystal belongs to the monoclinie system, space group P21/n with a = 10.110(2), b = 20.159(4), c = 17.861(4) A, β = 99.67(3)°, V= 3.5884(12) nm3, Mr= 901.47, Z = 4, Dc= 1.669 g·cm-3, μ= 0.798 mm-1, F(000) = 1840, the final R = 0.0713 and wR = 0.1853. The complex forms a 1-D chain bridged by HCAM, protonated 4,4-bipyridines link the 1-D chains to construct 2-D networks via N-H…O hydrogen bonds, and networks are further extended via π-π stacking and hydrogen bonds into 3-D supramolecular framework.

  18. Synthesis, photophysical and preliminary investigation of the dye-sensitized solar cells properties of functionalized anthracenyl-based bipyridyl and phenanthrolyl Ru(II) complexes

    Indian Academy of Sciences (India)

    Adewale O Adeloye; Peter A Ajibade; Frances R Cummings; Lukas J Le Roux; Sampson N Mamphweli; Edson L Meyer

    2013-01-01

    Four new amphiphilic ligands: 4-(2,3-dimethylacrylic acid)-2,2'-bipyridine (L1), 4-(9-anthracenyl-10-(2,3-dimethylacrylic acid)-2,2'-bipyridine (L2), 5-(2,3-dimethylacrylic acid)-1,10-phenanthroline (L3) and 5-(9-anthracenyl-10-(2,3-dimethylacrylic acid)-1,10-phenanthroline (L4), with their corresponding homonuclear ruthenium(II) complexes formulated as cis-[Ru-(L1)3(PF6)2] (C1), cis-[Ru-(L2)3(PF6)2] (C2), cis-[Ru-(L3)3(PF6)2] (C3) and cis-[Ru-(L4)3(PF6)2] (C4), have been synthesized and characterized by elemental analysis, 1H- and 13C- NMR, FT-IR, UV-Vis and photoluminescence spectroscopy. The complexes exhibit broad and intense metal-to-ligand charge transfer (MLCT) transition bands in the visible region (400-700 nm), and red light emitting properties at room temperature. By comparison however, complexes C1 and C2 bipyridine moiety gave lower molar absorptivity coefficient at relatively similar wavelength characteristics (410-520 nm) when compared to C3 and C4 with phenanthroline based molecules. Cyclic voltammograms of the complexes revealed complex C4 with most reduction potential which might be due to increase in the conjugation of the anthracene functionalized units. Preliminary investigation of the solar cell efficiency of the complexes on TiO2 nanocrystalline films gave the best result with efficiency of 0.103% for C1 under illumination at 1000 W/m2 AM 1.5. Electrochemical impedance spectroscopy (EIS) technique however, revealed the charge transfer resistances (Rct) of the electrons on the TiO2 semiconductor.

  19. Dye-sensitization of nanocrystalline semiconductor electrodes

    Science.gov (United States)

    Stipkala, Jeremy M.

    Electron transfer from excited sensitizer molecules into colloidal titanium dioxide thin film electrodes in the absence of an intimate covalent bond has been exploited to convert light into electricity. A brief review of research reported in the literature is given, which focuses on the kinetics of interfacial charge transfer events at sensitized sol-gel processed semiconductor particles. It was found that forward electron transfer from the sensitizer to the semiconductor is several orders of magnitude faster than the energy wasting recombination in the most successful systems. The novel results included here detail two new approaches to the problem of immobilizing sensitizers on the surface of the semiconductor. First, linkage ligands 4-methyl-4sp'-R-2,2sp'-bipyridine, where R = -COOH, -(CHsb2)sb3COOH, and -(CHsb2)sb3COCHsb2COOCsb2Hsb5 were synthesized. These ligands were incorporated into the sensitizer RuspII(dmb)sb2LL(PFsb6)sb2, where dmb = 4,4sp'-dimethyl-2,2sp'-bipyridine, and LL is the linkage ligand. The performance of these ruthenium sensitizers in regenerative solar cells was measured. It was found that the presence of the propylene spacer slows the recombination of the injected electron in the semiconductor with the oxidized sensitizer by a factor of 3-4. Second, electropolymerization of RuspII(vbpy) compounds, where vbpy is 4-methyl-4sp'-vinyl-2,2sp'-bipyridine, is explained. If the polymerization conditions are kept within narrow parameters, it is possible to add polymeric sensitizer to the semiconductor electrode and improve the cell performance. It was often observed, however, that the addition of polymer increased the dye surface coverage but lowered light-to-electricity conversion efficiencies. Evidence for self-quenching and iodide diffusion inhibition as mechanistic explanations for the reduced efficiencies from polymeric samples is given.

  20. Fully Enzymatic Membraneless Glucose|Oxygen Fuel Cell That Provides 0.275 mA cm(-2) in 5 mM Glucose, Operates in Human Physiological Solutions, and Powers Transmission of Sensing Data.

    Science.gov (United States)

    Ó Conghaile, Peter; Falk, Magnus; MacAodha, Domhnall; Yakovleva, Maria E; Gonaus, Christoph; Peterbauer, Clemens K; Gorton, Lo; Shleev, Sergey; Leech, Dónal

    2016-02-16

    Coimmobilization of pyranose dehydrogenase as an enzyme catalyst, osmium redox polymers [Os(4,4'-dimethoxy-2,2'-bipyridine)2(poly(vinylimidazole))10Cl](+) or [Os(4,4'-dimethyl-2,2'-bipyridine)2(poly(vinylimidazole))10Cl](+) as mediators, and carbon nanotube conductive scaffolds in films on graphite electrodes provides enzyme electrodes for glucose oxidation. The recombinant enzyme and a deglycosylated form, both expressed in Pichia pastoris, are investigated and compared as biocatalysts for glucose oxidation using flow injection amperometry and voltammetry. In the presence of 5 mM glucose in phosphate-buffered saline (PBS) (50 mM phosphate buffer solution, pH 7.4, with 150 mM NaCl), higher glucose oxidation current densities, 0.41 mA cm(-2), are obtained from enzyme electrodes containing the deglycosylated form of the enzyme. The optimized glucose-oxidizing anode, prepared using deglycosylated enzyme coimmobilized with [Os(4,4'-dimethyl-2,2'-bipyridine)2(poly(vinylimidazole))10Cl](+) and carbon nanotubes, was coupled with an oxygen-reducing bilirubin oxidase on gold nanoparticle dispersed on gold electrode as a biocathode to provide a membraneless fully enzymatic fuel cell. A maximum power density of 275 μW cm(-2) is obtained in 5 mM glucose in PBS, the highest to date under these conditions, providing sufficient power to enable wireless transmission of a signal to a data logger. When tested in whole human blood and unstimulated human saliva maximum power densities of 73 and 6 μW cm(-2) are obtained for the same fuel cell configuration, respectively. PMID:26750758

  1. Flexible sorption and transformation behavior in a microporous metal-organic framework.

    Science.gov (United States)

    Cussen, Edmund J; Claridge, John B; Rosseinsky, Matthew J; Kepert, Cameron J

    2002-08-14

    Crystals of the metal-organic framework material Ni(2)(4,4'-bipyridine)(3)(NO(3))(4) (A) have been grown by reaction of Ni(NO(3))(2).6H(2)O and 4,4'-bipyridine in methanol solution. Single-crystal X-ray diffraction experiments show that the ladder structure of the framework is maintained after desolvation of the material, resulting in the production of a porous solid stable to 215(4) degrees C. Powder X-ray diffraction has been employed to confirm the bulk purity and temperature stability of this material. The crystal structure indicates that the pore window has an area of 12.3 A(2). However, sorption experiments show these windows will admit toluene, which has a minimum cross-sectional area of 26.6 A(2), with no significant change in the structure. Monte Carlo docking calculations show that toluene can be accommodated within the large pores of the structure. Exposure of the related microporous material Ni(2)(4,4'-bipyridine)(3)(NO(3))(4).2C(2)H(5)OH (B) to methanol vapor causes a guest-driven solid-state transformation to A which is observed using powder X-ray diffraction. This structural rearrangement proceeds directly from crystalline B to crystalline A and is complete in less than 1 day. Mechanisms for the transformation are proposed which require breaking of at least one in six of the covalent bonds that confer rigidity on the framework. PMID:12167052

  2. Action of chelators on solid iron in phosphate-containing aqueous solutions

    International Nuclear Information System (INIS)

    To study the effect of strong iron-ligands on steel corrosion, mild steel electrodes were immersed in solutions containing 20 mM phosphate buffer (pH=7.2) and between 0.01 mM and 1 M of either the iron(II)-chelators 2,2'-bipyridine or FerroZine, or the iron(III)-chelators citrate or acetylacetonate. Resulting surface reactions were investigated by quantifying the electrochemical potential (E), the electrochemical polarization resistance (Rp), the corrosion current (Icorr) and the release of iron into solution. The surface was further analyzed by scanning electron microscopy (SEM/SEM-EDAX) and atomic force microscopy. Concentrations of 0.1 mM of any of the chelators led to slight, temporary changes in E, Icorr and Rp. Concentrations of 10 mM resulted in characteristic changes of E, which were the same for all chelators and in the precipitation of FePO4 in the case of citrate and acetylacetonate, or vivianite [Fe3(PO4)2 · 8H2O] in the case of bipyridine and FerroZine. Concentrations of 1 mM of both iron(III)-chelators led to a temporary drop of E similar to that found with 0.1 mM chelator. With iron(II)-chelators, E dropped to about -500 mV before oscillating for several days. The amplitudes of the oscillations were up to 200 mV with periods of 30 and 20-25 min for bipyridine and FerroZine, respectively

  3. Post-Synthetic Shaping of Porosity and Crystal Structure of Ln-Bipy-MOFs by Thermal Treatment

    Directory of Open Access Journals (Sweden)

    Philipp R. Matthes

    2015-07-01

    Full Text Available The reaction of anhydrous lanthanide chlorides together with 4,4′-bipyridine yields the MOFs 2∞[Ln2Cl6(bipy3]·2bipy, with Ln = Pr − Yb, bipy = 4,4′-bipyridine, and 3∞[La2Cl6(bipy5]·4bipy. Post-synthetic thermal treatment in combination with different vacuum conditions was successfully used to shape the porosity of the MOFs. In addition to the MOFs microporosity, a tuneable mesoporosity can be implemented depending on the treatment conditions as a surface morphological modification. Furthermore, thermal treatment without vacuum results in several identifiable crystalline high-temperature phases. Instead of collapse of the frameworks upon heating, further aggregation under release of bipy is observed. 3∞[LaCl3(bipy] and 2∞[Ln3Cl9(bipy3], with Ln = La, Pr, Sm, and 1∞[Ho2Cl6(bipy2] were identified and characterized, which can also exhibit luminescence. Besides being released upon heating, the linker 4,4′-bipyridine can undergo activation of C-C bonding in ortho-position leading to the in-situ formation of 4,4′:2′,2′′:4′′,4′′′-quaterpyridine (qtpy. qtpy can thereby function as linker itself, as shown for the formation of the network 2∞[Gd2Cl6(qtpy2(bipy2]·bipy. Altogether, the manuscript elaborates the influence of thermal treatment beyond the usual activation procedures reported for MOFs.

  4. Electrochemical reduction of /Ru edta L/ compounds in aqueous solution

    International Nuclear Information System (INIS)

    Electrochemical reduction of the complexes [Ru edta L], [L= 2,2' bipyridine (2,2' bipy) pyrazinamide (pz CONH2); 4-cyanopyridine 4-cyanopyridine (4-CNpy); nicotinamide (NIC); hydroxil; 3-aminophenol (3-NH2 φ OH) and 2-aminopyridine (2-NH2 py)] in aqueous solution (acetate buffer, pH 4.65 or phosphate buffer, pH=8.2), μ=0,2 M p-cH3φSO3Li is investigated. The measurements have been made by cyclic voltammetry technique, using platinum, gold and mercury pool as working electrodes. (M.J.C.)

  5. Nickel-Catalyzed Carbon–Carbon Bond-Forming Reactions of Unactivated Tertiary Alkyl Halides: Suzuki Arylations

    OpenAIRE

    Zultanski, Susan L.; Fu, Gregory C.

    2013-01-01

    The first Suzuki cross-couplings of unactivated tertiary alkyl electrophiles are described. The method employs a readily accessible catalyst (NiBr[subscript 2]·diglyme/4,4′-di-tert-butyl-2,2′-bipyridine, both commercially available) and represents the initial example of the use of a group 10 catalyst to cross-couple unactivated tertiary electrophiles to form C–C bonds. This approach to the synthesis of all-carbon quaternary carbon centers does not suffer from isomerization of the alkyl group,...

  6. Synthesis, Spectral study of Ni (II) and CU (II) metal ions with Heterocyclic Ligands

    OpenAIRE

    Sachin R Joshi; Seema I. Habib

    2014-01-01

    Four Complexes of Cu (II) and Ni (II) Schiff bases have been prepared. The Schiff bases are derived by the reaction of Salisylaldoxime primary ligand with heterocyclic compounds such as 2-aminopyridine (S-L2), 2-2- bipyridine (S-L4) to form the secondary ligand, which than react with the metal halides to form corresponding complexes. The elemental analysis data shows that the metal to ligand ratio in all Ni(II) and Cu(II) simple complexes are 1:2 while for mixed ligand complexes having ratio ...

  7. Living atom transfer radical polymerization of 4-acetoxystyrene

    DEFF Research Database (Denmark)

    Gao, Bo; Chen, Xianyi; Ivan, Bela;

    1997-01-01

    Living atom transfer radical polymerization (ATRP) of 4-acetoxystyrene (1), a protected 4-vinylphenol, leading to poly(4-acetoxystyrene) with well-defined molecular weight and narrow molecular weight distribution was carried out in bulk with a,a'-dibromoxylene(2)/CuBr/2,2-bipyridine(bpy) as...... initiating system. A linear (M) over bar(n), versus monomer conversion plot was found in good accordance with the theoretical line, indicating 100% initiating efficiency. The polymerization is first order in respect to monomer up to about 70% monomer conversion. Deviations from linearity at higher conversion...

  8. Light induced electron transfer reactions of metal complexes

    International Nuclear Information System (INIS)

    Properties of the excited states of tris(2,2'-bipyridine) and tris(1,10-phenanthroline) complexes of chromium(III), iron(II), ruthenium(II), osmium(II), rhodium(III), and iridium(III) are described. The electron transfer reactions of the ground and excited states are discussed and interpreted in terms of the driving force for the reaction and the distortions of the excited states relative to the corresponding ground states. General considerations relevant to the conversion of light into chemical energy are presented and progress in the use of polypyridine complexes to effect the light decomposition of water into hydrogen and oxygen is reviewed

  9. Ferrocene and cobaltocene derivatives for non-aqueous redox flow batteries.

    Science.gov (United States)

    Hwang, Byunghyun; Park, Min-Sik; Kim, Ketack

    2015-01-01

    Ferrocene and cobaltocene and their derivatives are studied as new redox materials for redox flow cells. Their high reaction rates and moderate solubility are attractive properties for their use as active materials. The cyclability experiments are carried out in a static cell; the results showed that these materials exhibit stable capacity retention and predictable discharge potentials, which agree with the potential values from the cyclic voltammograms. The diffusion coefficients of these materials are 2 to 7 times higher than those of other non-aqueous materials such as vanadium acetylacetonate, iron tris(2,2'-bipyridine) complexes, and an organic benzene derivative. PMID:25428116

  10. Crossbar nanoarchitectonics of the crosslinked self-assembled monolayer

    OpenAIRE

    Hamoudi, Hicham

    2014-01-01

    A bottom-up approach was devised to build a crossbar device using the crosslinked SAM of the 5,5′-bis (mercaptomethyl)-2,2′-bipyridine-Ni2+ (BPD- Ni2+) on a gold surface. To avoid metal diffusion through the organic film, the author used (i) nanoscale bottom electrodes to reduce the probability of defects on the bottom electrodes and (ii) molecular crosslinked technology to avoid metal diffusion through the SAMs. The properties of the crosslinked self-assembled monolayer were determined by XP...

  11. Multifunctional sensing ability of a new Pt/Zn-based luminescent coordination polymer

    OpenAIRE

    Kobayashi, Atsushi; Hara, Hirofumi; Noro, Shin-ichiro; Kato, Masako

    2010-01-01

    We synthesized a new Pt/Zn-based coordination polymer, {Zn[Pt(CN)2(5,5'-dcbpy)]・4H2O}n, (5,5'-H2dcbpy = 5,5'-dicarboxy-2,2'-bipyridine), which exhibits reversible colour changes in response to temperature change or exposure to chemical vapours and liquids. Such chromic behaviour shows promise for sensing not only changes in temperature but also for detecting chemical solvents and vapours. The single crystal X-ray structure indicates that one-dimensional coordination polymeric chains formed by...

  12. Single-Molecule Electrochemical Transistor Utilizing a Nickel-Pyridyl Spinterface

    OpenAIRE

    Brooke, Richard J.; Jin, Chengjun; Szumski, Douglas S; Nichols, Richard J; Mao, Bing-Wei; Thygesen, Kristian S.; Schwarzacher, Walther

    2015-01-01

    Using a scanning tunnelling microscope break-junction technique, we produce 4,4′-bipyridine (44BP) single-molecule junctions with Ni and Au contacts. Electrochemical control is used to prevent Ni oxidation and to modulate the conductance of the devices via nonredox gating—the first time this has been shown using non-Au contacts. Remarkably the conductance and gain of the resulting Ni-44BP-Ni electrochemical transistors is significantly higher than analogous Au-based devices. Ab-initio calcula...

  13. 4,4′-Bipyridine–4-(p-toluene­sulfonamido)­benzoic acid (1/2)

    Science.gov (United States)

    Huang, Miao-Ling

    2011-01-01

    In the title compound, C14H13NO4S·0.5C10H8N2, the two benzene rings are nearly perpendicular to each other [dihedral angle = 83.21 (10)°]. The bipyridine mol­ecule is centrosymmetric, the mid-point of the C—C bond linking the pyridine rings being located on an inversion center. Inter­molecular N—H⋯O and O—H⋯N hydrogen bonds and weak inter­molecular C—H⋯O hydrogen bonds are present in the crystal structure. PMID:22059045

  14. 4,4′-Bipyridine–4-(p-toluene­sulfonamido)­benzoic acid (1/2)

    OpenAIRE

    Huang, Miao-Ling

    2011-01-01

    In the title compound, C14H13NO4S·0.5C10H8N2, the two benzene rings are nearly perpendicular to each other [dihedral angle = 83.21 (10)°]. The bipyridine mol­ecule is centrosymmetric, the mid-point of the C—C bond linking the pyridine rings being located on an inversion center. Inter­molecular N—H⋯O and O—H⋯N hydrogen bonds and weak inter­molecular C—H⋯O hydrogen bonds are present in the crystal structure.

  15. Luminescence quenching of Ru(phen)$^{2+}_{3}$ by some polymer-cobalt(III) complexes - Effect of micelles and DNA

    Indian Academy of Sciences (India)

    R Senthil Kumar; K Sasikala; S Arunachalam

    2007-05-01

    Studies on the luminescence quenching of Ru(phen)$^{2+}_{3}$ (phen = 1,10-phenanthroline) by the polymer-cobalt(III) complex ions, cis-[Co(phen)2(BPEI)Cl]2+ and cis-[Co(bpy)2(BPEI)Cl]2+ (bpy = 2,2'-bipyridine, BPEI = branched polyethyleneimine) in DNA as well as in various micellar media by steadystate emission spectroscopic technique have been reported. The quenching rate constants were arrived through Stern-Volmer equation. The results have been analysed based on hydrophobic as well as electrostatic binding between polymer-cobalt(III) complexes and DNA/micelles.

  16. Lewis acid-base interactions between platinum(ii) diaryl complexes and bis(perfluorophenyl)zinc: strongly accelerated reductive elimination induced by a Z-type ligand.

    Science.gov (United States)

    Liberman-Martin, Allegra L; Levine, Daniel S; Ziegler, Micah S; Bergman, Robert G; Tilley, T Don

    2016-05-19

    Z-type interactions between bis(perfluorophenyl)zinc and platinum(ii) diaryl complexes supported by 1,10-phenanthroline (phen), 2,2'-bipyridine (bpy), and bis(dimethylphosphino)ethane (dmpe) ligands are reported. In the solid state, the nature of the Pt-Zn interaction depends on the bidentate ligand; the phen-supported complex exhibits an unsupported Pt-Zn bond, while the dmpe derivative features additional bridging aryl interactions. A strongly accelerated rate of reductive elimination is observed for phen- and bpy-supported complexes, while aryl exchange between Pt and Zn is observed for the dmpe complex. PMID:27161155

  17. Self-assembly of heteroleptic dinuclear metallosupramolecular kites from multivalent ligands via social self-sorting

    Directory of Open Access Journals (Sweden)

    Christian Benkhäuser

    2015-05-01

    Full Text Available A Tröger's base-derived racemic bis(1,10-phenanthroline ligand (rac-1 and a bis(2,2'-bipyridine ligand with a central 1,3-diethynylbenzene unit 2 were synthesized. Each of these ligands acts as a multivalent entity for the binding of two copper(I ions. Upon coordination to the metal ions these two ligands undergo selective self-assembly into heteroleptic dinuclear metallosupramolecular kites in a high-fidelity social self-sorting manner as evidenced by NMR spectroscopy and mass spectrometry.

  18. Sensitization of n-type Ti O{sub 2} electrode by a novel isoquinoline ruthenium (II) poly pyridyl complex

    Energy Technology Data Exchange (ETDEWEB)

    Garcia, Christian Graziani; Iha, Neyde Yukie Murakami [Sao Paulo Univ., SP (Brazil). Inst. de Quimica; Argazzi, Roberto; Bignozzi, Carlo Alberto [Ferrara Univ. (Italy). Dipt. di Chimica

    1998-02-01

    The effective sensitization of Ti O{sub 2} to visible light by cis-[(dcbH{sub 2})2 Ru (isq)2](Cl O{sub 4}){sub 2}, where dcb H{sub 2} = 4,4'-(C O{sub 2}H){sub 2}-2,2'- bipyridine and isq = isoquinoline, is reported. The photocurrent action spectrum obtained for the regenerative cell with dye coated nanocrystalline Ti O{sub 2} films resulted in IPCE values up to 40%. This novel compound acts as an efficient Ti O{sub 2} photoanode sensitizer in thin-layer sandwich solar cells. (author)

  19. Dielectric and magnetic anisotropy of a nematic ytterbium complex

    International Nuclear Information System (INIS)

    The sign and the magnitude of the dielectric anisotropy of an ytterbium-based paramagnetic nematic liquid crystal complex, namely, tris[1-(4-(4-propylcyclohexyl)phenyl)octane-1,3-dione]-[5,5'-di (heptadecile)-2,2'-bipyridine]ytterbium, are determined. The temperature dependence of the permittivity components of the complex is obtained in the temperature range of a nematic phase. The sign of the anisotropy of the magnetic susceptibility of this compound is experimentally determined

  20. Dielectric and magnetic anisotropy of a nematic ytterbium complex

    Energy Technology Data Exchange (ETDEWEB)

    Dobrun, L. A., E-mail: l.dobrun@spbu.ru; Sakhatskii, A. S.; Kovshik, A. P.; Ryumtsev, E. I.; Kolomiets, I. P. [St. Petersburg State University (Russian Federation); Knyazev, A. A.; Galyametdinov, Yu. G. [Kazan National Research Technological University (Russian Federation)

    2015-05-15

    The sign and the magnitude of the dielectric anisotropy of an ytterbium-based paramagnetic nematic liquid crystal complex, namely, tris[1-(4-(4-propylcyclohexyl)phenyl)octane-1,3-dione]-[5,5'-di (heptadecile)-2,2'-bipyridine]ytterbium, are determined. The temperature dependence of the permittivity components of the complex is obtained in the temperature range of a nematic phase. The sign of the anisotropy of the magnetic susceptibility of this compound is experimentally determined.

  1. Microwave synthesis of mixed ligand diimine–thiosemicarbazone complexes of ruthenium(ii): biophysical reactivity and cytotoxicity†

    OpenAIRE

    Beckford, Floyd A.; Shaloski, Michael; LeBlanc, Gabriel; Thessing, Jeffrey; Lewis-Alleyne, Lesley C.; Holder, Alvin A.; LI, LIYA; Seeram, Navindra P.

    2009-01-01

    A novel microwave-assisted synthetic method has been used to synthesise a series of mixed ligand ruthenium(ii) compounds containing diimine as well as bidentate thiosemicarbazone ligands. The compounds contain the diimine 1,10-phenanthroline (phen) or 2,2′-bipyridine (bpy) and the thiosemicarbazone is derived from 9-anthraldehyde. Based on elemental analyses and spectroscopic data, the compounds are best formulated as [(phen)2Ru(thiosemicarbazone)](PF6)2 and [(phen)2Ru(thiosemicarbazone)](PF6...

  2. Epoxidation of Alkenes with Molecular Oxygen Catalyzed by Immobilized Co(acac)2 and Co(bpy)2Cl2 Complexes within Nanoreactors of Al-MCM-41

    OpenAIRE

    Farzaneh, F; Jalalian, M; Tayebi, L.

    2012-01-01

    Cobalt complexes with different ligands such as bipyridine, and acetylacetonate were immobilized within nanoreactors of Al-MCM-41, designated as Co(acac)2/Al-MCM-41 and Co(bipy)22+/Al-MCM41. The immobilized complexes were characterized by XRD, N2-adsorption desorption, FT-IR and UV-Vis techniques. It was found that Co(bipy)22+/Al-MCM41 and Co(acac)2/Al-MCM-41 successfully catalyze the oxidation of norbornene, styrene, cis-stilbene, trans-stilbene, and cyclohexene with 68% to 100% conversion a...

  3. Studies on some simple and mixed ligated oxovanadium(V) complexes of hydroxamic acids

    International Nuclear Information System (INIS)

    Some simple and mixed ligands complexes of oxovanadium(V) with benzo-, and salicyl-hydroxamic acids as primary ligands and 2,2-bipyridine and 1,10-phenanthroline as secondary ligands have been prepared and characterised. The structures of the complexes have been assigned on the basis of electronic and infra red spectral data. The IR spectra of the simple complexes reveal the bidentate nature of the primary ligands, whereas in the mixed complexes these ligands exhibit monodentate nature. Magnetic moment studies show that the complexes are diamagnetic. (author). 13 refs., 1 tab., 1 fig

  4. Star polymers by ATRP of styrene and acrylates employing multifunctional initiators

    DEFF Research Database (Denmark)

    Jankova, Katja Atanassova; Bednarek, Melania; Hvilsted, Søren

    2005-01-01

    Multifunctional initiators for atom transfer radical polymerization (ATRP) are prepared by converting ditrimethylolpropane with four hydroxyl groups, dipentaerythritol with six hydroxyl groups, and poly(3-ethyl-3-hydroxymethyl-oxetane) with similar to 11 hydroxyl groups to the corresponding 2......-bromoisobutyrates or 2-bromopropionates as obtained by reaction with acid bromides. Star polystyrene (PS) is produced by using these macroinitiators and neat styrene in a controlled manner by ATRP at 110 degrees C, employing the catalytic system CuBr and bipyridine. M. up to 51,000 associated with narrow molecular...

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

    Indian Academy of Sciences (India)

    Paladugu Suresh; Ganesan Prabusankar

    2014-09-01

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

  6. Design of molecular architectures to mimic photosynthesis

    International Nuclear Information System (INIS)

    Our researches on photo-induced energy or electron transfer for artificial photosynthesis relies on the utilization of conjugated spacers to perform these two processes over long distance. This article describes the synthesis and the characterization of dyads composed of a tris-bipyridine ruthenium complex as sensitizer, a fullerene or a naphthalene bis-imide as acceptor and a oligo(phenylene-ethynylene) as spacer. These systems exhibit electron or energy transfer from the excited state of the ruthenium complex to the acceptor. (authors)

  7. Synthesis and Preliminary Characterization of a PPE-Type Polymer Containing Substituted Fullerenes and Transition Metal Ligation Sites

    Directory of Open Access Journals (Sweden)

    Corinne A. Basinger

    2015-01-01

    Full Text Available A substituted fullerene was incorporated into a PPE-conjugated polymer repeat unit. This subunit was then polymerized via Sonogashira coupling with other repeat units to create polymeric systems approaching 50 repeat units (based on GPC characterization. Bipyridine ligands were incorporated into some of these repeat units to provide sites for transition metal coordination. Photophysical characterization of the absorption and emission properties of these systems shows excited states located on both the fullerene and aromatic backbone of the polymers that exist in a thermally controlled equilibrium. Future work will explore other substituted polyaromatic systems using similar methodologies.

  8. Thermal Thiocyanate Ligand Substitution Kinetics of the Solar Cell Dye N719 by Acetonitrile, 3-Methoxypropionitrile, and 4-tert-Butylpyridine

    DEFF Research Database (Denmark)

    Nguyen, Thai Hoang; Minh, Ha; Lund, Torben

    2007-01-01

    The kinetics of the thiocyanate substitution of the solar cell sensitizer [Ru(Hdcbpy)B2B(NCS)B2B]P2-P, 2 (n-CB4BHB9B)B4BNP+)P, (HB2Bdcbpy = L = 2,2´-bipyridine-4,4´-dicarboxylic acid), known as N719, by acetonitrile, 3-methoxypropionitrile, and 4-tert-butylpyridine (4-TBP) have been determined in...... factor of 2-10; it thus may be used as an additive to prevent the thermal degradation of thiocyanate-based ruthenium complexes in DSSC solar cells....

  9. Rectangular Coordination Polymer Nanoplates: Large-Scale, Rapid Synthesis and Their Application as a Fluorescent Sensing Platform for DNA Detection

    OpenAIRE

    Yingwei Zhang; Yonglan Luo; Jingqi Tian; Asiri, Abdullah M.; Al-Youbi, Abdulrahman O.; Xuping Sun

    2012-01-01

    In this paper, we report on the large-scale, rapid synthesis of uniform rectangular coordination polymer nanoplates (RCPNs) assembled from Cu(II) and 4,4'-bipyridine for the first time. We further demonstrate that such RCPNs can be used as a very effective fluorescent sensing platform for multiple DNA detection with a detection limit as low as 30 pM and a high selectivity down to single-base mismatch. The DNA detection is accomplished by the following two steps: (1) RCPN binds dye-labeled sin...

  10. Self-assembly of heteroleptic dinuclear metallosupramolecular kites from multivalent ligands via social self-sorting.

    Science.gov (United States)

    Benkhäuser, Christian; Lützen, Arne

    2015-01-01

    A Tröger's base-derived racemic bis(1,10-phenanthroline) ligand (rac)-1 and a bis(2,2'-bipyridine) ligand with a central 1,3-diethynylbenzene unit 2 were synthesized. Each of these ligands acts as a multivalent entity for the binding of two copper(I) ions. Upon coordination to the metal ions these two ligands undergo selective self-assembly into heteroleptic dinuclear metallosupramolecular kites in a high-fidelity social self-sorting manner as evidenced by NMR spectroscopy and mass spectrometry. PMID:26124873

  11. Synthesis, structure, electrochemistry, and photophysics of methyl-substituted phenylpyridine ortho-metalated iridium(III) complexes

    International Nuclear Information System (INIS)

    Synthetic, structural, photophysical, and electrochemical characterizations of ortho-metalated [Ir(NC)2Cl]2 dimeric and [Ir(NC)2NN]Cl monomeric complexes, where NC = 2(p-tolyl)pyridine (ptpy) or 3-methyl-2-phenylpyridine (mppy) and NN = 2,2'-bipyridine (bpy) are described. Structural characterizations by 1H and 13C nuclear magnetic resonance (NMR) indicate the presence of symmetry elements in these complexes. The ultraviolet-visible absorption properties of these complexes are reported. The results of voltametric measurements of these complexes are included. 55 references, 10 figures, 6 tables

  12. 4,4′-Bipyridine–4-(p-toluenesulfonamidobenzoic acid (1/2

    Directory of Open Access Journals (Sweden)

    Miao-Ling Huang

    2011-09-01

    Full Text Available In the title compound, C14H13NO4S·0.5C10H8N2, the two benzene rings are nearly perpendicular to each other [dihedral angle = 83.21 (10°]. The bipyridine molecule is centrosymmetric, the mid-point of the C—C bond linking the pyridine rings being located on an inversion center. Intermolecular N—H...O and O—H...N hydrogen bonds and weak intermolecular C—H...O hydrogen bonds are present in the crystal structure.

  13. Tuning the Solubility of Copper Complex in Atom Transfer Radical Self-Condensing Vinyl Polymerizations to Control Polymer Topology via One-Pot to the Synthesis of Hyperbranched Core Star Polymers

    OpenAIRE

    Zong-Cheng Chen; Chia-Ling Chiu; Chih-Feng Huang

    2014-01-01

    In this paper, we propose a simple one-pot methodology for proceeding from atom transfer reaction-induced conventional free radical polymerization (AT-FRP) to atom transfer self-condensing vinyl polymerization (AT-SCVP) through manipulation of the catalyst phase homogeneity (i.e., CuBr/2,2'-bipyridine (CuBr/Bpy)) in a mixture of styrene (St), 4-vinyl benzyl chloride (VBC), and ethyl 2-bromoisobutyrate. Tests of the solubilities of CuBr/Bpy and CuBr2/Bpy under various conditions revealed that ...

  14. Electrocatalytic detection of polysaccharides at picomolar concentrations

    Czech Academy of Sciences Publication Activity Database

    Paleček, Emil; Trefulka, Mojmír

    2011-01-01

    Roč. 136, č. 2 (2011), s. 321-326. ISSN 0003-2654 R&D Projects: GA MŠk(CZ) ME09038; GA AV ČR KAN400310651; GA AV ČR(CZ) GPP301/10/P548; GA MŠk(CZ) LC06035; GA ČR(CZ) GAP301/11/2055 Institutional research plan: CEZ:AV0Z50040507; CEZ:AV0Z50040702 Keywords : electrochemical detection of polysaccharides * Os(VI)-bipyridine complex * cyclic voltammography Subject RIV: BO - Biophysics Impact factor: 4.230, year: 2011

  15. Electron Transfer Mediators for Photoelectrochemical Cells Based on Cu(I Metal Complexes

    Directory of Open Access Journals (Sweden)

    Michele Brugnati

    2007-01-01

    Full Text Available The preparation and the photoelectrochemical characterization of a series of bipyridine and pyridyl-quinoline Cu(I complexes, used as electron transfer mediators in regenerative photoelectrochemical cells, are reported. The best performing mediators produced maximum IPCEs of the order of 35–40%. The J-V curves recorded under monochromatic light showed that the selected Cu(I/(II couples generated higher Vocs and fill factors compared to an equivalent I-/I3- cell, due to a decreased dark current.

  16. Accessibility studies of ionic and non-ionic fluorophores embedded in sol-gel materials and new functionalised polyhedral silsesquioxanes

    OpenAIRE

    Ruiz Abad, David

    2009-01-01

    The knowledge about the diffusion of products and educts into and out of porous materials is of high importance for the development of new porous sol-gel processed hybrid catalysts. Therefore the accessibility of active centers embedded in sol-gel materials was studied by luminescence spectroscopy. Modified tris(2,2’- bipyridine)ruthenium(II) and pyrenemethanol were co-condensed with tetramethoxysilane (TMOS) in a buffer system. The buffer enforces the pH to remain constant during the sol-gel...

  17. Cytotoxicity of Cyclometalated Platinum Complexes Based on Tridentate NCN and CNN-coordinating ligands: Remarkable Coordination Dependence

    OpenAIRE

    Vezzu, Dileep A. k.; Lu, Qun; Chen, Yan-Hua; Huo, Shouquan

    2014-01-01

    A series of cyclometalated platinum complexes with diverse coordination patterns and geometries were screened for their anticancer activity. It was discovered that the NʌCʌN-coordinated platinum complex based on 1,3-di(pyridyl)benzene displayed much higher cytotoxicity against human lung cancer cells NCI-H522, HCC827, and NCI-H1299, and human prostate cancer cell RV1 than cisplatin. In a sharp contrast, the CʌNʌN-coordinated platinum complex based on 6-phenyl-2,2′-bipyridine was ineffective o...

  18. Synthesis of asymmetric supramolecular compounds using a Ni(0) catalysed homo-coupling approach

    OpenAIRE

    Cassidy, Lynda; Horn, Sabine; Cleary, Laura; Halpin, Yvonne; Browne, Wesley R.; Vos, Johannes G.

    2009-01-01

    The synthesis and characterisation of a series of dinuclear ruthenium and osmium polypyridyl metal complexes based on the bridging ligands [5-(5'-bipyridin-2',2 ''-yl)-3-(pyridin-2-yl)]-1,2,4-triazole (Hpytr-bipy), 2,2 ''-bis(pyridin-2 '' yl)-5,5 ''-bis(pyridin-3 ''-yl) (bipy-bipy) and 5,5'-bis(pyridin-2 ''-yl)-3,3'-bis(1,2,4-triazole) (Hpytr-Hpytr) are reported. The dinuclear complexes have been synthesised via a Ni(0) catalysed cross-coupling reaction from brominated precursors. With this a...

  19. Electron Flow through Nitrotyrosinate in Pseudomonas aeruginosa Azurin

    OpenAIRE

    Warren, Jeffrey J.; Herrera, Nadia; Hill, Michael G.; Winkler, Jay R.; Gray, Harry B.

    2013-01-01

    We have designed ruthenium-modified Pseudomonas aeruginosa azurins that incorporate 3-nitrotyrosine (NO_(2)YOH) between Ru(2,2′-bipyridine)_2(imidazole)(histidine) and Cu redox centers in electron transfer (ET) pathways. We investigated the structures and reactivities of three different systems: RuH107NO_(2)YOH109, RuH124NO_(2)YOH122, and RuH126NO_(2)YOH122. RuH107NO_(2)YOH109, unlabeled H124NO_(2)YOH122, and unlabeled H126NO_(2)YOH122 were structurally characterized. The pKa’s of NO_(2)YOH a...

  20. Cobalt (Ⅱ) Complexes of Dibenzoylmethane (Hdbm): Crystal Structures and Axial Metathetical Reaction of the Complexes with Pyridine or its Derivatives%钴的二苯甲酰甲烷配合物:晶体结构及其轴向置换反应

    Institute of Scientific and Technical Information of China (English)

    卢会杰; 高洁; 杜晨霞; 樊耀亭; 侯红卫; 丁德刚; 翟俊玲

    2003-01-01

    Cobalt (Ⅱ) can form complexes with Hdbm in different environments. Hdbm reacted with cobalt nitrate to give complex 1 [Co(dbm)2 @ 2H2O]. When complex 1 reacted with pyridine, α-stilbazole or 4, 4'-bipyridine respectively, complex 2 [Co(DBM)2Py2] (Py= pyridine), 3 [Co(DBM)2Sbz2] (Sbz =α-stilbazole) or 4 [Co(DBM)2BPy] n was obtained in turn through metathetical reaction. The coordination modes are octahedral polyhedrons. In the crystal structures, the two dbms take the plane position and two other donor molecules take the axial position. CCDC: 196070 for complex 2; 186859 for complex 3.

  1. Iron and zinc availability in maize lines

    OpenAIRE

    Valéria Aparecida Vieira Queiroz; Paulo Evaristo de Oliveira Guimarães; Luciano Rodrigues Queiroz; Estefânia de Oliveira Guedes; Vanessa Diniz Barcelos Vasconcelos; Lauro José Guimarães; Paulo Eduardo de Aquino Ribeiro; Robert Eugene Schaffert

    2011-01-01

    The aim of this study was to characterize the Zn and Fe availability by phytic acid/Zn and phytic acid/Fe molar ratios, in 22 tropical maize inbred lines with different genetic backgrounds. The Zn and Fe levels were determined by atomic absorption spectrophotometry and the P through colorimetry method. Three screening methods for phytic acid (Phy) analysis were tested and one, based on the 2,2'-bipyridine reaction, was select. There was significant variability in the contents of zinc (17.5 to...

  2. Single Walled Carbon Nanohorns as Catalytic Counter Electrodes for Co(III)/(II) Electron Mediators in Dye Sensitized Cells.

    Science.gov (United States)

    Carli, Stefano; Casarin, Laura; Syrgiannis, Zois; Boaretto, Rita; Benazzi, Elisabetta; Caramori, Stefano; Prato, Maurizio; Bignozzi, Carlo Alberto

    2016-06-15

    The electrochemical properties of both pristine single walled carbon nanohorns (SWCNHS) and their chemically oxidized form (ox-SWCNHS) spray coated onto fluorine doped SnO2 (FTO) were investigated in the framework of the fabrication of cobalt based transparent dye sensitized solar cells (DSSCs). These new nanocarbon substrates, evaluated in conjunction with the Co(bpy)3(2+/3+) (bpy = 2,2'-bipyridine) redox mediator, are endowed with excellent electrocatalytic properties, ease of fabrication, and very promising stability and display a great potential for replacing the best noble metal and conductive polymer catalytic materials in the building of semitransparent counter electrodes in new generation photoelectrochemical devices. PMID:27227738

  3. Poly[[bis­(μ-4,4′-bipyridyl-κ2 N:N′)bis­(thio­cyanato-κN)manganese(II)] diethyl ether disolvate

    OpenAIRE

    Mario Wriedt; Inke Jess; Christian Näther

    2010-01-01

    In the title compound, {[Mn(NCS)2(C10H8N2)2]·2C4H10O}n, the MnII ion is coordinated by four N-bonded 4,4′-bipyridine (bipy) ligands and two N-bonded thiocyanate anions in a distorted octahedral coordination geometry. The asymmetric unit consists of one MnII ion and two bipy ligands each located on a twofold rotation axis, as well as one thiocyanate anion and one diethyl ether molecule in general positions. In the crystal structure, the metal centers with terminally bonded t...

  4. The azido ligand: a useful tool in designing chain compounds exhibiting alternating ferro- and antiferro-magnetic interactions

    OpenAIRE

    Viau, Guillaume; Lombardi, Maria Grazia; De Munno, Giovanni; Julve Olcina, Miguel; Lloret Pastor, Francisco; Faus, Juan; Caneschi, Andrea; Clemente Juan, Juan Modesto

    1997-01-01

    A one-pot reaction of NiII 1, CoII 2, FeII 3 and MnII 4 with 2,2A-bipyridine (bipy) and azide in water leads to [M(bipy)(N3)2]n chains where the metal ion is alternatively bridged by double end-on (EO) and end-to-end (EE) azido bridges; theoretical analysis of the variable-temperature magnetic susceptibility data of 1 and 4 reveals the occurrence of intrachain alternating ferro- (through EO) and antiferro-magnetic (through EE) interactions. Julve Olcina, Miguel, ; Lloret...

  5. Synthesis of new pyrrole–pyridine-based ligands using an in situ Suzuki coupling method

    Directory of Open Access Journals (Sweden)

    Matthias Böttger

    2012-07-01

    Full Text Available The compounds 6-(pyrrol-2-yl-2,2‘-bipyridine, 2-(pyrrol-2-yl-1,10-phenanthroline and 2-(2-(N-methylbenz[d,e]imidazole-6-(pyrrol-2-yl-pyridine were synthesized by using an in situ generated boronic acid for the Suzuki coupling. Crystals of the products could be grown and exhibited interesting structures by X-ray analysis, one of them showing a chain-like network with the adjacent molecules linked to each other via intermolecular N–H…N hydrogen bonds.

  6. Nickel-catalyzed regiodivergent opening of epoxides with aryl halides: co-catalysis controls regioselectivity.

    Science.gov (United States)

    Zhao, Yang; Weix, Daniel J

    2014-01-01

    Epoxides are versatile intermediates in organic synthesis, but have rarely been employed in cross-coupling reactions. We report that bipyridine-ligated nickel can mediate the addition of functionalized aryl halides, a vinyl halide, and a vinyl triflate to epoxides under reducing conditions. For terminal epoxides, the regioselectivity of the reaction depends upon the cocatalyst employed. Iodide cocatalysis results in opening at the less hindered position via an iodohydrin intermediate. Titanocene cocatalysis results in opening at the more hindered position, presumably via Ti(III)-mediated radical generation. 1,2-Disubstituted epoxides are opened under both conditions to form predominantly the trans product. PMID:24341892

  7. Synthesis, Crystal Structure and Thermal Stability of a One-dimensional Chain Cobalt Coordination Polymer [ Co( 4,4 '-bipy)( 2,4,6- TMBA)2( CH3CH2OH)2]n

    Institute of Scientific and Technical Information of China (English)

    LI Wei; LI Chang-Hong; YANG Ying-Qun; CHEN Zhi-Min; KUANG Dai-Zhi; ZHANG Chun-Hua; KANG Yun-Fei

    2006-01-01

    A one-dimensional chain cobalt(Ⅱ) coordination polymer with 2,4,6-trimethylbenzoic acid, 4,4'-bipyridine and cobalt perchlorate anhydrous has been synthesized and characterized in the mixture solvent of water and alcohol. Crystal data for this complex: monoclinic, space group C2/c, a = 2.3805(8), b = 1.1464(4), c = 1.5807(5) nm, γ = 128.435(4)°, V= 3.3791(18) nm3,Dc = 1.246 g/cm3, Z = 4, F(000) = 1340, final GooF = 1.009, R = 0.0504 and wR = 0.1287.Structural analysis shows that the cobalt ion is coordinated with two nitrogen atoms of one 4,4'-bipyridine molecule and four oxygen atoms from two 2,4,6-trimethylbenzoic acid molecules and two alcohol molecules, giving a distorted octahedral coordination geometry. The result of TG analysis indicates that the title complex is stable till 200 ℃.

  8. Synthesis and Structure of a Manganese(Ⅱ) Complex [Mn·(p-Methoxybenzoato)2·(2,2'- bipy)·H2O]·(p-methoxybenzoic Acid)

    Institute of Scientific and Technical Information of China (English)

    WANG Jian; HUANG Mei-Hua; CHENG Wen-Dan; LIU Ping

    2007-01-01

    The title compound,{[MnL2·(2,2'-bipy)·H2O]·(HL)},has been synthesized (HL =p-methoxybenzoic acid,2,2'-bipy = 2,2'-bipyridine) by the reaction of MnCl2·6H2O with p-methoxybenzoic and 2,2'-bipyridine in an alcohol-water solution.It crystallizes in the triclinic system,space group P1 with a = 10.1138(5),b = 11.2811(5),c = 16.2210(8)(A),a = 77.5920(10),β= 72.1890(10),γ = 66.2320(10)°,Mr = 683.56,V= 1603.65(13) (A)3,Z= 2,Dc = 1.416 g/cm3,F(000)= 710,μ =0.473 mm-1,the final R = 0.0619 and wR = 0.1571 for 4724 observed reflections with I > 2σ(I).The structure determined demonstrated that it is an isomeric modification of the structure reported before.The Mn atom is six-coordinated by two N and four O atoms,forming a distorted octahedral geometry.All Mn-O and Mn-N distances range from 2.113(3)~2.410(3) (A).There also.exists a dissociative p-methoxybenzoic acid beside the octahedron.

  9. Stretchable Self-Healing Polymeric Dielectrics Cross-Linked Through Metal-Ligand Coordination.

    Science.gov (United States)

    Rao, Ying-Li; Chortos, Alex; Pfattner, Raphael; Lissel, Franziska; Chiu, Yu-Cheng; Feig, Vivian; Xu, Jie; Kurosawa, Tadanori; Gu, Xiaodan; Wang, Chao; He, Mingqian; Chung, Jong Won; Bao, Zhenan

    2016-05-11

    A self-healing dielectric elastomer is achieved by the incorporation of metal-ligand coordination as cross-linking sites in nonpolar polydimethylsiloxane (PDMS) polymers. The ligand is 2,2'-bipyridine-5,5'-dicarboxylic amide, while the metal salts investigated here are Fe(2+) and Zn(2+) with various counteranions. The kinetically labile coordination between Zn(2+) and bipyridine endows the polymer fast self-healing ability at ambient condition. When integrated into organic field-effect transistors (OFETs) as gate dielectrics, transistors with FeCl2 and ZnCl2 salts cross-linked PDMS exhibited increased dielectric constants compared to PDMS and demonstrated hysteresis-free transfer characteristics, owing to the low ion conductivity in PDMS and the strong columbic interaction between metal cations and the small Cl(-) anions which can prevent mobile anions drifting under gate bias. Fully stretchable transistors with FeCl2-PDMS dielectrics were fabricated and exhibited ideal transfer characteristics. The gate leakage current remained low even after 1000 cycles at 100% strain. The mechanical robustness and stable electrical performance proved its suitability for applications in stretchable electronics. On the other hand, transistors with gate dielectrics containing large-sized anions (BF4(-), ClO4(-), CF3SO3(-)) displayed prominent hysteresis due to mobile anions drifting under gate bias voltage. This work provides insights on future design of self-healing stretchable dielectric materials based on metal-ligand cross-linked polymers. PMID:27099162

  10. Synthesis of New Ruthenium(Ⅱ)Bipyridyl Complexes and Studies on Their Photophysical and Photoelectrochemical Properties

    Institute of Scientific and Technical Information of China (English)

    宋林青; 刘普会; 王雪松; 侯原军; 张宝文; 曹怡; 李维盈; 张敬波; 肖绪瑞; 林原

    2003-01-01

    Two new mixed-ligand ruthenium(Ⅱ) complexes,Ru(dcbpy)-(LL)NCS)2[where dcbpy=4,4'-dicarboxyl-2,2''-bipyridine,LL=4,4'-bis(N-methyl-anilinomethyl)-2,2''-bipyridine(2)],were synthesized,and the tphotophysical properties of these complexes were studied.The metal-to-ligand charge transfer (MLCT) transitions of these complexes exhibited solvatochromic effect due to the existence of NCS ligands.The MLCT energies also strongly depend on the pH values of the solutions because of protonation and deprotonation of the carboxyl groups.The pKa values of the ground state,4.0 for 1 and 3.8 for 2,were obtained from the titration curves.The photoelectrochemical properties of 1 and 2 as sensitizers in sandwich-type solar cells have been studied.Complex 1 exhibited better photoelectrochemical behavior than complex 2 as expected.It was proved that the design of mixed-ligand complex by introducing electron donating group in one of the ligands should be a promising approach.

  11. The induction of apoptosis in HepG-2 cells by ruthenium(II) complexes through an intrinsic ROS-mediated mitochondrial dysfunction pathway.

    Science.gov (United States)

    Zeng, Chuan-Chuan; Lai, Shang-Hai; Yao, Jun-Hua; Zhang, Cheng; Yin, Hui; Li, Wei; Han, Bing-Jie; Liu, Yun-Jun

    2016-10-21

    Four new ruthenium(II) polypyridyl complexes [Ru(N-N)2(dhbn)](ClO4)2 (N-N = dmb: 4,4'-dimethyl-2,2'-bipyridine 1; bpy = 2,2'-bipyridine 2; phen = 1,10-phenanthroline 3; dmp = 2,9-dimethyl-1,10-phenanthroline 4) were synthesized and characterized. The cytotoxicity in vitro of the ligand and complexes toward HepG-2, HeLa, MG-63 and A549 were assayed by MTT method. The IC50 values of the complexes against the above cells range from 17.7 ± 1.1 to 45.1 ± 2.8 μM. The cytotoxic activity of the complexes against HepG-2 cells follows the order of 4 > 2 > 3 > 1. Ligand shows no cytotoxic activity against the selected cell lines. Cellular uptake, apoptosis, comet assay, reactive oxygen species, mitochondrial membrane potential, cell cycle arrest, and the expression of proteins involved in apoptosis pathway induced by the complexes were investigated. The results indicate that complexes 1-4 induce apoptosis in HepG-2 cells through an intrinsic ROS-mediated mitochondrial dysfunction pathway. PMID:27344489

  12. Development of redox-labeled electrochemical immunoassay for polycyclic aromatic hydrocarbons with controlled surface modification and catalytic voltammetric detection.

    Science.gov (United States)

    Wei, Ming-Yuan; Wen, Shou-Dong; Yang, Xi-Qiang; Guo, Liang-Hong

    2009-05-15

    A redox-labeled direct competitive electrochemical immunoassay for polycyclic aromatic hydrocarbons (PAHs) was developed. A ruthenium tris(bipyridine)-pyrenebutyric acid conjugate was synthesized as the redox-labeled tracer. Its recognition by an anti-PAH monoclonal antibody was confirmed by surface plasmon resonance. In the immunoassay, the antibody was immobilized on (3-glycidoxypropyl)-trimethoxysilane (GPTMS)-modified indium tin oxide (ITO) electrodes. The assay was quantified by measuring the electro-catalytic current of the redox label in an oxalate-containing electrolyte which served as a sacrificial electron donor to amplify the current signal. Formation of GPTMS film on ITO and subsequent antibody immobilization were characterized by X-ray photoelectron spectroscopy (XPS) and electrochemistry. Using a ruthenium tris(bipyridine)-conjugated IgG (IgG-Ru) as the surface-bound redox probe, the highest electrochemical signal was obtained on GPTMS electrodes with 1 h modification. Under the optimized conditions for ITO modification, antibody immobilization and tracer concentration, competition curves for benzo[a]pyrene and pyrenebutyric acid were obtained with a detection limit of 2.4 and 10 ng mL(-1), respectively. The redox-labeled electrochemical immunoassay with signal amplification mechanism offers a potential analytical method for the simultaneous detection of multiple environmental organic pollutants on antibody biochips. PMID:19321333

  13. Novel Cytotoxic Oxopyridoindolizines: iso-Propyl-7,8,9-trichloro-6,7,8,9-tetrahydro-5-oxopyrido[2,3-a]-indolizine-10-carboxylates (OPIC

    Directory of Open Access Journals (Sweden)

    Taibi Ben-Hadda

    2002-08-01

    Full Text Available A series of eight new alkyl-7,8,9-trichloro-6,7,8,9-tetrahydro-5-oxopyrido[2,3-a]-indolizine-10-carboxylates (OPIC, analogues of camptothecin (CPT, were prepared in a one-pot reaction of 2,2'-bipyridine-3,3'-dicarboxylic acid (BPA with a mixture of thionyl chloride/chlorine, followed by addition of the appropriate alcohol. This led to a mixture of OPIC compounds 3a-d, 4a-d and 3,3'-dialkoxycarbonyl-2,2'-bipyridines (BPE, 2a-d. The isopropyl OPIC 3c and its corresponding diastereoisomer 4c showed marked activity against three cancer cell lines compared to other analogs. These same diastereoisomers also displayed high cytotoxic activity against five leukemia cell lines, thus the presence of an isopropyl substituent on the carboxylic ester, as opposed to other alkyl substituents, appears to play a key role in the cytotoxic potency of this new class of compounds.

  14. Osmium-Based Pyrimidine Contrast Tags for Enhanced Nanopore-Based DNA Base Discrimination.

    Directory of Open Access Journals (Sweden)

    Robert Y Henley

    Full Text Available Nanopores are a promising platform in next generation DNA sequencing. In this platform, an individual DNA strand is threaded into nanopore using an electric field, and enzyme-based ratcheting is used to move the strand through the detector. During this process the residual ion current through the pore is measured, which exhibits unique levels for different base combinations inside the pore. While this approach has shown great promise, accuracy is not optimal because the four bases are chemically comparable to one another, leading to small differences in current obstruction. Nucleobase-specific chemical tagging can be a viable approach to enhancing the contrast between different bases in the sequence. Herein we show that covalent modification of one or both of the pyrimidine bases by an osmium bipyridine complex leads to measureable differences in the blockade amplitudes of DNA molecules. We qualitatively determine the degree of osmylation of a DNA strand by passing it through a solid-state nanopore, and are thus able to gauge T and C base content. In addition, we show that osmium bipyridine reacts with dsDNA, leading to substantially different current blockade levels than exhibited for bare dsDNA. This work serves as a proof of principle for nanopore sequencing and mapping via base-specific DNA osmylation.

  15. Coupling of metal-based light-harvesting antennas and electron-donor subunits: Trinuclear Ruthenium(II) complexes containing tetrathiafulvalene-substituted polypyridine ligands

    DEFF Research Database (Denmark)

    Campagna, Sebastiano; Serroni, Scolastica; Puntoriero, Fausto;

    2002-01-01

    )(4,4'-Mebpy)](2+) (4,4'-Mebpy = 4,4'-dimethyl-2,2'-bipyridine) and [{(bpy)(2)Ru(mu-2,3-dpp)}(2)Ru(bpy)](6+). The absorption spectra and redox behavior of all the new metal compounds can be interpreted by a multicomponent approach, in which specific absorption features and redox processes can be assigned to......(mu-2,3-dpp)}(2)Ru(bpy-TTF1)](PF6)(6) (9; bpy=2,2'-bipyridine; 2,3-dpp = 2,3-bis(2'-pyridyl)pyrazine) and [{(bpy)(2)Ru(mu-2,3-dpp)}(2)Ru(bpy-TTF2)](PF6)(6) (10). These compounds can be viewed as coupled antennas and charge-separation systems, in which the multichromophoric trinuclear metal subunits act...... compounds in fluid solution at room temperature. Time-resolved transient absorption spectroscopy confirmed that the potentially luminescent MLCT states of 7-10 are significantly shorter lived than the corresponding states of the model species. Photoinduced electron-transfer processes from the TTF moieties...

  16. Study of the selectivity of poly-nitrogenous extracting molecules in the complexation of actinides (III) and lanthanides (III) in solution in anhydrous pyridine

    International Nuclear Information System (INIS)

    The aim of this work is to better understand the factors which contribute to the separation of lanthanides(III) and actinides(III). Polydentate nitrogenous molecules present an interesting selectivity. A thermodynamic study of the complexation in pyridine of lanthanide and uranium by the bipyridine ligand (bipy) has been carried out. The formation constants and the thermodynamic values of the different complexes have been determined. It has been shown that the bipy complexes formation is controlled by the enthalpy and unfavored by the entropy. The conductometry has revealed too a significant difference in the uranium and lanthanides complexation by the bipyridine ligand. The use of the phenanthroline ligand induces a better complexation of the metallic ions but the selectivity is not improved. On the other hand, the decrease of the basicity and the increase of the ligand denticity (for instance in the case of the use of ter-pyridine) favour the selectivity without improving the complexation. The selectivity difference for the complexation of actinides(III) and lanthanides(III) by the different studied ligands (independent systems) has been confirmed by experiments of inter-metals competition. (O.M.)

  17. Anion Effects on Lanthanide(III) Tetrazole-1-acetate Dinuclear Complexes Showing Slow Magnetic Relaxation and Photofluorescent Emission.

    Science.gov (United States)

    Lu, Ying-Bing; Jiang, Xiao-Ming; Zhu, Shui-Dong; Du, Zi-Yi; Liu, Cai-Ming; Xie, Yong-Rong; Liu, Liang-Xian

    2016-04-18

    Three types of lanthanide complexes based on the tetrazole-1-acetic acid ligand and the 2,2'-bipyridine coligand were prepared and characterized by single-crystal X-ray diffraction, IR spectroscopy, and elemental analyses; the formulas of these complexes are [Ln2(1-tza)4(NO3)2(2,2'-bipy)2] (Ln = Sm (1), Eu (2), Gd (3), Tb (4), Dy (5)), [Dy2(1-tza)4Cl2(2,2'-bipy)2] (6), and [Yb2(1-tza)4(NO3)2(2,2'-bipy)2] (7) (1-tza = tetrazole-1-acetate and 2,2'-bipy = 2,2'-bipyridine). They are dinuclear complexes possessing similar structures but different lanthanide(III) ion coordination geometries because of the distinction of peripheral anions (such as NO3(-) and Cl(-)) and the effect of lanthanide contraction. The variable-temperature magnetic susceptibilities of 1-6 were measured. Both Dy(III) complexes (5 and 6) display field-induced single-molecule magnet behaviors. Ab initio calculations revealed that the Dy(III) complex 6 possesses a more anisotropic Dy(III) ion in comparison to that in 5. The room-temperature photoluminescence spectra of Sm(III) (1), Eu(III) (2), Tb(III) (4), and Dy(III) (5 and 6) complexes exhibit strong characteristic emissions in the visible region, whereas the Yb(III) (7) complex shows near-infrared (NIR) luminescence. PMID:27023680

  18. Synthesis of Fe–Li–Cr Multinuclear Complexes as Molecular Magnet Materials

    Directory of Open Access Journals (Sweden)

    Iis Siti Jahro

    2008-03-01

    Full Text Available Multinuclear complexes have received considerable interest as molecular magnet materials. Up to now, several complex compounds based on bidentate ligand 2,2’ bipyridine have been synthesized. In this research, the Fe-Li-Cr multinuclear complexes with derivative 2’2- bipyridine ligands: 2-(2’-pyridylquinoline(pq, 2,2’-Pyridil(pdl have been synthesized. The oxalate (ox ligand has also been used as a bridging ligand in these multinuclear complexes. The chemical formula of Li[FeCr(ox2(pq(BF42(H2O2] and [Fe(pdln][LiCr(ox3] complexes have been verified using metal and C, H, N elemental analysis data. The IR spectra in 350 – 4000 cm-1 range exhibit characteristic absorptions, which support the proposed structure of complex. The plausible structure of the compounds has been drawn based on complex formation mechanism. The magnetic susceptibility at room temperature of the pq-complex is about 5.7 BM and of the pdl- complexes are 4.8 and 5.5 BM. These indicated that both spin states of iron(II exist in the multinuclear complexes.

  19. Luminescent host–guest materials of electrostatically adsorbed Eu3+(tta)3-tpyIL on zeolite L crystals

    International Nuclear Information System (INIS)

    Graphical abstract: Luminescent host–guest materials exhibiting tunable emission colors by changing the excitation wavelength are obtained by surface modification of terbium(III) bipyridine-loaded zeolite L crystals with the ionic europium(III) complexes. - Highlights: • Luminescent ionic europium(III) complex was synthesized. • Outer surface of zeolite L was modified by electrostatic adsorption of the ionic complex. • Luminescent host–guest material with tunable emission color was obtained. - Abstract: The surface modification of zeolite L crystals with lanthanide complexes was achieved by electrostatic adsorption of ionic europium(III) complexes that are prepared by the reaction of tris(2-thenoyltrifluoroacetonate) europium(III) dehydrate with an organic salt containing terpyridine moieties on the negative charge-bearing surfaces of zeolite L crystals. Luminescent host–guest materials exhibiting tunable emission colors by changing the excitation wavelength are obtained by surface modification of terbium(III) bipyridine-loaded zeolite L crystals with the ionic europium(III) complexes

  20. Luminescent host–guest materials of electrostatically adsorbed Eu{sup 3+}(tta){sub 3}-tpyIL on zeolite L crystals

    Energy Technology Data Exchange (ETDEWEB)

    Li, Peng; Wang, Dongyue [Hebei Provincial Key Lab of Green Chemical Technology and High Efficient Energy Saving, School of Chemical Engineering and Technology, Hebei University of Technology, Tianjin 300130 (China); Liang, Dong [Tangshan Zhonghao chemical co. Ltd., Hebei 300130 (China); Zhang, Li; Zhang, Shuming [Hebei Provincial Key Lab of Green Chemical Technology and High Efficient Energy Saving, School of Chemical Engineering and Technology, Hebei University of Technology, Tianjin 300130 (China); Wang, Yige, E-mail: wangyige@hebut.edu.cn [Hebei Provincial Key Lab of Green Chemical Technology and High Efficient Energy Saving, School of Chemical Engineering and Technology, Hebei University of Technology, Tianjin 300130 (China)

    2014-07-01

    Graphical abstract: Luminescent host–guest materials exhibiting tunable emission colors by changing the excitation wavelength are obtained by surface modification of terbium(III) bipyridine-loaded zeolite L crystals with the ionic europium(III) complexes. - Highlights: • Luminescent ionic europium(III) complex was synthesized. • Outer surface of zeolite L was modified by electrostatic adsorption of the ionic complex. • Luminescent host–guest material with tunable emission color was obtained. - Abstract: The surface modification of zeolite L crystals with lanthanide complexes was achieved by electrostatic adsorption of ionic europium(III) complexes that are prepared by the reaction of tris(2-thenoyltrifluoroacetonate) europium(III) dehydrate with an organic salt containing terpyridine moieties on the negative charge-bearing surfaces of zeolite L crystals. Luminescent host–guest materials exhibiting tunable emission colors by changing the excitation wavelength are obtained by surface modification of terbium(III) bipyridine-loaded zeolite L crystals with the ionic europium(III) complexes.

  1. A novel porous anionic metal-organic framework with pillared double-layer structure for selective adsorption of dyes

    Science.gov (United States)

    Sheng, Shu-Nan; Han, Yi; Wang, Bin; Zhao, Cui; Yang, Fan; Zhao, Min-Jian; Xie, Ya-Bo; Li, Jian-Rong

    2016-01-01

    A novel porous anionic metal-organic framework, (Me2NH2)2[Zn2L1.5bpy]·2DMF (BUT-201; H4L=4,8-disulfonaphthalene-2,6-dicarboxylic acid; bpy=4,4-bipyridine; DMF=N,N-dimethylformamide), with pillared double-layer structure has been synthesized through the reaction of a sulfonated carboxylic acid ligand and Zn(NO3)2·6H2O with 4,4-bipyridine as a co-ligand. It is found that BUT-201 can rapidly adsorb cationic dyes with a smaller size such as Methylene Blue (MB) and Acriflavine Hydrochloride (AH) by substitution of guest (CH3)2NH2+, but has no adsorption towards the cationic dyes with a lager size such as Methylene Violet (MV), the anionic dyes like C. I. Acid Yellow 1 (AY1) and neutral dyes like C. I. Solvent Yellow 7 (SY7), respectively. The results show that the adsorption behavior of BUT-201 relates not only to the charge but also to the size/shape of dyes. Furthermore, the adsorbed dyes can be gradually released in the methanol solution of LiNO3.

  2. A functional ruthenium(ii) complex for imaging biothiols in living bodies.

    Science.gov (United States)

    Ye, Zhiqiang; Gao, Quankun; An, Xin; Song, Bo; Yuan, Jingli

    2015-05-01

    A unique ruthenium(ii) complex, [Ru(bpy)2(DNS-bpy)](PF6)2 [bpy: 2,2'-bipyridine, DNS-bpy: 4-(2,4-dinitrophenylthio)-2,2'-bipyridine], that can act as a probe for the recognition and luminescence sensing of biothiols has been designed and synthesized. Due to the presence of effective photo-induced electron transfer (PET) from the potent electron donor (Ru-bpy centre) to the strong electron acceptor (2,4-dinitrophenyl moiety), the Ru(ii) complex itself is weakly luminescent. Reaction of [Ru(bpy)2(DNS-bpy)](PF6)2 with biothiols leads to the replacement of the 2,4-dinitrophenyl moiety by biothiols, which results in the loss of PET within the complex, to allow recovery of the MLCT-based emission of the Ru(ii) complex with an 80-fold increase in luminescence intensity. Taking advantage of the high specificity and sensitivity, and the excellent photophysical properties of Ru(ii) complexes, [Ru(bpy)2(DNS-bpy)](PF6)2 was successfully applied to the luminescence imaging of biothiols in living Daphnia magna. The results demonstrated the practical applicability of [Ru(bpy)2(DNS-bpy)](PF6)2 as a luminescent probe for the monitoring of biothiols in living bodies. PMID:25851565

  3. Coupling of metal-based light-harvesting antennas and electron-donor subunits: Trinuclear Ruthenium(II) complexes containing tetrathiafulvalene-substituted polypyridine ligands

    DEFF Research Database (Denmark)

    Campagna, Sebastiano; Serroni, Scolastica; Puntoriero, Fausto; Loiseau, Frédérique; De Cola, Luisa; Kleverlaan, Cornelis J.; Becher, Jan; Sørensen, Ane Plough; Hascoat, Philippe; Thorup, Niels

    2002-01-01

    (mu-2,3-dpp)}(2)Ru(bpy-TTF1)](PF6)(6) (9; bpy=2,2'-bipyridine; 2,3-dpp = 2,3-bis(2'-pyridyl)pyrazine) and [{(bpy)(2)Ru(mu-2,3-dpp)}(2)Ru(bpy-TTF2)](PF6)(6) (10). These compounds can be viewed as coupled antennas and charge-separation systems, in which the multichromophoric trinuclear metal subunits act...... as light-harvesting antennas and the tetrathiafulvalene electron donors can induce charge separation. The absorption spectra, redox behavior, and luminescence properties (both at room temperature in acetonitrile and at 77 K in a rigid matrix of butyronitrile) of the trinuclear metal complexes have......)(4,4'-Mebpy)](2+) (4,4'-Mebpy = 4,4'-dimethyl-2,2'-bipyridine) and [{(bpy)(2)Ru(mu-2,3-dpp)}(2)Ru(bpy)](6+). The absorption spectra and redox behavior of all the new metal compounds can be interpreted by a multicomponent approach, in which specific absorption features and redox processes can be assigned to...

  4. A novel samarium(ii) complex bearing a dianionic bis(phenolate) cyclam ligand: synthesis, structure and electron-transfer reactions.

    Science.gov (United States)

    Maria, Leonor; Soares, Marina; Santos, Isabel C; Sousa, Vânia R; Mora, Elsa; Marçalo, Joaquim; Luzyanin, Konstantin V

    2016-02-18

    The reaction of the hexadentate dianionic 1,4,8,11-tetraazacyclotetradecane-based bis(phenolate) ligand, ((tBu2)ArO)2Me2-cyclam(2-), with [SmI2(thf)2] in thf resulted in the formation of the divalent samarium complex [Sm(κ(6)-{((tBu2)ArO)2Me2-cyclam})] (). X-ray diffraction studies revealed that after recrystallization from n-hexane/thf complex has a monomeric structure and does not contain thf molecules coordinated to the Sm(ii) center. However, UV-vis and (1)H NMR spectroscopy of evidenced the formation of thf-solvated complexes in neat thf. Reductive studies show that complex can act as a single electron-transfer reagent and form well-defined Sm(iii) species. The reaction of with several substrates, namely, TlBPh4, pyridine N-oxide, OPPh3, SPPh3 and bipyridines, are reported. Spectroscopy studies, including NMR, and single crystal X-ray diffraction data are in agreement with the formation of cationic Sm(iii) species, monochalcogenide bridged Sm(iii) complexes and Sm(iii) complexes with bipyridine radical ligand, respectively. PMID:26818107

  5. Supramolecular Photoinduced Electron Transfer between a Redox-Active Hexanuclear Metal-Organic Cylinder and an Encapsulated Ruthenium(II) Complex.

    Science.gov (United States)

    Yang, Lu; He, Cheng; Liu, Xin; Zhang, Jing; Sun, Hui; Guo, Huimin

    2016-04-01

    By using redox-active nickel(II) ions as the connect nodes, a hexanuclear metal-organic cylinder (Ni-YL) was achieved through self-assembly with a large cavity and an opening windows capable to accommodate guest molecules. The suitable cavity of Ni-YL provides an opportunity to encapsulate the anionic ruthenium bipyridine derivative [Ru(dcbpy)3 ] (dcbpy=2,2'-bipyridine-4,4'-dicarboxylic acid) as the photosensitizer for light-driven reactions. The host-guest behavior between Ni-YL and [Ru(dcbpy)3 ] was investigated by mass spectrometry, NMR spectroscopy, and computational studies, revealing an effective binding of the guest [Ru(dcbpy)3 ] within the cavity of Ni-YL. Optical experiments suggested a pseudo-intramolecular photoinduced electron transfer (PET) process between the [Ru(dcbpy)3 ] and the host Ni-YL, leading to an efficient light-driven hydrogen production based on this system. Control experiments with a mononuclear Ni complex as a reference photocatalyst and the inactive [Fe(dcbpy)3 ] as an inhibitor for comparison were also performed to confirm such a supramolecular photocatalysis process. PMID:26923780

  6. Surface-enhanced Raman scattering active gold nanostructure fabricated by photochemical reaction of synchrotron radiation

    International Nuclear Information System (INIS)

    The deposition of gold nanoparticles in an electroplating solution containing gold (I) trisodium disulphite under synchrotron X-ray radiation was investigated. The nanoparticles grew and aggregated into clusters with increasing radiation time. This behavior is explained by evaluating the effect of Derjaguin-Landau-Verweyand-Overbeek (DLVO) interactions combining repulsive electrostatic and attractive van der Waals forces on the particle deposition process. The surface-enhanced Raman scattering (SERS) of 4,4′ -bipyridine (4bpy) in aqueous solution was measured using gold nanoparticles immobilized on silicon substrates under systematically-varied X-ray exposure. The substrates provided an in situ SERS spectrum for 1 nM 4bpy. This demonstration creates new opportunities for chemical and environmental analyses through simple SERS measurements. - Highlights: • Gold nanoparticles were produced by photochemical reaction of synchrotron radiation. • The gold nanoparticles grew and aggregated into the higher-order nanostructure. • The behavior is qualitatively explained by analytical estimation. • The surface-enhanced Raman spectroscopy of 4,4′-bipyridine (4bpy) was demonstrated. • The substrate fabricated in a suitable condition provides in situ SERS for 1 nM 4bpy

  7. Terpyridine and Quaterpyridine Complexes as Sensitizers for Photovoltaic Applications

    Directory of Open Access Journals (Sweden)

    Davide Saccone

    2016-02-01

    Full Text Available Terpyridine and quaterpyridine-based complexes allow wide light harvesting of the solar spectrum. Terpyridines, with respect to bipyridines, allow for achieving metal-complexes with lower band gaps in the metal-to-ligand transition (MLCT, thus providing a better absorption at lower energy wavelengths resulting in an enhancement of the solar light-harvesting ability. Despite the wider absorption of the first tricarboxylate terpyridyl ligand-based complex, Black Dye (BD, dye-sensitized solar cell (DSC performances are lower if compared with N719 or other optimized bipyridine-based complexes. To further improve BD performances several modifications have been carried out in recent years affecting each component of the complexes: terpyridines have been replaced by quaterpyridines; other metals were used instead of ruthenium, and thiocyanates have been replaced by different pinchers in order to achieve cyclometalated or heteroleptic complexes. The review provides a summary on design strategies, main synthetic routes, optical and photovoltaic properties of terpyridine and quaterpyridine ligands applied to photovoltaic, and focuses on n-type DSCs.

  8. Reversible, Selective Trapping of Perchlorate from Water in Record Capacity by a Cationic Metal-Organic Framework.

    Science.gov (United States)

    Colinas, Ian R; Silva, Rachel C; Oliver, Scott R J

    2016-02-16

    We report the capture of ppm-level aqueous perchlorate in record capacity and kinetics via the complete anion exchange of a cationic metal-organic framework. Ambient conditions were used for both the synthesis of silver 4,4'-bipyridine nitrate (SBN) and the exchange, forming silver 4,4'-bipyridine perchlorate (SBP). The exchange was complete within 90 min, and the capacity was 354 mg/g, representing 99% removal. These values are greater than current anion exchangers such as the resins Amberlite IRA-400 (249 mg/g), Purolite A530E (104 mg/g), and layered double hydroxides (28 mg/g). Moreover, unlike resins and layered double hydroxides, SBN is fully reusable and displays 96% regeneration to SBN in nitrate solution, with new crystal formation allowing the indefinite cycling for perchlorate. We show seven cycles as proof of concept. Perchlorate contamination of water represents a serious health threat because it is a thyroid endocrine disruptor. This noncomplexing anionic pollutant is significantly mobile and environmentally persistent. Removal of other anionic pollutants from water such as chromate, pertechnetate, or arsenate may be possible by this methodology. PMID:26765213

  9. The effect of ligand substituent on crystal packing: Structural and theoretical studies of two Ga(III) supramolecular compounds

    Science.gov (United States)

    Soleimannejad, Janet; Nazarnia, Esfandiar

    2016-07-01

    A new Ga(III) supramolecular compound (4,4‧-bipyH2)[Ga(hpydc)2]2·7H2O (2) (where H2hpydc = 4-hydroxy-pyridine-2,6-dicarboxylic acid and 4,4‧-bipy = 4,4‧-bipyridine) was synthesized using the proton transfer reaction. Compound 2 was structurally characterized using single crystal X-ray diffraction, and it was shown that its asymmetric unit consists of two independent anionic Ga(III) complexes, one fully protonated 4,4‧-bipyridine and seven uncoordinated water molecules. In order to understand the effect of pyridine OH substituent on supramolecular interactions and crystal packing, compound 2 was compared with (bipyH2)[Ga(pydc)2]·(H2pydc)·4H2O (1) (where H2pydc = pyridine-2,6-dicarboxylic acid), that does not have an OH group on the pyridine ligand. The Density Functional Theory (DFT) and Natural Bond Orbital (NBO) calculations and also Atoms in Molecules (AIM) analysis were used to analyze the non-covalent interactions in both complexes. The calculation of non-covalent interactions' energy provides a useful means to investigate their effects in the crystal packing.

  10. The First Molybdenum(VI) and Tungsten(VI) Oxoazides MO2(N3)2, MO2(N3)2⋅2 CH3CN, (bipy)MO2(N3)2, and [MO2(N3)4](2-) (M=Mo, W).

    Science.gov (United States)

    Haiges, Ralf; Skotnitzki, Juri; Fang, Zongtang; Dixon, David A; Christe, Karl O

    2015-08-10

    Molybdenum(VI) and tungsten(VI) dioxodiazide, MO2(N3)2 (M=Mo, W), were prepared through fluoride-azide exchange reactions between MO2F2 and Me3SiN3 in SO2 solution. In acetonitrile solution, the fluoride-azide exchange resulted in the isolation of the adducts MO2(N3)2⋅2 CH3CN. The subsequent reaction of MO2(N3)2 with 2,2'-bipyridine (bipy) gave the bipyridine adducts (bipy)MO2(N3)2. The hydrolysis of (bipy)MoO2(N3)2 resulted in the formation and isolation of [(bipy)MoO2N3]2O. The tetraazido anions [MO2(N3)4](2-) were obtained by the reaction of MO2(N3)2 with two equivalents of ionic azide. Most molybdenum(VI) and tungsten(VI) dioxoazides were fully characterized by their vibrational spectra, impact, friction, and thermal sensitivity data and, in the case of (bipy)MoO2(N3)2, (bipy)WO2(N3)2, [PPh4]2[MoO2(N3)4], [PPh4]2[WO2(N3)4], and [(bipy)MoO2N3]2O by their X-ray crystal structures. PMID:26178877

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

    Science.gov (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

    2015-11-01

    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.

  12. Reactions of the excited state of polypyridyl chromium(III) ion

    Energy Technology Data Exchange (ETDEWEB)

    Steffan, C.

    1990-09-21

    There has been much recent interest in the photochemistry and photophysics of transition metal polypyridine complexes due to the possibility of their use in solar energy conversion systems. The excited state of these compounds are known to undergo useful electron transfer and energy transfer reactions. This work attempts to elucidate the mechanism of the quenching of *CrL{sub 3}{sup 3+} (where L = 2,2{prime}-bipyridine, 4,4{prime}-dimethyl-2,2{prime}-bipyridine, 1,10-phenanthroline, 5-chloro-1,10-phenanthroline, 5-methyl-1,10-phenanthroline) by oxalate ions in neutral pH. Evidence suggests an ion-pairing pre-equilibrium followed by rate limiting electron transfer to produce CrL{sub 3}{sup 2+} and CO{sub 2}{sup {minus}} can then react with ground state chromium(III) species to produce another mole of the reduced product or it can produce a secondary transient as in the case of phenanthroline and substituted phenanthroline complexes. The secondary transient reacts to produce CrL{sub 3}{sup 2+} in a subsequent reaction. 85 refs., 24 figs., 7 tabs.

  13. Chromium(III)-trisoxalate, a versatile building block for luminescent materials

    International Nuclear Information System (INIS)

    Chromium(III)-trisoxalate, [Cr(ox)3]3− (ox=C2O42−), incorporated into polymeric networks of composition [NaCr(ox)3][MII(bpy)3] and [NaCr(ox)3][MIII(bpy)3]ClO4 (ox=C2O42−, bpy=2,2′-bipyridine, MII=Zn, Fe, Ru; MIII=Rh, Cr), results in interesting features ranging from phonon-assisted and resonant energy migration within the R1 line the 2E state to persistent spectral side-hole burning via the latter, and manifestations of specific nearest-neighbour π–π interactions between bipyridine and oxalate. - Highlights: ► We present the multifaceted photophysical behaviour of chromium(III)-tris-oxalate. ► We differentiate between phonon-assisted and resonant energy migration. ► Resonant energy migration results in spectral diffusion. ► Resonant energy transfer can be tuned via pressure dependant spectral overlap. ► π–π interactions with the second coordination sphere create specific spectroscopic sites.

  14. Turn-On Fluorescent Chemosensor for Fluoride Based on Pyreneamide Derivative

    International Nuclear Information System (INIS)

    A new chemosensor with pyreneamide derivative of bipyridine is synthesized. In the free ligand, pyreneamide derivative has nearly no fluorescence in acetonitrile solution. However, in the presence of fluoride ion, a 'turn-on' fluorescence was observed. Simultaneously, the colorless ligand solution became markedly orange when fluoride ion was added to pyreneamide derivative in acetonitrile. This phenomenon suggest that the PET (photoinduced electron transfer) between anion electron and pyrene unit was changed the π-π interaction between bipyridine and pyrene that was modified structure by deprotonation. On account of the important roles of anion in biological, clinical, environmental, catalysis, and chemical processes, the selective and efficient recognition of anion is an area of growing interest in supramolecular chemistry. In particular, the studies of chemosensors toward F- anion are quite intriguing because of its beneficial effects in human physiology. Also, fluoride is interest due to its established role in dental care and osteoporosis. However, an excess of fluoride ion can lead to fluorosis. Therefore, the development of reliable sensors for F- is needed for environment and human health care. Color changes that can be detected by the naked eye are widely used as signals for events owing to the inexpensive equipment required or no equipment at all

  15. Study of DNA light switch Ru(II) complexes: synthesis, characterization, photocleavage and antimicrobial activity.

    Science.gov (United States)

    Yata, Praveen Kumar; Shilpa, M; Nagababu, P; Reddy, M Rajender; Kotha, Laxma Reddy; Gabra, Nazar Md; Satyanarayana, S

    2012-05-01

    The three Ru(II) complexes of [Ru(phen)(2)dppca](2+) (1) [Ru(bpy)(2)dppca](2+) (2) and [Ru(dmb)(2)dppca](2+) (3) (where phen = 1,10 phenanthroline, bpy = 2,2-bipyridine, dmb = 2 ,2-dimethyl 2',2'-bipyridine and polypyridyl ligand containing a single carboxylate functionality dppca ligand (dipyridophenazine-11-carboxylic acid) have been synthesized and characterized. These complexes have been shown to act as promising calf thymus DNA intercalators and a new class of DNA light switches, as evidenced by UV-visible and luminescence titrations with Co(2+) and EDTA, steady-state emission quenching by [Fe(CN)(6)](4-) and KI, DNA competitive binding with ethidium bromide, viscosity measurements, and DNA melting experiments. The results suggest that 1, 2, and 3 complexes bind to CT-DNA through intercalation and follows the order 1 > 2 > 3. Under irradiation at 365 nm, the three complexes have also been found to promote the photocleavage of plasmid pBR322 DNA. PMID:22194001

  16. Synthesis, characterization; DNA binding and antitumor activity of ruthenium(II) polypyridyl complexes.

    Science.gov (United States)

    Srishailam, A; Gabra, Nazar Mohammed; Kumar, Yata Praveen; Reddy, Kotha Laxma; Devi, C Shobha; Anil Kumar, D; Singh, Surya S; Satyanarayana, S

    2014-12-01

    Three new ruthenium(II) polypyridyl complexes [Ru(phen)2BrIPC](2+) (1), [Ru(bpy)2 BrIPC](2+) (2) and [Ru(dmb)2BrIPC](2+) (3) where, BrIPC = (6-bromo-3-(1H-imidazo[4,5-f] [1,10]-phenanthroline, phen = 1,10-phenanthroline, bpy = 2,2' bipyridine, dmb = 4,4'-dimethyl 2,2' bipyridine, were synthesised and characterised. DNA-binding nature was investigated by spectroscopic titrations and mode of binding was assessed by viscosity measurements. The DNA-binding constants Kb of complexes 1, 2 and 3 were determined to be in the order of 10(5). Experimental results showed that these complexes interact with CT-DNA by intercalative mode. Photocleavage and antimicrobial activities were complex concentration dependent, at high concentration, high activity and vice versa. MTT assay was performed on HeLa cell lines, IC50 values of complexes in the order of 3 > 2 > 1 > cisplatin. From comet assay, cellular uptake studies, we observed that complexes could enter into the cell membrane and accumulate inside the nucleus. Molecular docking studies support the DNA binding affinity with hydrogen bonding and van der Waals attractions between base pairs and phosphate backbone of DNA with metal complexes. PMID:25318017

  17. Synthesis, DNA-binding, cytotoxicity, photo cleavage, antimicrobial and docking studies of Ru(II) polypyridyl complexes.

    Science.gov (United States)

    Srishailam, A; Kumar, Yata Praveen; Gabra, Nazar M D; Reddy, P Venkat; Deepika, N; Veerababu, Nageti; Satyanarayana, S

    2013-09-01

    Three Ruthenium(II) polypyridine complexes, [Ru(phen)2(mipc)](2+)(1), [Ru(bpy)2(mipc)](2+) (2) and [Ru(dmb)2(mipc)](2+)(3) [mipc = 2-(6-methyl-3-(1H-imidazo[4, 5-f][1,10]-phenanthroline-2-yl)-4H-chromene-4-one, phen = 1,10-phenanthroline,bpy = 2, 2'bipyridine,dmb = 4, 4'-dimethyl-2, 2'-bipyridine] have been synthesized and characterized by elemental analysis, IR, UV-Vis, (1)H& (13)C NMR and mass spectra. The DNA-binding properties of the Ruthenium(II) complexes were investigated by spectrophotometric methods, viscosity measurements and light switch studies. These three complexes have been focused on photo activated cleavage studies with pBR-322 and antimicrobial studies. Experimental results indicate that the three complexes intercalate into DNA base pairs and follows the order of 1 > 2 > 3 respectively. Molecular docking studies also support the DNA interactions with complexes through hydrogen bonding and vander Waal's interactions. Cytotoxicity studies with Hela cell lines has been revealing about anti tumor activity of these complexes. PMID:23553642

  18. Mixed ligand complex formation of FeIII with boric acid and typical N-donor multidentate ligands

    Indian Academy of Sciences (India)

    G N Mukherjee; Ansuman Das

    2002-06-01

    Equilibrium study of the mixed ligand complex formation of FeIII with boric acid in the absence and in the presence of 2,2'-bipyridine, 1,10-phenanthroline, diethylenetriamine and triethylenetetramine (L) in different molar ratios provides evidence of formation of Fe(OH)2+, Fe(OH)$^{+}_{2}$, Fe(L)3+, Fe(H2BO4), Fe(OH)(H2BO4)-, Fe(OH)2(H2BO4)2-, Fe(L)(H2BO4) and Fe2(L)2(BO4)+ complexes. Fe(L)$^{3+}_{2}$, Fe(L)2(H2BO4) and Fe2(L)4(BO4)+ complexes are also indicated with 2,2'-bipyridine and 1,10-phenanthroline. Complex formation equilibria and stability constants of the complexes at 25 ± 0 × 1° C in aqueous solution at a fixed ionic strength, = 0.1 mol -3 (NaNO3) have been determined by potentiometric method.

  19. Chromophore-immobilized luminescent metal-organic frameworks as potential lighting phosphors and chemical sensors.

    Science.gov (United States)

    Wang, Fangming; Liu, Wei; Teat, Simon J; Xu, Feng; Wang, Hao; Wang, Xinlong; An, Litao; Li, Jing

    2016-08-11

    An organic chromophore H4tcbpe-F was synthesized and immobilized into metal-organic frameworks along with two bipyridine derivatives as co-ligands to generate two strongly luminescent materials [Zn2(tcbpe-F)(4,4'-bpy)·xDMA] (1) and [Zn2(tcbpe-F)(bpee)·xDMA] (2) [4,4'-bpy = 4,4'-bipyridine, bpee = 4,4'-bipyridyl-ethylene, tcbpe-F = 4',4''',4''''',4'''''''-(ethene-1,1,2,2-tetrayl)tetrakis(3-fluoro-[1,1'-biphenyl]-4-carboxylic acid), DMA = N,N-dimethylacetamide]. Compounds 1 and 2 are isoreticular and feature a 2-fold interpenetrated three-dimensional porous structure. Both compounds give green-yellow emission under blue light excitation. Compound 1 has a high internal quantum yield of ∼51% when excited at 455 nm and shows selective luminescence signal change (e.g. emission energy and/or intensity) towards different solvents, including both aromatic and nonaromatic volatile organic species. These properties make it potentially useful as a lighting phosphor and a chemical sensor. PMID:27465685

  20. Transport of Carbonate Ions by Novel Cellulose Fiber Supported Solid Membrane

    Directory of Open Access Journals (Sweden)

    A. G. Gaikwad

    2012-06-01

    Full Text Available Transport of carbonate ions was explored through fiber supported solid membrane. A novel fiber supported solid membrane was prepared by chemical modification of cellulose fiber with citric acid, 2′2-bipyridine and magnesium carbonate. The factors affecting the permeability of carbonate ions such as immobilization of citric acid-magnesium metal ion -2′2-bipyridine complex (0 to 2.5 mmol/g range over cellulose fiber, carbon-ate ion concentration in source phase and NaOH concentration in receiving phase were investigated. Ki-netic of carbonate, sulfate, and nitrate ions was investigated through fiber supported solid membrane. Transport of carbonate ions with/without bubbling of CO2 (0 to 10 ml/min in source phase was explored from source to receiving phase. The novel idea is to explore the adsorptive transport of CO2 from source to receiving phase through cellulose fiber containing magnesium metal ion organic framework. Copyright © 2012 BCREC UNDIP. All rights reserved.Received: 25th November 2011; Revised: 17th December 2011; Accepted: 19th December 2011[How to Cite: A.G. Gaikwad. (2012. Transport of Carbonate Ions by Novel Cellulose Fiber Supported Solid Membrane. Bulletin of Chemical Reaction Engineering & Catalysis, 7 (1: 49– 57.  doi:10.9767/bcrec.7.1.1225.49-57][How to Link / DOI: http://dx.doi.org/10.9767/bcrec.7.1.1225.49-57 ] | View in 

  1. Study of the selectivity of poly-nitrogenous extracting molecules in the complexation of actinides (III) and lanthanides (III) in solution in anhydrous pyridine; Etude de la selectivite de molecules extractantes polyazotees dans la complexation des actinides (III) et des lanthanides (III) en solution dans la pyridine anhydre

    Energy Technology Data Exchange (ETDEWEB)

    Riviere, Ch

    2000-10-05

    The aim of this work is to better understand the factors which contribute to the separation of lanthanides(III) and actinides(III). Polydentate nitrogenous molecules present an interesting selectivity. A thermodynamic study of the complexation in pyridine of lanthanide and uranium by the bipyridine ligand (bipy) has been carried out. The formation constants and the thermodynamic values of the different complexes have been determined. It has been shown that the bipy complexes formation is controlled by the enthalpy and unfavored by the entropy. The conductometry has revealed too a significant difference in the uranium and lanthanides complexation by the bipyridine ligand. The use of the phenanthroline ligand induces a better complexation of the metallic ions but the selectivity is not improved. On the other hand, the decrease of the basicity and the increase of the ligand denticity (for instance in the case of the use of ter-pyridine) favour the selectivity without improving the complexation. The selectivity difference for the complexation of actinides(III) and lanthanides(III) by the different studied ligands (independent systems) has been confirmed by experiments of inter-metals competition. (O.M.)

  2. Human Collagen Prolyl 4-Hydroxylase Is Activated by Ligands for Its Iron Center.

    Science.gov (United States)

    Vasta, James D; Raines, Ronald T

    2016-06-14

    Collagen is the most abundant protein in animals. The posttranslational hydroxylation of proline residues in collagen contributes greatly to its conformational stability. Deficient hydroxylation is associated with a variety of disease states, including scurvy. The hydroxylation of proline residues in collagen is catalyzed by an Fe(II)- and α-ketoglutarate-dependent dioxygenase, collagen prolyl 4-hydroxylase (CP4H). CP4H has long been known to suffer oxidative inactivation during catalysis, and the cofactor ascorbate (vitamin C) is required to reactivate the enzyme by reducing its iron center from Fe(III) to Fe(II). Herein, we report on the discovery of the first synthetic activators of CP4H. Specifically, we find that 2,2'-bipyridine-4-carboxylate and 2,2'-bipyridine-5-carboxylate serve as ligands for the iron center in human CP4H that enhance the rate of ascorbate-dependent reactivation. This new mode of CP4H activation is available to other biheteroaryl compounds but does not necessarily extend to other prolyl 4-hydroxylases. As collagen is weakened in many indications, analogous activators of CP4H could have therapeutic benefits. PMID:27183028

  3. Development of a ruthenium(II) complex based luminescent probe for imaging nitric oxide production in living cells.

    Science.gov (United States)

    Zhang, Run; Ye, Zhiqiang; Wang, Guilan; Zhang, Wenzhu; Yuan, Jingli

    2010-06-18

    A unique ruthenium(II) complex, bis(2,2'-bipyridine)(4-(3,4-diaminophenoxy)-2,2'-bipyridine)ruthenium(II) hexafluorophosphate ([(Ru(bpy)(2)(dabpy)][PF(6)](2)), has been designed and synthesized as a highly sensitive and selective luminescence probe for the imaging of nitric oxide (NO) production in living cells. The complex can specifically react with NO in aqueous buffers under aerobic conditions to yield its triazole derivative with a high reaction rate constant at the 10(10) M(-1) s(-1) level; this reaction is accompanied by a remarkable increase of the luminescence quantum yield from 0.13 to 2.2 %. Compared with organic probes, the new Ru(II) complex probe shows the advantages of a large Stokes shift (>150 nm), water solubility, and a wide pH-availability range (pH independent at pH>5). In addition, it was found that the new probe could be easily transferred into both living animal cells and plant cells by the coincubation method, whereas the triazole derivative was cell-membrane impermeable. The probe was successfully used for luminescence-imaging detection of the exogenous NO in mouse macrophage cells and endogenous NO in gardenia cells. The results demonstrated the efficacy and advantages of the new probe for NO detection in living cells. PMID:20458707

  4. Copper-mediated C-H activation/C-S cross-coupling of heterocycles with thiols

    KAUST Repository

    Ranjit, Sadananda

    2011-11-04

    We report the synthesis of a series of aryl- or alkyl-substituted 2-mercaptobenzothiazoles by direct thiolation of benzothiazoles with aryl or alkyl thiols via copper-mediated aerobic C-H bond activation in the presence of stoichiometric CuI, 2,2′-bipyridine and Na 2CO 3. We also show that the approach can be extended to thiazole, benzimidazole, and indole substrates. In addition, we present detailed mechanistic investigations on the Cu(I)-mediated direct thiolation reactions. Both computational studies and experimental results reveal that the copper-thiolate complex [(L)Cu(SR)] (L: nitrogen-based bidentate ligand such as 2,2′-bipyridine; R: aryl or alkyl group) is the first reactive intermediate responsible for the observed organic transformation. Furthermore, our computational studies suggest a stepwise reaction mechanism based on a hydrogen atom abstraction pathway, which is more energetically feasible than many other possible pathways including β-hydride elimination, single electron transfer, hydrogen atom transfer, oxidative addition/reductive elimination, and σ-bond metathesis. © 2011 American Chemical Society.

  5. The niobium oxoazides [NbO(N3)3], [NbO(N3)3·2CH3CN], [(bipy)NbO(N3)3], Cs2[NbO(N3)5] and [PPh4]2[NbO(N3)5].

    Science.gov (United States)

    Haiges, Ralf; Vasiliu, Monica; Dixon, David A; Christe, Karl O

    2016-06-28

    Niobium oxotriazide, [NbO(N3)3], was prepared in a fluoride-azide exchange reaction between [NbOF3] and an excess of Me3SiN3 in SO2 solution. In acetonitrile solution, the fluoride-azide exchange resulted in the isolation of the adduct [NbO(N3)3·2CH3CN]. The subsequent reaction of [NbO(N3)3] with 2,2'-bipyridine (bipy) resulted in the isolation of the bipyridine adduct [(bipy)NbO(N3)3]. The pentaazido anion [NbO(N3)5](2-) was obtained by the reaction of [NbO(N3)3] with two equivalents of ionic azide. The novel niobium oxoazides were fully characterized by their vibrational spectra, impact, friction and thermal sensitivity data and, in the case of [(bipy)NbO(N3)3], Cs2[NbO(N3)5], and [PPh4]2[NbO2(N3)5] by their X-ray crystal structures. PMID:27198621

  6. Surface-enhanced Raman scattering active gold nanostructure fabricated by photochemical reaction of synchrotron radiation

    Energy Technology Data Exchange (ETDEWEB)

    Yamaguchi, Akinobu, E-mail: yamaguti@lasti.u-hyogo.ac.jp [Laboratory of Advance Science and Technology for Industry, University of Hyogo, 3-1-2 Koto, Kamigori, Ako, Hyogo 678-1205 (Japan); Matsumoto, Takeshi [Laboratory of Advance Science and Technology for Industry, University of Hyogo, 3-1-2 Koto, Kamigori, Ako, Hyogo 678-1205 (Japan); Okada, Ikuo; Sakurai, Ikuya [Synchrotoron Radiation Research Center, Nagoya University, Furo-cho, Chikusa-ku, Nagoya, Aichi 464-8603 (Japan); Utsumi, Yuichi [Laboratory of Advance Science and Technology for Industry, University of Hyogo, 3-1-2 Koto, Kamigori, Ako, Hyogo 678-1205 (Japan)

    2015-06-15

    The deposition of gold nanoparticles in an electroplating solution containing gold (I) trisodium disulphite under synchrotron X-ray radiation was investigated. The nanoparticles grew and aggregated into clusters with increasing radiation time. This behavior is explained by evaluating the effect of Derjaguin-Landau-Verweyand-Overbeek (DLVO) interactions combining repulsive electrostatic and attractive van der Waals forces on the particle deposition process. The surface-enhanced Raman scattering (SERS) of 4,4′ -bipyridine (4bpy) in aqueous solution was measured using gold nanoparticles immobilized on silicon substrates under systematically-varied X-ray exposure. The substrates provided an in situ SERS spectrum for 1 nM 4bpy. This demonstration creates new opportunities for chemical and environmental analyses through simple SERS measurements. - Highlights: • Gold nanoparticles were produced by photochemical reaction of synchrotron radiation. • The gold nanoparticles grew and aggregated into the higher-order nanostructure. • The behavior is qualitatively explained by analytical estimation. • The surface-enhanced Raman spectroscopy of 4,4′-bipyridine (4bpy) was demonstrated. • The substrate fabricated in a suitable condition provides in situ SERS for 1 nM 4bpy.

  7. Ultraviolet spectrophotometric characterization of copper(II) complexes with imidazole N-methyl derivatives of ?-histidine in aqueous solution

    Science.gov (United States)

    Prenesti, Enrico; Berto, Silvia; Daniele, Pier Giuseppe

    2003-01-01

    In this study we considered π-methyl- L-histidine (π-methis) and τ-methyl- L-histidine (τ-methis) as ligands for copper(II) ion, in order to clarify, by means of ultraviolet (UV) spectroscopy in aqueous solution ( T=25 °C, I=0.1 M), some aspects of the co-ordination mode with respect to other ligands of a previous study in which copper(II) complexes of L-histidine, N-acetyl- L-histidine, histamine, L-histidine methyl ester or carnosine were investigated. Particularly, UV spectra (300-400 nm) were recorded on solutions at various pH values, containing each binary system Cu-L; afterwards, an UV absorption spectrum for single complexes was calculated, taking into account the chemical model previously assessed, in order to fulfil a correct spectrum-structure correlation. The problem related to the eventual superimposition of the CT shoulder (≈330 nm) to copper(II) of OH - and imidazole pyridine nitrogen groups were now solved by means of a comparison of the UV spectra of dimer species formed by both π-methis or τ-methis. Finally, copper(II) complex formation with 2,2'-bipyridine was taken into account to compare the behaviour of pyridine (from 2,2'-bipyridine) and pyridine imidazole nitrogens (from π-methis or τ-methis) with respect to the UV charge transfer process to copper(II) ion.

  8. Polyoxometalate-based eight-connected self-catenated network and fivefold interpenetrating framework

    International Nuclear Information System (INIS)

    Two entangled compounds [(bpy)6CuI6Cl3(MoVW5O19)] (1) and [(bpy)7CuI7Cl2(BW12O40)].H2O (2) (bpy=4,4'-bipyridine), have been successfully synthesized under hydrothermal conditions and characterized by element analysis, IR spectroscopy, thermal gravimetric analysis, X-ray photoelectron spectroscopy, and single crystal X-ray diffraction analyses. Compound 1 represents the first eight-connected self-penetrating network constructed from cuprous chloride clusters [Cu6Cl3] and Lindquist-type polyoxoanions. Compound 2 exhibits an interesting fivefold interpenetrating network consisting of Keggin polyoxoanions and Cu+-metal-organic framework. Crystal data of the two compounds are following: 1, triclinic, P1-bar, a=11.502(2) A, b=13.069(3) A, c=13.296(3) A, α=90.55(3)o, β=113.74(3)o, γ=110.48(3)o, Z=1; 2, triclinic, P1-bar, a=12.341(3) A, b=13.119(3) A, c=15.367(3) A, α=99.12(3)o, β=90.53(3)o, γ=104.49(3)o, Z=1. - Graphical abstract: Compound 1 is the POM-based unprecedented eight-connected self-penetrating organic-inorganic hybrid network constructed from the cuprous chloride clusters [Cu6Cl3], Lindquist-type polyoxoanions [MoVW5O19], and the 4,4'-bipyridine ligands.

  9. Tetranuclear polybipyridyl complexes of Ru(II) and Mn(II), their electro- and photo-induced transformation into di-mu-oxo Mn(III)Mn(IV) hexanuclear complexes.

    Science.gov (United States)

    Romain, Sophie; Baffert, Carole; Dumas, Stéphane; Chauvin, Jérôme; Leprêtre, Jean-Claude; Daveloose, Denis; Deronzier, Alain; Collomb, Marie-Noëlle

    2006-12-28

    Three heterotetranuclear complexes, [{Ru(II)(bpy)(2)(L(n))}(3)Mn(II)](8+) (bpy = 2,2'-bipyridine, n = 2, 4, 6), in which a Mn(II)-tris-bipyridine-like centre is covalently linked to three Ru(II)-tris-bipyridine-like moieties using bridging bis-bipyridine L(n) ligands, have been synthesised and characterised. The electrochemical, photophysical and photochemical properties of these complexes have been investigated in CH(3)CN. The cyclic voltammograms of the three complexes exhibit two successive very close one-electron metal-centred oxidation processes in the positive potential region. The first, which is irreversible, corresponds to the Mn(II)/Mn(III) redox system (E(pa) approximately 0.82 V vs Ag/Ag(+) 0.01 M in CH(3)CN-0.1 M Bu(4)NClO(4)), whereas the second which is, reversible, is associated with the Ru(II)/Ru(III) redox couple (E(1/2) approximately 0.91 V). In the negative potential region, three successive reversible four electron systems are observed, corresponding to ligand-based reduction processes. The three stable dimeric oxidized forms of the complexes, [Mn(2)(III,IV)O(2){Ru(II)(bpy)(2)(L(n))}(4)](11+), [Mn(2)(IV,IV)O(2){Ru(II)(bpy)(2)(L(n))}(4)](12+) and [Mn(2)(IV,IV)O(2){Ru(III)(bpy)(2)(L(n))}(4)](16+) are obtained in fairly good yields by sequential electrolyses after consumption of respectively 1.5, 0.5 and 3 electrons per molecule of initial tetranuclear complexes. The formation of the di-micro-oxo binuclear complexes are the result of the instability of the {[Ru(II)(bpy)(2)(L(n))](3)Mn(III)}(9+) species, which react with residual water, via a disproportionation reaction and the release of one ligand, [Ru(II)(bpy)(2)(L(n))](2+). A quantitative yield can be obtained for these reactions if the electrochemical oxidations are performed in the presence of an added external base like 2,6-dimethylpyridine. Photophysical properties of these compounds have been investigated showing that the luminescence of the Ru(II)-tris-bipyridine-like moieties is little

  10. Cytotoxicity of Ru(II) piano-stool complexes with chloroquine and chelating ligands against breast and lung tumor cells: Interactions with DNA and BSA.

    Science.gov (United States)

    Colina-Vegas, Legna; Villarreal, Wilmer; Navarro, Maribel; de Oliveira, Clayton Rodrigues; Graminha, Angélica E; Maia, Pedro Ivo da S; Deflon, Victor M; Ferreira, Antonio G; Cominetti, Marcia Regina; Batista, Alzir A

    2015-12-01

    The synthesis and spectroscopic characterization of nine π-arene piano-stool ruthenium (II) complexes with aromatic dinitrogen chelating ligands or containing chloroquine (CQ), are described in this study: [Ru(η(6)-C10H14)(phen)Cl]PF6 (1), [Ru(η(6)-C10H14)(dphphen)Cl]PF6 (2), [Ru(η(6)-C10H14)(bipy)Cl]PF6 (3), [Ru(η(6)-C10H14)(dmebipy)Cl]PF6 (4) and [Ru(η(6)-C10H14)(bdutbipy)Cl]PF6 (5), [Ru(η(6)-C10H14)(phen)CQ](PF6)2 (6), [Ru(η(6)-C10H14)(dphphen)CQ](PF6)2 (7), [Ru(η(6)-C10H14)(bipy)CQ](PF6)2 (8), [Ru(η(6)-C10H14)(dmebipy)CQ](PF6)2 (9): [1,10-phenanthroline (phen), 4,7-diphenyl-1,10-phenanthroline (dphphen), 2,2'-bipyridine (bipy), 5,5'-dimethyl-2,2'-bipyridine (dmebipy), and 4,4'-di-t-butyl-2,2'-bipyridine (dbutbipy)]. The solid state structures of five ruthenium complexes (1-5) were determined by X-ray crystallography. Electrochemical experiments were performed by cyclic voltammetry to estimate the redox potential of the Ru(II)/Ru(III) couple in each case. Their interactions with DNA and BSA, and activity against four cell lines (L929, A549, MDA-MB-231 and MCF-7) were evaluated. Compounds 2, 6 through 9, interact with DNA which was comparable to the one observed for free chloroquine. The results of fluorescence titration revealed that these complexes strongly quenched the intrinsic fluorescence of BSA following a static quenching procedure. Binding constants (Kb) and the number of binding sites (n~1) were calculated using modified Stern-Volmer equations. The thermodynamic parameters ΔG at different temperatures were calculated and subsequently the values of ΔH and ΔS were also calculated, which revealed that hydrophobic and electrostatic interactions play a major role in the BSA-complex association. The MTT assay results indicated that complexes 2, 5 and 7 showed cytostatic effects at appreciably lower concentrations than those needed for cisplatin, chloroquine and doxorubicin. PMID:26277415

  11. Influence of selenocyanate ligands on the transition temperature and cooperativity of bapbpy-based Fe(II) spin-crossover compounds.

    Science.gov (United States)

    Zheng, Sipeng; Siegler, Maxime A; Roubeau, Olivier; Bonnet, Sylvestre

    2014-12-15

    Coordination of the ligand bapbpy (1, bapbpy = N,N'-di(pyrid-2-yl)-2,2'-bipyridine-6,6'-diamine), of one of its four dimethyl-substituted analogues 2-5 (R2bapbpy = N,N'-di(methylpyrid-2-yl)-2,2'-bipyridine-6,6'-diamine), or of one of its three bis(iso)quinoline analogues 6-8 (R2bapbpy= N,N'-di(quinolyl)-2,2'-bipyridine-6,6'-diamine), to Fe(NCSe)2, afforded eight new iron(II) compounds of the type [Fe(R2bapbpy)(NCSe)2] (9-16). Three of these compounds (11, 13, and 16) were structurally characterized by single crystal X-ray diffraction, which showed similar molecular geometry and packing compared to their thiocyanate analogues. Magnetic susceptibility measurements were carried out for all iron compounds and revealed thermal spin-crossover (SCO) behavior for compounds 9, 11, 13, 15, and 16. Compounds 11, 13, 15, and 16 show an increased transition temperature compared to the thiocyanate analogues. [Fe(bapbpy)(NCSe)2] (9) shows a gradual, one-step SCO, whereas its thiocyanate analogue [Fe(bapbpy)(NCS)2] is known for its cooperative two-step SCO. To discuss the influence of S-to-Se substitution on the cooperativity of the SCO, heat capacity measurements were carried out for compounds 9, 11, 13, 15, and 16, and fitted to the Sorai domain model. The number n of like-spin SCO centers per interacting domain, which is a quantitative measure of the cooperativity of the spin transition, was found to be high for compounds 11 and 15, and low for compounds 9, 11, and 13. Compound 15 is one of the few known SCO compounds that is more cooperative than its thiocyanate analogue. Altogether, X-ray diffraction, calorimetry, and magnetic data give a consistent structure-property relationship for this family of compounds: hydrogen-bonding networks made of intermolecular N-H···Se interactions are of paramount importance for the cooperativity of the SCO. PMID:25411921

  12. Synthesis, Characterization, and Crystal Structure Determination of a New Indium (III) Complex: [In(5,5’-DiMeBiPy)Cl3(DMSO)].2(DMSO)

    OpenAIRE

    Sadif A. Shirvan; Fereydoon Khazali; Sara Haydari Dezfuli

    2014-01-01

    [In(5,5’-DiMeBiPy)Cl3(DMSO)].2(DMSO) complex (5,5’-DiMeBiPy is 5,5’-Dimethyl-2,2’-bipyridine) was prepared from reaction of InCl3.4H2O with 5,5’-DiMeBiPy in 1.1 molar ratio in DMSO. This compound has been characterized by IR, 1H NMR, UV-Vis spectroscopy as well as X-ray crystallography. This compound crystallizes in the space group Pī of the triclinic system. The unit cell dimensions is: a = 8.6695(8) Å, b = 12.8456(14) Å, c = 13.0877(12) Å, a = 78.258(8)º, β = 85.270(8)º, g = 74.932(8)º. Acc...

  13. A New Luminescent Ruthenium(Ⅱ) Polypyridine-derived Dipicolylamine Complex as a Sensor for Cu2+ Ions%A New Luminescent Ruthenium(Ⅱ) Polypyridine-derived Dipicolylamine Complex as a Sensor for Cu2+ Ions

    Institute of Scientific and Technical Information of China (English)

    Li, Xianghong; Chen, Yuanbing; Meng, Jiahe; Lu, Kangle; Zhang, Aiqing; Zhang, Bingguang

    2011-01-01

    A chemo-sensor [Ru(bpy)2(bpy-DPF)](PF6)2 (1) (bpy = 2,2'-bipyridine, bpy-DPF = 2,2'-bipyridyl-4,4'- bis(N,N-di(2-picolyl))formylamide) for Cu2+ using di(2-picolyl)amine (DPA) as the recognition group and a ruthe- nium(II) complex as the reporting group was synthesized and characterized successfully. It demonstrates a high se- lectivity and efficient signaling behavior only for Cu2+ with obvious red-shifted MLCT (metal-to-ligand charge transfer transitions) absorptions and dramatic fluorescence quenching compared with Zn2+ and other metal ions.

  14. Ruthenium(ii) complexes with dppz: from molecular photoswitch to biological applications.

    Science.gov (United States)

    Li, Guanying; Sun, Lingli; Ji, Liangnian; Chao, Hui

    2016-09-14

    The DNA photoswitch [Ru(bpy)2dppz](2+) (bpy = 2,2'-bipyridine, dppz = dipyrido[3,2-a:2',3'-c]phenazine) has attracted much attention and become a powerful tool for studying the interaction of metal polypyridyl complexes with DNA. A large number of Ru-dppz complexes have been designed for a wide range of uses in many fields. In this perspective, we first introduce the latest results of Ru-dppz complexes that bind with DNA. The mechanisms of the light-switch effect and the structural modifications of Ru-dppz systems are also briefly introduced. We also review the recent advances in biological applications of the Ru-dppz system in DNA binders, cellular imaging, anticancer drugs, protein aggregation detection and chemosensors. PMID:27426487

  15. Chemisorption of a thiol-functionalized ruthenium dye on zinc oxide nanoparticles: Implications for dye-sensitized solar cells

    Science.gov (United States)

    Singh, Jagdeep; Im, Jisun; Whitten, James E.; Soares, Jason W.; Steeves, Diane M.

    2010-09-01

    ZnO is an alternative to TiO 2-based dye-sensitized solar cells (DSSCs). Adsorption of cis-ruthenium-bis[2,2'-bipyridine]-bis[4-thiopyridine] onto ZnO nanorods has been studied using X-ray and ultraviolet photoelectron spectroscopies (XPS and UPS). XPS indicates chemisorption with a surface density of ca. 1 × 10 15 molecules/cm 2, confirming the possibility of using thiol-terminated dyes for ZnO-based DSSC devices. The energy level diagram, based on UPS and absorbance spectroscopy, indicates that the LUMO of this dye is lower in energy than the ZnO conduction band edge, providing minimal enthalpic driving force for photovoltaic electron injection. However, optimization of thiol-functionalized Ru dyes could result in competitive ZnO-based DSSCs.

  16. Titania modification with a ruthenium(II) complex and gold nanoparticles for photocatalytic degradation of organic compounds

    OpenAIRE

    Zheng, Shuaizhi; Wei, Zhishun; Yoshiiri, Kenta; Braumueller, Markus; Ohtani, Bunsho; Rau, Sven; Kowalska, Ewa

    2016-01-01

    Titania of fine anatase nanoparticles (ST01) was modified successively with two components, i.e., a ruthenium(II) complex with phosphonic anchoring groups [Ru(bpy)(2)(4,4'-(CH2PO3H2)(2)bpy)](2+) bpy = 2,2'-bipyridine ((RuCP)-C-II) and gold nanoparticles (Au). Various compositions of two titania modifiers were investigated, i.e., Au, Au + (RuCP)-C-II, Au + 0.5Ru(II)CP, (RuCP)-C-II, 0.5Ru(II)CP and 0.25Ru(II)CP, where Au and (RuCP)-C-II correspond to 0.81 mol% and 0.34 mol% (with respect to tit...

  17. Single-Site Palladium(II) Catalyst for Oxidative Heck Reaction: Catalytic Performance and Kinetic Investigations

    Energy Technology Data Exchange (ETDEWEB)

    Duan, Hui; Li, Mengyang; Zhang, Guanghui; Gallagher, James R.; Huang, Zhiliang; Sun, Yu; Luo, Zhong; Chen, Hongzhong; Miller, Jeffrey T.; Zou, Ruqiang; Lei, Aiwen; Zhao, Yanli

    2015-01-01

    ABSTRACT: The development of organometallic single-site catalysts (SSCs) has inspired the designs of new heterogeneous catalysts with high efficiency. Nevertheless, the application of SSCs in certain modern organic reactions, such as C-C bond formation reactions, has still been less investigated. In this study, a single-site Pd(II) catalyst was developed, where 2,2'-bipyridine-grafted periodic mesoporous organosilica (PMO) was employed as the support of a Pd(II) complex. The overall performance of the single-site Pd(II) catalyst in the oxidative Heck reaction was then investigated. The investigation results show that the catalyst displays over 99% selectivity for the product formation with high reaction yield. Kinetic profiles further confirm its high catalytic efficiency, showing that the rate constant is nearly 40 times higher than that for the free Pd(II) salt. X-ray absorption spectroscopy reveals that the catalyst has remarkable lifetime and recyclability.

  18. Effect of particle size and alloying with different metals on {sup 57}Fe Moessbauer spectra

    Energy Technology Data Exchange (ETDEWEB)

    Nazir, Rabia; Mazhar, Muhammad, E-mail: mazhar42pk@yahoo.com [Quaid-i-Azam University, Department of Chemistry (Pakistan); Siddique, Muhammad [PINSTECH, Physics Division (Pakistan); Hussain, S. Tajammul [Quaid-i-Azam University, Department of Chemistry (Pakistan)

    2009-02-15

    Iron nanoparticles of various sizes have been synthesized using the chemical route which involves the preparation of iron bipyridine complexes in presence of different capping agents followed by thermal decomposition at 450 deg. C in inert atmosphere. The bimetallic nanoalloys of Fe with Mg and Pd have also been prepared by following the same route. The resulting nanoparticles have been characterized by EDX-RF, XRD, AFM and {sup 57}Fe Moessbauer spectroscopy. The appearance of quadrupole doublets in the Moessbauer spectra of Fe nanoparticles indicates the absence of magnetic interaction and variation in parameters is due to the varying particle size. The Moessbauer spectrum of Fe-Mg{sub 2} bimetallic nanoalloy shows two doublets indicating the presence of superparamagnetism. The two doublets can be attributed to change in s-electron density of iron resulting from its two neighboring magnesium atoms. Fe-Pd nanoalloy Moessbauer spectrum is characterized by having a superparamagnetic doublet and a ferromagnetic sextet.

  19. Gradients of Rectification: Tuning Molecular Electronic Devices by the Controlled Use of Different-Sized Diluents in Heterogeneous Self-Assembled Monolayers.

    Science.gov (United States)

    Kong, Gyu Don; Kim, Miso; Cho, Soo Jin; Yoon, Hyo Jae

    2016-08-22

    Molecular electronics has received significant attention in the last decades. To hone performance of devices, eliminating structural defects in molecular components inside devices is usually needed. We herein demonstrate this problem can be turned into a strength for modulating the performance of devices. We show the systematic dilution of a monolayer of an organic rectifier (2,2'-bipyridine-terminated n-undecanethiolate) with electronically inactive diluents (n-alkanethiolates of different lengths), gives remarkable gradients of rectification. Rectification is finely tunable in a range of approximately two orders of magnitude, retaining its polarity. Trends of rectification against the length of the diluent indicate the gradient of rectification is extremely sensitive to the molecular structure of the diluent. Further studies reveal that noncovalent intermolecular interactions within monolayers likely leads to gradients of structural defect and rectification. PMID:27443577

  20. Role of substituents on the reactivity and electron density profile of diimine ligands: A density functional theory based study

    Indian Academy of Sciences (India)

    Bhakti S Kulkarni; Deepti Mishra; Sourav Pal

    2013-09-01

    In this paper, we study the reactivity of diimines like 2, 2'-bipyridine, 1, l0-phenanthroline and 1, 2, 4-triazines using density-based reactivity descriptors. We discuss the enhancement or diminution in the reactivity of these ligands as a function of two substituent groups, namely methyl (-CH3) group and phenyl (-C6H5) group. The global reactivity descriptors explain the global affinity and philicity of these ligands, whereas the local softness depicts the particular site selectivity. The inter-molecular reactivity trends for the same systems are analysed through the philicity and group philicity indices. The -donor character of these ligands is quantified with the help of electron density profile. In addition, the possible strength of interaction of these ligands with metal ions is supported with actual reaction energies of Ru-L complexes.

  1. Quantifying the relative molecular orbital alignment for molecular junctions with similar chemical linkage to electrodes

    Science.gov (United States)

    Bâldea, Ioan

    2014-11-01

    Estimating the relative alignment between the frontier molecular orbitals (MOs) that dominates the charge transport through single-molecule junctions represents a challenge for theory. This requires approaches beyond the widely employed framework provided by the density functional theory, wherein the Kohn-Sham ‘orbitals’ are treated as if they were real MOs, which is not the case. In this paper, we report results obtained by means of quantum chemical calculations, including the equation-of-motion coupled-cluster singles and doubles, which is the state-of-the-art of quantum chemistry for medium-size molecules like those considered here. These theoretical results are validated against data on the MO energy offset relative to the electrodes’ Fermi energy extracted from experiments for junctions based on 4,4’-bipyridine and 1,4-dicyanobenzene.

  2. Quantifying the relative molecular orbital alignment for molecular junctions with similar chemical linkage to electrodes

    International Nuclear Information System (INIS)

    Estimating the relative alignment between the frontier molecular orbitals (MOs) that dominates the charge transport through single-molecule junctions represents a challenge for theory. This requires approaches beyond the widely employed framework provided by the density functional theory, wherein the Kohn–Sham ‘orbitals’ are treated as if they were real MOs, which is not the case. In this paper, we report results obtained by means of quantum chemical calculations, including the equation-of-motion coupled-cluster singles and doubles, which is the state-of-the-art of quantum chemistry for medium-size molecules like those considered here. These theoretical results are validated against data on the MO energy offset relative to the electrodes’ Fermi energy extracted from experiments for junctions based on 4,4’-bipyridine and 1,4-dicyanobenzene. (paper)

  3. Fabrication and photoelectrochemical properties of electron donor-acceptor assemblies via titanium oxide interlayers

    Energy Technology Data Exchange (ETDEWEB)

    Nitahara, Satoshi; Terasaki, Nao; Akiyama, Tsuyoshi; Yamada, Sunao

    2003-08-22

    Ultrathin molecular films consisting of electron donor (D)-acceptor (A) pairs via titanium oxide coordinative bonding have been fabricated on an indium-tinoxide electrode, by using the techniques of self-assembly and surface sol-gel process. Porphyrin and tris (2,2'-bipyridine) ruthenium (II) were used as D, while viologen as A, respectively. The degree of assembling of D and A were characterized by electrochemical and absorption measurements. In the case of the porphyrin-viologen pair, photocurrent generation based on photoinduced electron-transfer was realized, and multilayer formation of porphyrin increased the photocurrents. On the other hand, the ruthenium (II) complex-viologen pair showed very poor photocurrent responses, probably due to much poorer light absorptivity as compared with porphyrin.

  4. Fabrication and photoelectrochemical properties of electron donor-acceptor assemblies via titanium oxide interlayers

    International Nuclear Information System (INIS)

    Ultrathin molecular films consisting of electron donor (D)-acceptor (A) pairs via titanium oxide coordinative bonding have been fabricated on an indium-tinoxide electrode, by using the techniques of self-assembly and surface sol-gel process. Porphyrin and tris (2,2'-bipyridine) ruthenium (II) were used as D, while viologen as A, respectively. The degree of assembling of D and A were characterized by electrochemical and absorption measurements. In the case of the porphyrin-viologen pair, photocurrent generation based on photoinduced electron-transfer was realized, and multilayer formation of porphyrin increased the photocurrents. On the other hand, the ruthenium (II) complex-viologen pair showed very poor photocurrent responses, probably due to much poorer light absorptivity as compared with porphyrin

  5. Fluorescent tetraruthenated porphyrins embedded in monolithic SiO2 gels by the sol-gel process.

    Science.gov (United States)

    Santos, Shirleny F; Santos, Marcelo L; Almeida, Luis E; Costa, Nivan B; Gimenez, Iara F; Araki, Koiti; Mayer, Ildemar; Engelmann, Fabio Monaro; Toma, Henrique Eisi; Barreto, Ledjane S

    2007-01-15

    In this work silica gels have been prepared by a sol-gel method using tetraethylorthosilicate as gel precursor. The tetraruthenated porphyrins H2(3-TRPyP), Co(3-TRPyP), and H2(4-TRPyP) were incorporated into the systems during gel formation without problems commonly found in the process, such as aggregation. Spectroscopic studies of the resulting silica gels revealed the presence of absorption bands in the range 200-400 nm associated with the transitions of the groups ruthenium-bipyridine, along with the Soret band at the same wavelengths observed in solution. The porphyrins were found to preserve fluorescence emission properties in the range 650-700 nm even after the aging period. Study of the thermal behavior and decomposition kinetics evidenced that the porphyrin H2(4-TRPyP) is the least stable of the group and that all compounds decompose according to first-order kinetics. PMID:17074358

  6. Extending the Newns-Anderson model to molecules with floppy degrees of freedom. Validation by electronic structure calculations

    CERN Document Server

    Baldea, Ioan

    2012-01-01

    In cases where reorganization is important, present theoretical studies of molecular transport have inherently to resort to models. The Newns-Anderson model is ubiquitous for this purpose but, to author's knowledge, attempts to validate/challenge this model by microscopic calculations are missing in the literature. In this work, results of electronic structure calculations are presented, which demonstrate that the conventional Newns-Anderson model fails to describe redox-active tunneling junctions of recent experimental interest. For the case considered, the ($4, 4^\\prime$)-bipyridine molecule, the failure traces back to the floppy degree of freedom represented by the relative rotation of the two pyridine rings. Expressions that generalize the Newns-Anderson model are deduced, which include significant anharmonicities. These expressions can be straightforwardly utilized as input information in calculations of the partially coherent transport.

  7. Molecular orientation of hydrogen-bonded liquid crystal (6BA){sub 2}-(BPy){sub x} as Studied by {sup 2}H NMR

    Energy Technology Data Exchange (ETDEWEB)

    Mizuno, M., E-mail: mizuno@se.kanazawa-u.ac.jp; Higashima, Y.; Yamashita, A.; Ishida, Y.; Miyatou, T.; Kumagai, Y.; Ohashi, R.; Ida, T. [Kanazawa University, Kakuma, Department of Chemistry, Graduate School of Natural Science & Technology (Japan)

    2015-04-15

    The thermal properties of hydrogen-bonded liquid crystal (6BA){sub 2}-(BPy){sub x} (6BA: 4-n-hexylbenzoicacid, BPy: 4,4’-bipyridine) were investigated by DSC. Two liquid crystal phases (LC{sub I}, LC{sub II}) were found for (6BA){sub 2}-(BPy){sub 0.5}. In LC{sub II}, the distribution of the orientation of molecules was larger than in LC{sub I}. The order parameter S of molecular orientation in the liquid crystal phase was estimated from a {sup 2}H NMR spectrum. S decreased rapidly around the LC{sub I}-LC{sub II} phase transition. The increase in orientational fluctuation of the 6BA dimer with an open dimer structure is predicted to cause the rapid decrease of S.

  8. 1D Ladder-like Chain and 1D Channeled 3D Supramolecular Architectures Based on Benzophenone-2,4'-dicarboxylic Acid

    Institute of Scientific and Technical Information of China (English)

    YANG Xiao-Gang; LI Dong-Sheng; FU Feng; WU Ya-Pan; WANG Ji-Jiang; WANG Yao-Yu

    2008-01-01

    The hydrothermal reactions of AgNO3, 2,2'-bipyridyl, and benzophenone-2,4'-dicarboxylic acid gave rise to two benzophenone-2,4'-dicarboxylic acid). The two compounds are extended by hydrogen bonds in two different apbonding between H2L ligands and water molecules, then extended to a 3D supramolecular architecture. Compound 2 possesses 3D supramolecular architecture containing 1D open channels, which are driven due to the strong H-bonding interactions occurring between the HL anions and water molecules; interestingly, [Ag(bpy)2]+ cations vestigated, the emission maxima for 2 exhibits red-shift compared with that of free ligand and 1 due to chelating effect of the 2,2'-bipyridine ligand to the silver ion and the presence of aromatic π-packing.

  9. Cyclic Water Clusters in Tape-Like and Cage-Like Structures

    Directory of Open Access Journals (Sweden)

    Fuhou Lei

    2011-04-01

    Full Text Available Controlling the ratio of 2,2′-bpy to benzene-1,3,5-tricarboxylic acid produces two interesting complexes, namely [Co(2,2′-bpy3] (SO4 8.5H2O (1 and [Cu2(BTCA (2,2′-bpy4] (OH (2,2′-bpy0.5·14H2O (2 (H3BTCA = benzene-1,3,5-tricarboxylic acid, 2,2′-bpy = 2,2′-bipyridine. We report the structural evidence in the solid state of discrete lamellar water cluster conformations. These units are found to act as supramolecular glue in the aggregation of cobalt (II or copper (II complexes to give three dimensional cage-like networks through hydrogen-bonding. It is interesting that the structure of complex 1 contains a 3D negatively charged cage.

  10. [U(TpMe2)2(bipy)]+: A cationic uranium(III) complex with single molecule magnet behavior

    International Nuclear Information System (INIS)

    The addition of 2,2'-bipyridine to [U(TpMe2)2I] (1) results in the displacement of the iodide and the formation of the cationic uranium(III) complex [U(TpMe2)2(bipy)]I (2). This compound was isolated as a dark-green solid in good yield and characterized by IR and NMR spectroscopies, and its molecular structure was determined by single-crystal X-ray diffraction. Studies of its magnetic properties revealed a frequency dependence of magnetization with a blocking temperature of 4.5 K and, at lower temperatures, a slow relaxation of magnetization with an energy barrier of 18.2 cm-1, characteristic of single-molecule-magnet behavior. (authors)

  11. A quantum chemical study from a molecular perspective: ionization and electron attachment energies for species often used to fabricate single-molecule junctions

    CERN Document Server

    Baldea, Ioan

    2015-01-01

    The accurate determination of the lowest electron attachment ($EA$) and ionization ($IP$) energies for molecules embedded in molecular junctions is important for correctly estimating, \\emph{e.g.}, the magnitude of the currents ($I$) or the biases ($V$) where an $I-V$-curve exhibits a significant non-Ohmic behavior. Benchmark calculations for the lowest electron attachment and ionization energies of several typical molecules utilized to fabricate single-molecule junctions characterized by n-type conduction (4,4'-bipyridine, 1,4-dicyanobenzene, and 4,4'-dicyano-1,1'-biphenyl) and p-type conduction (benzenedithiol, biphenyldithiol, hexanemonothiol, and hexanedithiol] based on the EOM-CCSD (equation-of-motion coupled-cluster singles and doubles) state-of-the-art method of quantum chemistry are presented. They indicate significant differences from the results obtained within current approaches to molecular transport. The present study emphasizes that, in addition to a reliable quantum chemical method, basis sets m...

  12. Theoretical oxidation state analysis of Ru-(bpy)3: Influence of water solvation and Hubbard correction in first-principles calculations

    International Nuclear Information System (INIS)

    Oxidation state is a powerful concept that is widely used in chemistry and materials physics, although the concept itself is arguably ill-defined quantum mechanically. In this work, we present impartial comparison of four, well-recognized theoretical approaches based on Lowdin atomic orbital projection, Bader decomposition, maximally localized Wannier function, and occupation matrix diagonalization, for assessing how well transition metal oxidation states can be characterized. Here, we study a representative molecular complex, tris(bipyridine)ruthenium. We also consider the influence of water solvation through first-principles molecular dynamics as well as the improved electronic structure description for strongly correlated d-electrons by including Hubbard correction in density functional theory calculations

  13. Nanoparticules de photocommutateurs moleculaires bases sur des complexes de fe(II) a conversion de spin et a ligands photo-isomerisables

    OpenAIRE

    Nguyen, Luong-Lam

    2014-01-01

    Enquête sur le fer(II) noyau transition de spin centrée métal coordonner avec des ligands photo-actif (isomérisation tran / cis) et l'étude de la lumière induite par le changement de spin conduit ligand (LD-LISC) propriétés en fer(II) fonctionnalisé complexes sous la forme de nanoparticules dispersées dans des films minces transparents. Pour cette étude, nous avons choisi un ensemble de complexes mononucléaires incorporant un ligand bipyridine substitué soit par un groupe méthyle (de la fonct...

  14. Scanning electrochemical microscopy. 36. A combined scanning electrochemical microscope-quartz crystal microbalance instrument for studying thin films.

    Science.gov (United States)

    Cliffel, D E; Bard, A J

    1998-05-01

    The design of a combined scanning electrochemical microscope-quartz crystal microbalance (SECM-QCM) with separate potential control of the tip and substrate is described. Both lateral and vertical tip movements near the substrate affect the QCM resonant frequency because of perturbations of the longitudinal and shear waves of the quartz crystal (QC) acoustic wave sensor. The SECM-QCM was used to study etching of a thin Ag layer deposited on the QC contact by generating an etchant, iron(III) tris(bipyridine), at the tip near the surface. The SECM-QCM was also used to monitor film mass and surrounding electrolyte composition during potential cycling of a film of C(60) on an electrode. PMID:21651290

  15. Direct electrochemical measurements inside a 2000 angstrom thick polymer film by scanning electrochemical microscopy.

    Science.gov (United States)

    Mirkin, M V; Fan, F R; Bard, A J

    1992-07-17

    An extremely small, conically shaped Pt microelectrode tip (with a radius of 30 nanometers) and the precise positioning capabilities of the scanning electrochemical microscope were used to penetrate a thin (200 nanometers) polymer film and obtain directly the standard potential and kinetic parameters of an electrode reaction within the film. The thickness of the film was determined while it was immersed in and swollen by an electrolyte solution. The film studied was the perfluorosulfonate Nafion containing Os(bpy)(3)(2+) (bpy, 2,2'-bipyridine) cast on an indium tin oxide surface. The steady-state response at the ultramicroelectrode allowed direct determination of the rate constant for heterogeneous electron transfer K(o) and the diffusion coefficient D without complications caused by transport in the liquid phase, charge exchange at the liquid-polymer interface, and resistive drop. PMID:17832832

  16. Self-Powered Sugar Indicator Using CNT-Enzyme Ensemble Film

    Science.gov (United States)

    Ogawa, Y.; Yoshino, S.; Kato, K.; Magome, T.; Yamada, T.; Miyake, T.; Hata, K.; Nishizawa, M.

    2013-12-01

    We report the stepwise modification of Os-complex mediator (polyvinylimidazole-[Os(bipyridine)2Cl] (PVI-[Os(bpy)2Cl]) and glucose oxidase (GOD) within the inner nano-space of a carbon nanotube forest (CNTF) film. Owing to the controlled alignment of enzyme/mediator/electrode in the ensemble, the prepared film electrode has both a high-efficiency (turnover rate of ca. 650 s-1) and a large net oxidation current (ca. 15 mA cm-2). The previous GOD electrodes developed by monolayer-based and polymer-based approaches have either of the performances (efficiency or net activity). In addition, the present GOD electrode is a flexible film that could be used by winding on needle devices.

  17. Self–Powered Sugar Indicator Using CNT–Enzyme Ensemble Film

    International Nuclear Information System (INIS)

    We report the stepwise modification of Os-complex mediator (polyvinylimidazole-[Os(bipyridine)2Cl] (PVI-[Os(bpy)2Cl]) and glucose oxidase (GOD) within the inner nano-space of a carbon nanotube forest (CNTF) film. Owing to the controlled alignment of enzyme/mediator/electrode in the ensemble, the prepared film electrode has both a high-efficiency (turnover rate of ca. 650 s−1) and a large net oxidation current (ca. 15 mA cm−2). The previous GOD electrodes developed by monolayer-based and polymer-based approaches have either of the performances (efficiency or net activity). In addition, the present GOD electrode is a flexible film that could be used by winding on needle devices

  18. Electron transfer patterns of the di-heme protein cytochrome c(4) from Pseudomonas stutzeri

    DEFF Research Database (Denmark)

    Raffalt, Anders Christer; Schmidt, L.; Christensen, Hans Erik Mølager;

    2009-01-01

    We report kinetic data for the two-step electron transfer (ET) oxidation and reduction of the two-domain di-heme redox protein Pseudomonas stutzeri cytochrome (cyt) c(4) by [Co(bipy)(3)](2- 3-) (bipy = 2,2'-bipyridine). Following earlier reports, the data accord with both bi- and tri......-exponential kinetics. A complete kinetic scheme includes both "cooperative" intermolecular ET between each heme group and the external reaction partner, and intramolecular ET between the two heme groups. A now data analysis scheme shows unequivocally that two-ET oxidation and reduction of P. stutzeri cyt c(4) is...... entirely dominated by intermolecular ET between the heme groups and the external reaction partner in the ms time range, with virtually no contribution from intramolecular interheme ET in this time range. This is in striking contrast to two-ET electrochemical oxidation or reduction of P. stutzeri cyt c(4...

  19. Optimizations of large area quasi-solid-state dye-sensitized solar cells

    DEFF Research Database (Denmark)

    Biancardo, M.; West, K.; Krebs, Frederik C

    2006-01-01

    In this paper, we address optimizations of dye sensitized solar cells (DSSCs) through the combination of important issues like semi-transparency, quasi-solid-state constructions and low-cost realization of serially connected modules. DSSCs with a transparency of 50% in the visible region, moderate...... efficiency similar to 1%, and long lifetime allow solar cells application in building elements like windows, facades and semi-transparent roofs. The use in DSSCs of gel polymer electrolytes prepared by liquid electrolyte incorporation into a polymer matrix such as poly-methyl-methacrylate presents...... encouraging results. A short circuit current (I-sc) of 4.45 mA cm(-2) with an open circuit voltage (V-oc) of 0.5 V were recorded in standard solar cells sensitized by cis-bis(thiocyano) ruthenium(II)-bis-2, 2'-bipyridine-4, 4'-dicarboxylate. Up-scaling tests demonstrate the easy realization of a 625 cm(2...

  20. New Polyazine-Bridged Ru(II),Rh(III) and Ru(II),Rh(I) Supramolecular Photocatalysts for Water Reduction to Hydrogen Applicable for Solar Energy Conversion and Mechanistic Investigation of the Photocatalytic Cycle

    OpenAIRE

    Zhou, Rongwei

    2014-01-01

    The goal of this research is to test the design constraints of active dpp-bridged RuII,RhIII (dpp = 2,3-bis(2-pyridyl)pyrazine)) supramolecular photocatalysts for water reduction to H2 and provide mechanistic insights into the catalytic cycle. Two member of a new RuII,RhIII motifs with only one Rh-'Cl bond, [(bpy)2Ru(dpp)RhCl(tpy)](PF6)4 ( bpy = 2,2'-bipyridine, tpy = 2,2':6,2"-terpyridine) and [(bpy)2Ru(dpp)RhCl(tpm)](PF6)4, (tpm = tris(1-pyrazolyl)methane), and a cis-RhCl2 model system, [(b...

  1. Fluorescence quenching effect of metal ions for α,α'-diamine containing conjugated polymers in solid films

    Institute of Scientific and Technical Information of China (English)

    TIAN Leilei; ZHANG Ming; LU Ping; ZHANG Wu; YANG Bing; MA Yuguang

    2004-01-01

    The fluorescence quenching effect of the conjugated polymers P1 and P2 (the molecular recognitions are twisted 2,2′-bipyridine (bpy) and planar 1,10-phenanthrolin (phen), respectively) films upon the addition of metal ions has been studied. And the results showed that P2 exhibited stronger fluorescence quenching ability upon the addition of both transition metal ions and main group metal ions compared with that of P1. The 20° twist angle between the two consecutive pyridine rings of bpy unit in the P1 main chain is the reason for the weaker fluorescence quenching ability compared with P2, in which the planar phen unit can chelate with metal ions relatively freely without the conformational transition. So P2 is a kind of material with better properties for solid film devices, such as sensors for metal ions recognition.

  2. Dearomatization Reactions of N-Heterocycles Mediated by Group 3 Complexes

    Energy Technology Data Exchange (ETDEWEB)

    Miller, Kevin L [Univ. of California, Los Angeles, CA (United States); Williams, Bryan N [Univ. of California, Los Angeles, CA (United States); Benitez, Diego [California Inst. of Technology (CalTech), Pasadena, CA (United States); Carver, Colin T [Univ. of California, Los Angeles, CA (United States); Ogilby, Kevin R [Univ. of California, Los Angeles, CA (United States); Tkatchouk, Ekaterina [California Inst. of Technology (CalTech), Pasadena, CA (United States); Goddard, William A [California Inst. of Technology (CalTech), Pasadena, CA (United States); Diaconescu, Paula L [Univ. of California, Los Angeles, CA (United States)

    2010-01-13

    Group 3 (Sc, Y, Lu, La) benzyl complexes supported by a ferrocene diamide ligand are reactive toward aromatic N-heterocycles by mediating their coupling and, in a few cases, the cleavage of their C-N bonds. When these complexes reacted with 2,2'-bipyridine or isoquinoline, they facilitated the alkyl migration of the benzyl ligand onto the pyridine ring, a process accompanied by the dearomatization of the N-heterocycle. The products of the alkyl-transfer reactions act as hydrogen donors in the presence of aromatic N-heterocycles, ketones, and azobenzene. Experimental and computational studies suggest that the hydrogen transfer takes place through a concerted mechanism. An interesting disproportionation reaction of the dearomatized, alkyl-substituted isoquinoline complexes is also reported.

  3. A mercuric ensemble based on a cycloruthenated complex as a visual probe for iodide in aqueous solution

    Science.gov (United States)

    Su, Xianlong; Guo, Lieping; Ma, Yajuan; Li, Xianghong

    2016-01-01

    A new water-soluble cycloruthenated complex Ru(bthiq)(dcbpy)2+ (1, Hbthiq = 1-(2-benzo[b]thiophenyl)isoquinoline, dcbpy = 4,4‧-dicarboxylate-2,2‧-bipyridine) was designed and synthesized to form its mercuric ensemble (1-Hg2+) to achieve visual detection of iodide anions. The binding constant of 1-Hg2+ is calculated to be 2.40 × 104 M-1, which is lower than that of HgI2. Therefore, the addition of I- to the aqueous solution of 1-Hg2+lead to significant color changes from yellow to deep-red by the release of 1. The results showed that iodide anions could be easily detected by the naked eyes. The detection limit of iodide anion is calculated as 0.77 μM. In addition, an easily-prepared test strip of 1-Hg2+ was obtained successfully to detect iodide anions.

  4. Synthesis,crystal structures,electrochemical and spectroscopic properties of ruthenium(Ⅱ) complexes containing diamino-1,3,5-triazine derivatives

    Institute of Scientific and Technical Information of China (English)

    2010-01-01

    Three Ru(Ⅱ) complexes [Ru(bpy)2(1-IQTNH)](ClO4)2 (1), [Ru(bpy)2(2-QTNH)](ClO4)2 (2) and [Ru(bpy)2(3-IQTNH)](ClO4)2 (3) (bpy = 2,2′-bipyridine, 1-IQTNH = 6-(isoquinolin-1-yl)-1,3,5-triazine-2,4-diamine, 2-QTNH = 6-(quinolin-2-yl)-1,3,5-triazine-2,4-diamine, 3-IQTNH = 6-(isoquinolin-3-yl)-1,3,5-triazine-2,4-diamine) have been synthesized and characterized by elemental analysis, 1H NMR spectroscopy, electrospray ionization mass spectrometry and X-ray crystallography. The electrochemical and spectroscopic properties of the complexes differ from those of [Ru(bpy)3]2+ owing to the structural differences between the ligands and their complexes.

  5. Molecular and electronic structure of osmium complexes confined to Au(111) surfaces using a self-assembled molecular bridge

    Energy Technology Data Exchange (ETDEWEB)

    Llave, Ezequiel de la; Herrera, Santiago E.; Adam, Catherine; Méndez De Leo, Lucila P.; Calvo, Ernesto J.; Williams, Federico J., E-mail: fwilliams@qi.fcen.uba.ar [INQUIMAE-CONICET, Departamento de Química Inorgánica, Analítica y Química-Física, Facultad Ciencias Exactas y Naturales, Universidad de Buenos Aires, Ciudad Universitaria, Pabellón 2, Buenos Aires C1428EHA (Argentina)

    2015-11-14

    The molecular and electronic structure of Os(II) complexes covalently bonded to self-assembled monolayers (SAMs) on Au(111) surfaces was studied by means of polarization modulation infrared reflection absorption spectroscopy, photoelectron spectroscopies, scanning tunneling microscopy, scanning tunneling spectroscopy, and density functional theory calculations. Attachment of the Os complex to the SAM proceeds via an amide covalent bond with the SAM alkyl chain 40° tilted with respect to the surface normal and a total thickness of 26 Å. The highest occupied molecular orbital of the Os complex is mainly based on the Os(II) center located 2.2 eV below the Fermi edge and the LUMO molecular orbital is mainly based on the bipyridine ligands located 1.5 eV above the Fermi edge.

  6. Bis(μ-bis{[4-(2-pyridylpyrimidin-2-yl]sulfanyl}methanedisilver(I bis(perchlorate

    Directory of Open Access Journals (Sweden)

    Hai-Bin Zhu

    2010-12-01

    Full Text Available In the macrocyclic centrosymmetric dinuclear complex, [Ag2(C19H14N6S22](ClO42, the AgI atom, bis{[4-(2-pyridylpyrimidin-2-yl]sulfanyl}methane (2-bppt ligand and perchlorate anion each lie on a twofold rotation axis. The 2-bppt ligand chelates two four-coordinated AgI atoms through its two bipyridine-like arms. The O atoms of the perchlorate anion are disordered each over two positions of equal occupancy. Adjacent complex molecules are linked by π–π interactions between the pyridine and pyrimidine rings [centroid–centroid distance = 3.663 (8 Å].

  7. A solid-state electrochemiluminescence biosensing switch for detection of DNA hybridization based on ferrocene-labeled molecular beacon

    International Nuclear Information System (INIS)

    A solid-state electrochemiluminescence (ECL) biosensing switch incorporating quenching of ECL of ruthenium(II) tris-(bipyridine) (Ru(bpy)32+) by ferrocene (Fc) has been successfully developed for DNA hybridization detection. The important issue for this biosensing system is based on the ferrocene-labeled molecular beacon (Fc-MB), i.e. using the special Fc-MB to react with the target DNA and then change its structure, resulting in an ECL intensity change. Under the optimal conditions, the difference of ECL intensity before and after the hybridization reaction (ΔIECL) was linearly related to the concentration of the complementary sequence in the range of 10 fM-10 pM and the detection limit was down to 1.0 fM.

  8. Selective Alcohol Oxidation by a Copper TEMPO Catalyst: Mechanistic Insights by Simultaneously Coupled Operando EPR/UV-Vis/ATR-IR Spectroscopy.

    Science.gov (United States)

    Rabeah, Jabor; Bentrup, Ursula; Stößer, Reinhard; Brückner, Angelika

    2015-09-28

    The first coupled operando EPR/UV-Vis/ATR-IR spectroscopy setup for mechanistic studies of gas-liquid phase reactions is presented and exemplarily applied to the well-known copper/TEMPO-catalyzed (TEMPO=(2,2,6,6-tetramethylpiperidin-1-yl)oxyl) oxidation of benzyl alcohol. In contrast to previous proposals, no direct redox reaction between TEMPO and Cu(I) /Cu(II) has been detected. Instead, the role of TEMPO is postulated to be the stabilization of a (bpy)(NMI)Cu(II) -O2 (⋅-) -TEMPO (bpy=2,2'-bipyridine, NMI=N-methylimidazole) intermediate formed by electron transfer from Cu(I) to molecular O2 . PMID:26174141

  9. The synthesis and unexpected solution chemistry of thermochromic carborane-containing osmium half-sandwich complexes.

    Science.gov (United States)

    Pitto-Barry, Anaïs; South, Amy; Rodger, Alison; Barry, Nicolas P E

    2016-01-28

    The functionalisation of the 16-electron complex [Os(η(6)-p-cymene)(1,2-dicarba-closo-dodecarborane-1,2-dithiolato)] (1) with a series of Lewis bases to give the 18-electron complexes of general formula [Os(η(6)-p-cymene)(1,2-dicarba-closo-dodecarborane-1,2-dithiolato)(L)] (L = pyridine (2), 4-dimethylaminopyridine (3), 4-cyanopyridine (4), 4-methoxypyridine (5), pyrazine (6), pyridazine (7), 4,4'-bipyridine (8) and triphenylphosphine (9)) is reported. All 18-electron complexes are in equilibrium in solution with the 16-electron precursor, and thermochromic properties are observed in some cases (2, 3, 5, 8, and 9). The binding constants and Gibbs free energies of the equilibria are determined using UV-visible titrations and their stabilities investigated. Synthetic routes for forcing the formation of the 18-electron species are proposed, and analytical methods to characterise the equilibria are described. PMID:26700880

  10. Mixed-ligand complexes of ruthenium(II) incorporating a diazo ligand: Synthesis, characterization and DNA binding

    Indian Academy of Sciences (India)

    Megha S Deshpande; Avinash S Kumbhar

    2005-03-01

    Mixed-ligand complexes of the type [Ru(N-N)2(dzdf)]Cl2, where N-N is 2,2'-bipyridine (bpy), 1,10-phenanthroline (phen) and 9-diazo-4,5-diazafluorene (dzdf), have been synthesized and characterized by elemental analysis, UV-Vis, IR and NMR spectroscopy. Binding of these complexes with calf thymus DNA (CT-DNA) has been investigated by absorption spectroscopy, steady-state emission spectroscopy and viscosity measurements. The experimental results indicate that the size and shape of the intercalating ligands have marked effect on the binding affinity of the complexes to CT-DNA. The complex [Ru(phen)2(dzdf)]Cl2 binds with CT-DNA through an intercalative binding mode, while the complex [Ru(bpy)2(dzdf)]Cl2 binds electrostatically.

  11. Synthesis, DNA-binding and photocleavage studies of Ru(II) complexes of phenyl-(4,5,9,14-tetraaza-benzo[]triphenylen-1,1-)-methanone

    Indian Academy of Sciences (India)

    Li-Feng Tan; Xue-Jiao Chen; Jian-Liang Shen; Xi-Ling Liang

    2009-07-01

    A novel polypyridyl ligand phenyl-(4,5,9,14-tetraaza-benzo[]triphenylen-1,1-)-methanone (PTBM) and its complexes [Ru(phen)2(PTBM)]2+ (1) (phen = 1,10-phenanthroline) and [Ru(bpy)2 (PTBM)]2+ (2) (bpy = 2,2'-bipyridine) have been synthesized and characterized by elemental analysis, mass spectroscopy, and 1H NMR. The DNA-binding properties of the two complexes were investigated by spectroscopic and viscosity measurements. The results indicate that both complexes bind to DNA via an intercalative mode and the DNA-binding affinity of complex 1 is greater than that of complex 2. When irradiated at 365 nm, complex 1 was found to be a more-effective DNA-cleaving agent than complex 2.

  12. Ruthenium-Immobilized Periodic Mesoporous Organosilica: Synthesis, Characterization, and Catalytic Application for Selective Oxidation of Alkanes.

    Science.gov (United States)

    Ishito, Nobuhiro; Kobayashi, Hirokazu; Nakajima, Kiyotaka; Maegawa, Yoshifumi; Inagaki, Shinji; Hara, Kenji; Fukuoka, Atsushi

    2015-10-26

    Periodic mesoporous organosilica (PMO) is a unique material that has a crystal-like wall structure with coordination sites for metal complexes. A Ru complex, [RuCl2 (CO)3 ]2 , is successfully immobilized onto 2,2'-bipyridine (BPy) units of PMO to form a single-site catalyst, which has been confirmed by various physicochemical analyses. Using NaClO as an oxidant, the Ru-immobilized PMO oxidizes the tertiary C-H bonds of adamantane to the corresponding alcohols at 57 times faster than the secondary C-H bonds, thereby exhibiting remarkably high regioselectivity. Moreover, the catalyst converts cis-decalin to cis-9-decalol in a 63 % yield with complete retention of the substrate stereochemistry. The Ru catalyst can be separated by simple filtration and reused without loss of the original activity and selectivity for the oxidation reactions. PMID:26330333

  13. Tracking excited-state charge and spin dynamics in iron coordination complexes

    DEFF Research Database (Denmark)

    Zhang, Wenkai; Alonso-Mori, Roberto; Bergmann, Uwe;

    2014-01-01

    states and possible transitions result in phenomena too complex to unravel when faced with the indirect sensitivity of optical spectroscopy to spin dynamics(5) and the flux limitations of ultrafast X-ray sources(6,7). Such a situation exists for archetypal poly-pyridyl iron complexes, such as [Fe(2......Crucial to many light-driven processes in transition metal complexes is the absorption and dissipation of energy by 3d electrons(1-4). But a detailed understanding of such non-equilibrium excited-state dynamics and their interplay with structural changes is challenging: a multitude of excited......,2'-bipyridine)(3)](2+), where the excited-state charge and spin dynamics involved in the transition from a low-to a high-spin state (spin crossover) have long been a source of interest and controversy(6-15). Here we demonstrate that femtosecond resolution X-ray fluorescence spectroscopy, with its sensitivity to...

  14. Molecular and electronic structure of osmium complexes confined to Au(111) surfaces using a self-assembled molecular bridge

    Science.gov (United States)

    de la Llave, Ezequiel; Herrera, Santiago E.; Adam, Catherine; Méndez De Leo, Lucila P.; Calvo, Ernesto J.; Williams, Federico J.

    2015-11-01

    The molecular and electronic structure of Os(II) complexes covalently bonded to self-assembled monolayers (SAMs) on Au(111) surfaces was studied by means of polarization modulation infrared reflection absorption spectroscopy, photoelectron spectroscopies, scanning tunneling microscopy, scanning tunneling spectroscopy, and density functional theory calculations. Attachment of the Os complex to the SAM proceeds via an amide covalent bond with the SAM alkyl chain 40° tilted with respect to the surface normal and a total thickness of 26 Å. The highest occupied molecular orbital of the Os complex is mainly based on the Os(II) center located 2.2 eV below the Fermi edge and the LUMO molecular orbital is mainly based on the bipyridine ligands located 1.5 eV above the Fermi edge.

  15. Molecular and electronic structure of osmium complexes confined to Au(111) surfaces using a self-assembled molecular bridge

    International Nuclear Information System (INIS)

    The molecular and electronic structure of Os(II) complexes covalently bonded to self-assembled monolayers (SAMs) on Au(111) surfaces was studied by means of polarization modulation infrared reflection absorption spectroscopy, photoelectron spectroscopies, scanning tunneling microscopy, scanning tunneling spectroscopy, and density functional theory calculations. Attachment of the Os complex to the SAM proceeds via an amide covalent bond with the SAM alkyl chain 40° tilted with respect to the surface normal and a total thickness of 26 Å. The highest occupied molecular orbital of the Os complex is mainly based on the Os(II) center located 2.2 eV below the Fermi edge and the LUMO molecular orbital is mainly based on the bipyridine ligands located 1.5 eV above the Fermi edge

  16. SYNTHESIS AND CHARACTERIZATION OF STRUCTURALLY WELL-DEFINED POLYMER-INORGANIC HYBRID NANOPARTICLES VIA ATRP

    Institute of Scientific and Technical Information of China (English)

    Jie Bai; Jie-bin Pang; Kun-yuan Qiu; Yen Wei

    2002-01-01

    Atom transfer radical polymerization (ATRP) using cuprous chloride/2,2'-bipyridine (bipy) was applied to graft polymerization of styrene on the surface of silica nanoparticles to synthesize polymer-inorganic hybrid nanoparticles. 2-(4-Chloromethylphenyl) ethyltriethoxysilane (CTES) was immobilized on the surface of silica nanoparticles through condensation reaction of the silanol groups on silica with triethoxysilane group of CTES. Then ATRP of St was initiated by this surface-modified silica nanoparticles bearing benzyl chloride groups, and formed PSt graft chains on the surface of silica nanoparticles. The thickness of the graft chains increased with reaction time. End group analysis confirmed the occurrence of ATRP. Thermal analysis indicated that thermal stabilization of these resulting hybrid nanoparticles also increases with polymerization conversion. The results above show that this "grafting from" reaction could be used for the preparation of polymer-inorganic hybrid nanoparticles with controlled structure of the polymer's end groups.

  17. Halloysite Nanotubes as a New Adsorbent for Solid Phase Extraction and Spectrophotometric Determination of Iron in Water and Food Samples

    Science.gov (United States)

    Samadi, A.; Amjadi, M.

    2016-07-01

    Halloysite nanotubes (HNTs) have been introduced as a new solid phase extraction adsorbent for preconcentration of iron(II) as a complex with 2,2-bipyridine. The cationic complex is effectively adsorbed on the sorbent in the pH range of 3.5-6.0 and efficiently desorbed by trichloroacetic acid. The eluted complex has a strong absorption around 520 nm, which was used for determination of Fe(II). After optimizing extraction conditions, the linear range of the calibration graph was 5.0-500 μg/L with a detection limit of 1.3 μg/L. The proposed method was successfully applied for the determination of trace iron in various water and food samples, and the accuracy was assessed through the recovery experiments and analysis of a certified reference material (NIST 1643e).

  18. Palladium coupling catalysts for pharmaceutical applications.

    Science.gov (United States)

    Doucet, Henri; Hierso, Jean-Cyrille

    2007-11-01

    This review discusses recent advances made in the area of palladium-catalyzed coupling reactions and describes a selection of the catalytic systems that are useful in the preparation of valuable compounds for the pharmaceutical industry. Most of these types of syntheses have used either simple palladium salts or palladium precursors associated with electron-rich mono- or bidentate phosphine ligands as catalysts. For some reactions, ligands such as triphenyl phosphine, 1,1'-bis(diphenylphosphino)ferrocene, a carbene or a bipyridine have also been employed. Several new procedures for the Suzuki cross-coupling reaction, the activation of aryl chlorides, the functionalization of aromatics and the synthesis of heteroaromatics are discussed. The C-H activation/ functionalization reactions of aryl and heteroaryl derivatives have emerged as powerful tools for the preparation of biaryl compounds, and the recent procedures and catalysts employed in this promising field are also highlighted herein. PMID:17987520

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

    Directory of Open Access Journals (Sweden)

    Hiroshi Kajiro

    2010-09-01

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

  20. Septipyridines as conformationally controlled substitutes for inaccessible bis(terpyridine-derived oligopyridines in two-dimensional self-assembly

    Directory of Open Access Journals (Sweden)

    Daniel Caterbow

    2011-07-01

    Full Text Available The position of the peripheral nitrogen atoms in bis(terpyridine-derived oligopyridines (BTPs has a strong impact on their self-assembly behavior at the liquid/HOPG (highly oriented pyrolytic graphite interface. The intermolecular hydrogen bonding interactions in these peripheral pyridine units show specific 2D structures for each BTP isomer. From nine possible constitutional isomers only four have been described in the literature. The synthesis and self-assembling behavior of an additional isomer is presented here, but the remaining four members of the series are synthetically inaccessible. The self-assembling properties of three of the missing four BTP isomers can be mimicked by making use of the energetically preferred N–C–C–N transoid conformation between 2,2'-bipyridine subunits in a new class of so-called septipyridines. The structures are investigated by scanning tunneling microscopy (STM and a combination of force-field and first-principles electronic structure calculations.

  1. Anion Transport with Chalcogen Bonds.

    Science.gov (United States)

    Benz, Sebastian; Macchione, Mariano; Verolet, Quentin; Mareda, Jiri; Sakai, Naomi; Matile, Stefan

    2016-07-27

    In this report, we introduce synthetic anion transporters that operate with chalcogen bonds. Electron-deficient dithieno[3,2-b;2',3'-d]thiophenes (DTTs) are identified as ideal to bind anions in the focal point of the σ holes on the cofacial endocyclic sulfur atoms. Anion binding in solution and anion transport across lipid bilayers are found to increase with the depth of the σ holes of the DTT anionophores. These results introduce DTTs and related architectures as a privileged motif to engineer chalcogen bonds into functional systems, complementary in scope to classics such as 2,2'-bipyrroles or 2,2'-bipyridines that operate with hydrogen bonds and lone pairs, respectively. PMID:27433964

  2. SYNTHESIS, CRYSTAL STRUCTURE AND LUMINESCENT PROPERTY OF A DINUCLEAR Tb(II COMPLEX WITH HOMOPHTHALIC ACID AND 2,2’-BIPYRIDYL

    Directory of Open Access Journals (Sweden)

    LI-HUA WANG

    2015-07-01

    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.

  3. Assembly of a Cyclic Dimer Silver(I) Complex Encapsulating Two BF4 - Ions

    International Nuclear Information System (INIS)

    Unusual twenty-membered cyclic dimer encapsulating two BF4- anions was obtained by the self-assembly of the tridentate N2S donor ligand and silver ion. We are currently investigating the subtle factors influencing the formation of discrete or continuous complexes using dipicolyl sulfide derivatives including. It is a challenging work to capture ionic species or small molecules as guests. Thus, the construction of self-assembled cyclic oligomer complexes composed of metal centres connected by acyclic organic ligands has been a subject of great interest together with the inclusion phenomena of macrocyclic ligands in the supramolecular chemistry. The majority of the organic-inorgaic hybrid macrocyclic structures reported so far have been based on bis-monodentate ligands such as 4,4'-bipyridine and its derivatives interconnected by rigid or flexible spacers. The same type of ligands has been also used for the formation of coordination network

  4. Synthesis and characterization of triblock copolymer by combining enzymatic condensation polymerization and ATRP

    Institute of Scientific and Technical Information of China (English)

    LI Dongshuang; SHA Ke; LI Yapeng; WANG Shuwei; WANG Jingyuan

    2006-01-01

    The polyester poly(1,10-decanediol /1,10-sebacate) (PSD) was synthesized by means of Novozyme 435 catalyzed condensation polymerization of 1,10-decanediol and 1,10-sebacic acid. Both hydroxyl chain ends of the resulting PSD were modified by esterification with α-bromopropionyl bromide to obtain difunctional macroinitiator, which was subsequently used in the ATRP of St using CuCl/2, 2′-bipyridine (bpy) as the catalyst system to afford the triblock copolymer, polystyrene-block-poly(1,10-decanediol/1,10-sebacate)-block-polystyrene (PS t-b-PSDb-PSt). Molecular weight distribution and structure of the resulting triblock copolymer was confirmed by Waters 410 Gel permeation chromatography (GPC)and measurements of nuclear magnetic resonance (NMR) analysis.

  5. Molecular orientation of hydrogen-bonded liquid crystal (6BA)2-(BPy)x as Studied by 2H NMR

    International Nuclear Information System (INIS)

    The thermal properties of hydrogen-bonded liquid crystal (6BA)2-(BPy)x (6BA: 4-n-hexylbenzoicacid, BPy: 4,4’-bipyridine) were investigated by DSC. Two liquid crystal phases (LCI, LCII) were found for (6BA)2-(BPy)0.5. In LCII, the distribution of the orientation of molecules was larger than in LCI. The order parameter S of molecular orientation in the liquid crystal phase was estimated from a 2H NMR spectrum. S decreased rapidly around the LCI-LCII phase transition. The increase in orientational fluctuation of the 6BA dimer with an open dimer structure is predicted to cause the rapid decrease of S

  6. Fast photo-switchable surfaces for boiling heat transfer applications

    Energy Technology Data Exchange (ETDEWEB)

    Hunter, C. N.; Glavin, N. R.; Voevodin, A. A. [Air Force Research Laboratory, Materials and Manufacturing Directorate, 2941 Hobson Way, Wright-Patterson Air Force Base, Ohio 45433 (United States); Turner, D. B.; Check, M. H. [Universal Technology Corporation, 1270 North Fairfield Road, Dayton, Ohio 45532 (United States); Jespersen, M. L.; Borton, P. T. [University of Dayton Research Institute, 300 College Park, Dayton, Ohio 45469 (United States)

    2012-11-05

    Several milligrams of the ruthenium-centered organometallic complex, ruthenium bis-4,4 Prime -di(thiomethyl)-2,2 Prime -bipyridine, mono-2 -(2-pyridyl)-1,3-oxathiane ([Ru{l_brace}(HS-CH{sub 2}){sub 2}-bpy{r_brace}{sub 2}{l_brace}pox{r_brace}](PF{sub 6}){sub 2}) were synthesized and used to produce a self assembled monolayer film on a gold substrate. X-ray photoelectron spectroscopy analysis of the film detected the presence of bound thiolate, which is an indication of a chemisorbed film. Water contact angle measurements were performed before and after 5 min of visible light irradiation using an ozone-free 1000 W Xe(Hg) arc source with a 425-680 nm long pass mirror. The contact angle changed from 52 Degree-Sign pre-irradiation (hydrophilic state) to 95 Degree-Sign post-irradiation (hydrophobic state).

  7. Heteroligand molecular "stirrups" using conformationally flexible ditopic pyridyl-pyrazolyl ligands.

    Science.gov (United States)

    Lu, Jinzhen; Turner, David R; Harding, Lindsay P; Batten, Stuart R

    2009-08-17

    Heteroligand molecular "stirrups" form by the self-assembly of flexible ditopic ligands in combination with 4,4'-bipyridine and [(dppp)Pd)](2+). Crystallographic analysis shows that the ligands, bis[3-(4-pyridyl)pyrazolyl]-m-xylene (mXy(4py3pz)) and bis[4-(4-pyridyl)pyrazolyl]-p-xylene (pXy(4py4pz)) form complexes of the type [{(dppp)Pd}(2)(4,4'-bipy)(L)].4OTf (1.4OTf and 2.4OTf, respectively) in the solid state, with remarkably similar structures considering the differences in substitution patterns between the two ligands. The self-assembly of both 1(4+) and 2(4+) is assisted by face-to-face pi interactions on the exterior of the macrocycle between the phenyl rings of the dppp ligands and the pyridyl groups of the ditopic ligands. PMID:19594137

  8. Is copper(I) really soft? Probing the hardness of Cu(I) with pyridinecarboxaldehyde ligands

    Indian Academy of Sciences (India)

    D Saravanabharathi; M Nethaji; A G Samuelson

    2002-08-01

    Cu(I) complexes of formula Cu(PPh3)2LClO4 [L = 2 or 3 pyridine carboxaldehyde] are synthesised and characterised to explore the coordination of an aldehyde, a hard and neutral oxygen donor to a soft Cu(I) centre. The structural and spectroscopic results illustrate that only in 2-pyridinecarboxaldehyde, the `C=O' group coordinates to soft Cu(I) centres due to a favourable chelate effect, while in 3-pyridinecarboxaldehyde, it remains uncoordinated. Upon chelation via N and O donors, 2-pyridinecarboxaldehyde resembles bipyridine or phenanthroline in terms of its bite angle and spectroscopic features. Such chelation can be easily challenged with coordinating anions like bromide, or more basic pyridines. A drastic change in the MLCT absorption signals the decomplexation of the `C=O’ group. The observed results point out that the Cu(I) centre can readily exchange the hard `O’ donor for softer ligands.

  9. Ultrasensitive gaseous NH3 sensor based on ionic liquid-mediated signal-on electrochemiluminescence.

    Science.gov (United States)

    Chen, Lichan; Huang, Danjun; Zhang, Yuanjin; Dong, Tongqing; Zhou, Chen; Ren, Shuyan; Chi, Yuwu; Chen, Guonan

    2012-08-01

    This work reports that ammonia (NH(3)) can be used as an efficient co-reactant for tris(2,2'-bipyridine)ruthenium(II) (Ru(bpy)(3)(2+)) electrochemiluminescence (ECL) in ionic liquids (ILs), on the basis of which a signal-on ECL sensor for directly detecting gaseous NH(3) has been developed. The NH(3) ECL sensor has a very high sensitivity, with a detection limit of 10 ppt NH(3) (at signal-to-noise ratio of 3) without any preconcentration. The high sensitivity is mainly due to the zero ECL background of Ru(bpy)(3)(2+) in the ILs, strong co-reactant ECL activity of NH(3), and high solubility of NH(3) in imidazolium-based ILs. Additionally, the ECL sensor shows an excellent selectivity against common interfering gases and a wide linear response range from 10 ppt to 10 ppm. PMID:22728516

  10. Highly stable gelatin layer-protected gold nanoparticles as surface-enhanced Raman scattering substrates.

    Science.gov (United States)

    Lee, Changwon; Zhang, Peng

    2014-06-01

    Amine and carboxylic groups rich gelatin was used as reducing and stabilizing agent to form highly stable gold nanoparticles for surface-enhanced Raman scattering (SERS) applications. The size of the particle was determined to be 13 nm by TEM with mono-dispersity. The size of the gold nanoparticles was little affected by the initial gelatin concentration. The gelatin-gold nanoparticles show strong SERS activity with Rhodamine 6G and Ruthenium bipyridine as reporter molecules. Both carboxylic acid groups and amine groups were identified by FT-IR to be present on the gelatin-gold nanoparticle surface, providing the possibility of further conjugation with other molecules. The gelatin-protected gold nanoparticles prepared by this simple, green, method displayed very good solubility and stability in many solvents, and good monodispersity, all desirable features as good SERS substrates. PMID:24738391

  11. The direct electrochemical synthesis of some thorium(IV) nitrate complexes

    International Nuclear Information System (INIS)

    The electrochemical oxidation of thorium in either nitric acid/tri-n-butyl phosphate (TBP) or dinitrogen tetroxide/ethyl acetate/acetonitrile media gives rise to non-aqueous solutions of thorium(IV) nitrate species. The only natural adduct which could be obtained from HNO3/TBP solution was Th(NO3)4.8dmso (dmso= dimethyl-sulphoxide). Salts of [Th(NO3)6]2- with Et4N+, [(bpyH)3NO3]2+, and [(phenH)3NO3]2+ (bpy = 2,2'-bipyridine; phen = 1,10-phenathroline) were also prepared by this route. Solutions in N2O4/EtOAc/CH3CN yield Th(NO3)4, and neutral adducts with dmso, bpy, phen, Ph3PO, and pyridine-N-oxide

  12. Probing the lowest coordination number of dianionic platinum-cyanide complexes in the gas phase: Dynamics of the charge dissociation process

    DEFF Research Database (Denmark)

    Bojesen, G; Hvelplund, P; Jørgensen, Thomas J. D.;

    2000-01-01

    Low-energy and high-energy collision induced dissociation techniques are used to study the dissociation behavior of the gaseous Pt(CN)(6)(2-) and Pt(CN)(4)(2-) dianion complexes in order to probe the smallest stable dianion complex. Loss of neutral molecules from Pt(CN)(6)(2-) occurs resulting in......(CN)(4)(2-), or that the dynamics of the dissociation process is slow. For comparison, the Ru(bipy)(3)(2+)*--> [Ru(bipy)(2)-H](+)+bipyH(+) reaction is associated with a kinetic-energy release of similar to0.3 eV (bipy=2,2(')-bipyridine). (C) 2000 American Institute of Physics. [S0021-9606(00)00240-3]....

  13. Study on DNA binding behavior and light switch effect of new coumarin-derived Ru(II) complexes

    Science.gov (United States)

    Liu, Xue-Wen; Shen, You-Ming; Li, Zhi-Xin; Zhong, Xiao; Chen, Yuan-Dao; Zhang, Song-Bai

    2015-10-01

    A new ligand mhcip (mhcip = 2-(4-methyl-7-hydroxyl-8-coumarinyl)imidazo[4,5-f]-[1,10]phenanthroline) and its ruthenium complexes, [Ru(L)2mhcip]2+ (L = bpy (2,2‧-bipyridine), phen (1,10-phenanthroline)), have been synthesized and characterized. The introduction of coumarin ring may play an important role in the strong fluorescence of the complexes. Intercalative binding mode between both complexes and CT-DNA was determined by UV-visible spectroscopy, fluorescence spectroscopy and viscosity measurements. The two complexes show efficient DNA photocleavage under irradiation at 365 nm. The cycling of light switch off and on has been achieved for both complexes through the introduction of Cu2+ and EDTA in the absence or presence of DNA.

  14. Characterization of screen printed carbon counter electrodes for Co(II)/(III) mediated photoelectrochemical cells

    Energy Technology Data Exchange (ETDEWEB)

    Ghamouss, Fouad [CEISAM, Universite de Nantes, CNRS, 2 rue de la Houssiniere, B.P. 92208, 44322, Nantes cedex 3 (France); Pitson, Robbin [Gwent Electronics Materials Ltd, Monmouth House, Mamhilad Park, Pontypool, NP4 0HZ (United Kingdom); Odobel, Fabrice [CEISAM, Universite de Nantes, CNRS, 2 rue de la Houssiniere, B.P. 92208, 44322, Nantes cedex 3 (France); Boujtita, Mohammed, E-mail: mohammed.boujtita@univ-nantes.f [CEISAM, Universite de Nantes, CNRS, 2 rue de la Houssiniere, B.P. 92208, 44322, Nantes cedex 3 (France); Caramori, Stefano [Dipartmento di Chimica, Universita di Ferrara, Via L.Borsari, 46, 44100 Ferrara (Italy); Bignozzi, Carlo A., E-mail: g4s@unife.i [Dipartmento di Chimica, Universita di Ferrara, Via L.Borsari, 46, 44100 Ferrara (Italy)

    2010-09-01

    A screen printed carbon electrode associated with Tris(4,4'-di-tert-butyl-2,2'-bipyridine)Cobalt(II) as redox mediator was investigated as possible alternative to the volatile and corrosive iodide/triodide system in dye sensitized solar cells (DSSCs). We report here a first study on the screen printing technology for the manufacturing of an advanced and stable carbon cathode for dye sensitized solar cell. The electrode surface was characterized by scanning electron microscopy (SEM) and X-ray photoelectron spectroscopy (XPS) while the electrochemical response towards the cobalt complex was evaluated by using cyclic voltammetry. Photocurrent-voltage characteristics of DSSCs based on the new cathode/Cobalt complex system were 30% lower than those recorded with Pt/iodide.

  15. Electroreduction of O{sub 2} at a mediated Melanocarpus albomyces laccase cathode in a physiological buffer

    Energy Technology Data Exchange (ETDEWEB)

    Kavanagh, Paul; Jenkins, Peter; Leech, Donal [Department of Chemistry, National University of Ireland, Galway (Ireland)

    2008-07-15

    We report on oxygen reduction in a physiological buffer solution (0.05 M phosphate buffer containing dissolved O{sub 2}, 0.1 M NaCl, pH 7.4, 37 C) by Melanocarpus albomyces laccase, co-immobilized with [Os(2,2'-bipyridine){sub 2}(polyvinylimidazole){sub 10}Cl]{sup +/2+} as a mediator, on glassy carbon electrodes. Such oxygen cathodes yielded current densities of 3.8 mA cm{sup -2} at 0.2 V vs. Ag/AgCl, the largest current density reported to date for a mediated laccase cathode in physiological buffer solutions, showing promise for development of biocatalytic fuel cell prototypes. (author)

  16. Synthesis of asymmetric supramolecular compounds using a Ni(0) catalysed homo-coupling approach.

    Science.gov (United States)

    Cassidy, Lynda; Horn, Sabine; Cleary, Laura; Halpin, Yvonne; Browne, Wesley R; Vos, Johannes G

    2009-05-28

    The synthesis and characterisation of a series of dinuclear ruthenium and osmium polypyridyl metal complexes based on the bridging ligands [5-(5'-bipyridin-2',2''-yl)-3-(pyridin-2-yl)]-1,2,4-triazole (Hpytr-bipy), 2,2'-bis(pyridin-2''yl)-5,5'-bis(pyridin-3''-yl) (bipy-bipy) and 5,5'-bis(pyridin-2''-yl)-3,3'-bis(1,2,4-triazole) (Hpytr-Hpytr) are reported. The dinuclear complexes have been synthesised via a Ni(0) catalysed cross-coupling reaction from brominated precursors. With this approach a mixture of three products is obtained, which are separated by chromatographic methods. The compounds obtained are characterised by elemental analysis, (1)H NMR, absorption and emission spectroscopy. The synthetic approach developed offers a new route to asymmetric multinuclear supramolecular structures that is complimentary to the complexes as ligands/complexes as metal approaches. PMID:19440590

  17. Sheet-like of MoV-SmIII assembly containing [MoV(CN)8]3- and Sm3+ ions as building blocks

    Indian Academy of Sciences (India)

    Shu-Lin Ma; Shi Ren; Yue Ma; Dai-Zheng Liao

    2009-07-01

    The reaction of [Mo(CN)8]3- with Sm3+ and 2,2'-bipyridine (bpy) lead to a sheet-like bimetallic complex, {Sm(H2O)9[Sm2(bpy)2(OH)2.75(NO3)0.25][Mo(CN)8]2} (1) in EtOH/H2O mixture solvent. The complex 1 crystallizes in monoclinic, space group 2/. The structural investigation denotes that the layers interaction with each other by - stacks and hydrogen bonds result in a 3D network, containing Sm(H2O)$^{3+}_{9}$ as guest molecules in the holes. The magnetic behaviour of the complex 1 has been studied.

  18. Self-assembly of a Co(II) dimer through H-bonding of water molecules to a 3D open-framework structure

    Indian Academy of Sciences (India)

    Sujit K Ghosh; Parimal K Bharadwaj

    2005-01-01

    Reaction of pyridine-2,4,6-tricarboxylic acid (ptcH3) with Co(NO3)2.6H2O in presence of 4,4'-bipyridine (4,4'-bpy) in water at room temperature results in the formation of {[Co2(ptcH)2(4,4'-bpy)(H2O)4].2H2O}, (1). The solid-state structure reveals that the compound is a dimeric Co(II) complex assembled to a 3D architecture via an intricate intra- and inter-molecular hydrogen-bonding interactions involving water molecules and carboxylate oxygens of the ligand ptcH2-. Crystal data: monoclinic, space group 21/, = 11.441(5) Å, = 20.212(2) Å, = 7.020(5) Å, = 103.77(5)°, = 1576.7(1) Å3, = 2, 1 = 0.0363, 2 = 0.0856, = 1.000.

  19. Polyvinylpyrrolidone- (PVP-) coated silver aggregates for high performance surface-enhanced Raman scattering in living cells

    International Nuclear Information System (INIS)

    A biocompatible and stable surface-enhanced Raman scattering (SERS) probe has been successfully synthesized through a simple route with silver aggregates. Polyvinylpyrrolidone (PVP), a biocompatible polymer, was utilized to control the aggregation process and improve the chemical stability of the aggregates. Extinction spectroscopy and TEM results show the aggregation degree and core-shell structure of the probe. It is found that when we employ 4-mercaptobenzoic acid (4MBA), crystal violet (CV), Rhodamine 6G (R6G) or 4,4'-bipyridine molecules as Raman reporters, the SERS signal from the proposed probe can remain at a high level under aggressive chemical environments, even after being incorporated into living cells. In comparison with the traditional probes without the PVP shell, the new ones exhibit strong surface-enhanced effects and low toxicity towards living cells. We demonstrate that the PVP-coated silver aggregates are highly SERS effective, for which the fabrication protocol is advantageous in its simplicity and reproducibility.

  20. Femtosecond X-ray Absorption Spectroscopy at a Hard X-ray Free Electron Laser

    DEFF Research Database (Denmark)

    Lemke, Henrik T.; Bressler, Christian; Chen, Lin X.;

    2013-01-01

    X-ray free electron lasers (XFELs) deliver short (<100 fs) and intense (similar to 10(12) photons) pulses of hard X-rays, making them excellent sources for time-resolved studies. Here we show that, despite the inherent instabilities of current (SASE based) XFELs, they can be used for measuring high......-quality X-ray absorption data and we report femtosecond time-resolved X-ray absorption near-edge spectroscopy (XANES) measurements of a spin-crossover system, iron(II) tris(2,2'-bipyridine) in water. The data indicate that the low-spin to high-spin transition can be modeled by single-exponential kinetics...