Sample records for bipyridines

  1. Forces and conductances in a single-molecule bipyridine junction

    DEFF Research Database (Denmark)

    Stadler, Robert; Thygesen, Kristian Sommer; Jacobsen, Karsten Wedel


    Inspired by recent measurements of forces and conductances of bipyridine nanojunctions, we have performed density functional theory calculations of structure and electron transport in a bipyridine molecule attached between gold electrodes for seven different contact geometries. The calculations...

  2. Synthesis and complexation characteristics of phenanthroline and bipyridine diols

    NARCIS (Netherlands)

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


    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. Synthesis of New Chiral Bis(BINOL) Substituted 2,2'-Bipyridine Ligands

    Institute of Scientific and Technical Information of China (English)

    BAI,Xiao-Li; GAO,Lian-Xun


    @@ Chiral 2,2'-bipyridines have been reported to be highly efficient catalysts and useful building blocks of supramolecular.[1,2] Chirality of bipyridines was introduced by chiral substituents. Because 1,1'-binaphthyl (BINOL) and its derivatives belong to the most important components of asymmetric catalysts, we would like to synthesize 5,5'-and 6,6'-positions substituted chiral bipyridine-type ligands, the chiral moieties of ligands originate from enationpure 1, 1'-binapthyl units.

  4. Different Photophysical Properties of Aryl-bipyridine Linked Pyrene and Anthracene

    Institute of Scientific and Technical Information of China (English)

    熊飞; 王双青; 何黎明; 李沙瑜; 甘泉; 张国齐; 李嫣; 杨国强


    6-Phenyl-2,2'-bipyridine linked pyrene and anthracene were synthesized and their photophysical properties were measured in different solvents with different polarity. 4-Pyren-1""-yl-6-phenyl-2,2'-bipyridine (Ppbpy) showed significant solvent-dependent properities while 4-anthracen-yl-9""-yl-6-phenyl-2,2'-bipyridine (Apbpy) displayed solvent-independence, although they had similar molecular structure. Because of different twist angle between thyarene and aryl-bipyridine, Ppbpy displayed intermixing behaviors of local excited state (1La and 1Lb) and intramolecular charge transfer (ICT), but Apbpy only showed the properties of local excited state 1La.

  5. 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:; Nguyen Bich, N.; Nguyen, H. [Hanoi National University of Education, Chemistry Department (Viet Nam); Van Meervelt, L., E-mail: [KU Leuven, Chemistry Department (Belgium)


    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.

  6. 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


    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.

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

    CERN Document Server

    Chelibanov, Vladimir P; Polubotko, Aleksey M


    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...

  8. The effect of peripheral bipyridine ligands on the photocatalytic hydrogen production activity of Ru/Pd catalysts

    NARCIS (Netherlands)

    Bindra, Gurmeet Singh; Schulz, Martin; Paul, Avishek; Soman, Suraj; Groarke, Robert; Inglis, Jane; Pryce, Mary T.; Browne, Wesley R.; Rau, Sven; Maclean, Brian J.; Vos, Johannes G.


    A pyrazine bridged ruthenium/palladium bimetallic photocatalyst with peripheral 4,4'-dicarboxyethyl-2,2'-bipyridine ligands, EtOOC-RuPd, is reported, together with its 2,2'-bipyridine analogue. Upon irradiation with visible light, EtOOC-RuPd catalyses the production of hydrogen gas whereas the compl

  9. Diethyl 2,2′-bipyridine-4,4′-dicarboxylate


    D. Paul Rillema; Curtis Moore; Venugopal KomReddy


    The title bipyridine derivative, C16H16N2O4, crystallized with two half molecules in the asymmetric unit. The whole molecules (A and B) are generated by inversion symmetry with the mid-points of the bridging C—C bonds of the bipyridine units being located on crystallographic inversion centers. In the crystal, molecules are linked by C—H...O hydrogen bonds, forming sheets parallel to (120). The sheets are linked by C—H...N hydrogen bonds, forming a three-dimensional framework.

  10. Diethyl 2,2′-bipyridine-4,4′-dicarboxylate

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    D. Paul Rillema


    Full Text Available The title bipyridine derivative, C16H16N2O4, crystallized with two half molecules in the asymmetric unit. The whole molecules (A and B are generated by inversion symmetry with the mid-points of the bridging C—C bonds of the bipyridine units being located on crystallographic inversion centers. In the crystal, molecules are linked by C—H...O hydrogen bonds, forming sheets parallel to (120. The sheets are linked by C—H...N hydrogen bonds, forming a three-dimensional framework.

  11. A heterogeneous-catalyst-based, microwave-assisted protocol for the synthesis of 2,2'-bipyridines. (United States)

    Moore, Lucas R; Vicic, David A


    A new method of preparing 2,2'-bipyridines with short reaction times by using microwave assistance and heterogeneous catalysts has been developed. With a Negishi-like protocol, it was found that Ni/Al(2)O(3)-SiO(2) afforded 2,2'-bipyridine products in up to 86% yield in 1 h. Palladium supported on alumina also provided yields of 2,2'-bipyridines comparable to those seen for homogeneous PEPPSI (1,3-diisopropylimidazol-2-ylidene)(3-chloropyridyl)palladium(II)dichloride) and tetrakis(triphenylphosphanyl)palladium complexes.

  12. Density Functional Theory Study of Hydrogen Bonds of Bipyridine with 1,3,5-Benzenetricarboxylic Acid

    Institute of Scientific and Technical Information of China (English)

    LI Quan; ZHAO Keqing


    The hydrogen-bonded dimer and trimer formed between 1,3,5-benzenetricarboxylic acid and bipyridine have been investigated using a density functional theory(DFT)method and 6-31++G** basis set.The interaction enerstretching modes in the dimer and trimer red-shifted relative to those of the 1,3,5-benzenetricarhoxylic acid monomer.The natural bond orbit analysis shows that the inter-molecular charge transfers are 0.60475e and 1.20225e for the dimer and trimer,respectively.Thermodynamic analysis indicates that the formation of trimer is an exothermic H-O intermolecular hydrogen bonds between bipyridine and 1,3,5-benzenetricarboxylic acid,which is in good agreement with the experimental results.

  13. Conformational control in a bipyridine linked π-conjugated oligomer: cation mediated helix unfolding and refolding. (United States)

    Divya, Kizhumuri P; Sreejith, Sivaramapanicker; Suresh, Cherumuttathu H; Ajayaghosh, Ayyappanpillai


    A chiral π-conjugated oligomer having alternate bipyridine and carbazole moieties connected through acetylinic bonds undergoes helical folding in chloroform-acetonitrile (40/60, v/v) as evident by fluorescence and circular dichroism changes. In the presence of transition metal cations such as Zn(2+) defolding of the helical conformation occurs. Upon decomplexation of the cation with EDTA, the helical conformation is regained.

  14. Pyridine ring opening at room temperature at a rhenium tricarbonyl bipyridine complex. (United States)

    Huertos, Miguel A; Pérez, Julio; Riera, Lucía


    Pyridine ring opening occurs in the reaction of [Re(CO)3(MeIm)(bipy)]OTf with KN(SiMe3)2 followed by double methylation with methyl trifluoromethanesulfonate. Analogues of the neutral product of the initial deprotonation and of the product of the first methylation were isolated by using mesitylimidazole (MesIm) in place of methylimidazole (MeIm) and/or 1,10-phenanthroline (phen) instead of 2,2'-bipyridine (bipy).

  15. Dichlorido(6-methyl-2,2′-bipyridine-κ2N,N′mercury(II

    Directory of Open Access Journals (Sweden)

    Amin Ebadi


    Full Text Available In the molecule of the title compound, [HgCl2(C11H10N2], the HgII atom is four-coordinated in a distorted tetrahedral configuration by two N atoms from a 6-methyl-2,2′-bipyridine ligand and two Cl atoms. There is a π–π contact between the pyridine rings [centroid–centroid distance = 3.9758 (5 Å].

  16. Rhenium and manganese bipyridine tricarbonyl catalysts for the electrochemical reduction of carbon dioxide (United States)

    Sampson, Matthew Dean

    Electrocatalytic reduction of carbon dioxide (CO2) is a profoundly challenging problem that is of interest, not only as a means of counteracting unsustainable emissions of CO2, but also as a method for the development of renewable fuels. Rhenium and manganese bipyridine tricarbonyl complexes are among the most active and robust catalysts for proton-coupled CO 2 reduction to carbon monoxide (CO). X- ray Absorption Spectroscopy studies are reported to reveal the electronic ground state of the Re catalysts, which help explain origins for high selectivity for CO2 reduction over proton reduction. Stopped-flow mixing in tandem with rapid-scan IR spectroscopy is utilized to probe the direct reaction of the Re catalysts with CO 2, observing, for the first time, the binding of CO2 to these catalysts. Manganese bipyridine catalysts are desirable, in comparison with their Re analogs, due to the earth-abundance of Mn and the ability for these catalysts to operate at lower overpotentials. One distinct difference between these Mn catalysts and their Re counterparts is a high tendency for dimerization after one-electron reduction, which contributes to the potential necessary to access their active state and to limiting their catalytic activity. Synthetic modification of the bipyridine ligand (by adding bulky mesityl groups) is used to completely eliminate dimerization for these Mn complexes, allowing the active catalyst to be generated at a 300 mV more positive potential than in typically Mn bipyridine complexes. CO2 reactivities in the presence of weak Bronsted acids, strong Bronsted acids, and Lewis acids have been explored in order to encourage this bulky Mn catalyst to reduce CO2 at low overpotentials. Mechanistic tools, including IR-spectroelectrochemistry, are described to gain insight into these unique catalytic processes. In order to further enhance stability and facilitate product separation, the use of metal-organic frameworks (MOFs) is explored as a means of anchoring

  17. Synthesis, structures, and dearomatization by deprotonation of iron complexes featuring bipyridine-based PNN pincer ligands. (United States)

    Zell, Thomas; Langer, Robert; Iron, Mark A; Konstantinovski, Leonid; Shimon, Linda J W; Diskin-Posner, Yael; Leitus, Gregory; Balaraman, Ekambaram; Ben-David, Yehoshoa; Milstein, David


    The synthesis and characterization of new iron pincer complexes bearing bipyridine-based PNN ligands is reported. Three phosphine-substituted pincer ligands, namely, the known (t)Bu-PNN (6-((di-tert-butylphosphino)methyl)-2,2'-bipyridine) and the two new (i)Pr-PNN (6-((di-iso-propylphosphino)methyl)-2,2'-bipyridine) and Ph-PNN (6-((diphenylphosphino)methyl)-2,2'-bipyridine) ligands were synthesized and studied in ligation reactions with iron(II) chloride and bromide. These reactions lead to the formation of two types of complexes: mono-chelated neutral complexes of the type [(R-PNN)Fe(X)2] and bis-chelated dicationic complexes of the type [(R-PNN)2Fe](2+). The complexes [(R-PNN)Fe(X)2] (1: R = (t)Bu, X = Cl, 2: R = (t)Bu, X = Br, 3: R = (i)Pr, X = Cl, and 4: R = (i)Pr, X = Br) are readily prepared from reactions of FeX2 with the free R-PNN ligand in a 1:1 ratio. Magnetic susceptibility measurements show that these complexes have a high-spin ground state (S = 2) at room temperature. Employing a 2-fold or higher excess of (i)Pr-PNN, diamagnetic hexacoordinated dicationic complexes of the type [((i)Pr-PNN)2Fe](X)2 (5: X = Cl, and 6: X = Br) are formed. The reactions of Ph-PNN with FeX2 in a 1:1 ratio lead to similar complexes of the type [(Ph-PNN)2Fe](FeX4) (7: X = Cl, and 8: X = Br). Single crystal X-ray studies of 1, 2, 4, 6, and 8 do not indicate electron transfer from the Fe(II) centers to the neutral bipyridine unit based on the determined bond lengths. Density functional theory (DFT) calculations were performed to compare the relative energies of the mono- and bis-chelated complexes. The doubly deprotonated complexes [(R-PNN*)2Fe] (9: R = (i)Pr, and 10: R = Ph) were synthesized by reactions of the dicationic complexes 6 and 8 with KO(t)Bu. The dearomatized nature of the central pyridine of the pincer ligand was established by X-ray diffraction analysis of single crystals of 10. Reactivity studies show that 9 and 10 have a slightly different behavior in

  18. Correlation between the Structure and Catalytic Activity of [Cp*Rh(Substituted Bipyridine)] Complexes for NADH Regeneration. (United States)

    Ganesan, Vinothkumar; Sivanesan, Dharmalingam; Yoon, Sungho


    A series of water-soluble half-sandwich [Cp*Rh(III)(N^N)Cl](+) (Cp* = pentamethylcyclopentadiene, N^N-substituted 2,2'-bipyridine) complexes containing electron-donating substituents around the 2,2'-bipyridyl ligand were synthesized and fully characterized for the regioselective reduction of nicotinamide coenzyme (NAD(+)). The influence of the positional effect of the substituents on the structural, electrochemical, and catalytic properties of the catalyst was systematically studied in detail. The catalytic efficiency of the substituted bipyridine Cp*Rh(III) complexes are inversely correlated with their redox potentials. The 5,5'-substituted bipyridine Cp*Rh(III) complex, which had the lowest reduction potential, most effectively regenerated NADH with a turnover frequency of 1100 h(-1). Detailed kinetic studies on the generation of intermediate(s) provide valuable mechanistic insight into this catalytic cycle and help to direct the future design strategy of corresponding catalysts.

  19. Synthesis of highly functionalized 2,2'-bipyridines by cyclocondensation of β-ketoenamides – scope and limitations (United States)

    Hommes, Paul


    Summary The scope of a flexible route to unsymmetrically functionalized bipyridines is described. Starting from 1,3-diketones 1a–e, the corresponding β-ketoenamines 2a–e were converted into different β-ketoenamides 3a–g by N-acylation with 2-pyridinecarboxylic acid derivatives. These β-ketoenamides were treated with a mixture of TMSOTf and Hünig’s base to promote the cyclocondensation to 4-hydroxypyridine derivatives. Their immediate O-nonaflation employing nonafluorobutanesulfonyl fluoride provided the expected 4-nonafloxy-substituted bipyridine derivatives 5a–g in moderate to good overall yields. The bipyridyl nonaflates are excellent precursors for palladium-catalyzed reactions as demonstrated by representative Suzuki and Sonogashira couplings. Thus, a library of specifically substituted bipyridine derivatives was generated, showing the versatility of the simple 1,3-diketone-based approach to this important class of ligands. PMID:27559368

  20. Synthesis of highly functionalized 2,2'-bipyridines by cyclocondensation of β-ketoenamides - scope and limitations. (United States)

    Hommes, Paul; Reissig, Hans-Ulrich


    The scope of a flexible route to unsymmetrically functionalized bipyridines is described. Starting from 1,3-diketones 1a-e, the corresponding β-ketoenamines 2a-e were converted into different β-ketoenamides 3a-g by N-acylation with 2-pyridinecarboxylic acid derivatives. These β-ketoenamides were treated with a mixture of TMSOTf and Hünig's base to promote the cyclocondensation to 4-hydroxypyridine derivatives. Their immediate O-nonaflation employing nonafluorobutanesulfonyl fluoride provided the expected 4-nonafloxy-substituted bipyridine derivatives 5a-g in moderate to good overall yields. The bipyridyl nonaflates are excellent precursors for palladium-catalyzed reactions as demonstrated by representative Suzuki and Sonogashira couplings. Thus, a library of specifically substituted bipyridine derivatives was generated, showing the versatility of the simple 1,3-diketone-based approach to this important class of ligands.

  1. Synthesis of highly functionalized 2,2'-bipyridines by cyclocondensation of β-ketoenamides – scope and limitations

    Directory of Open Access Journals (Sweden)

    Paul Hommes


    Full Text Available The scope of a flexible route to unsymmetrically functionalized bipyridines is described. Starting from 1,3-diketones 1a–e, the corresponding β-ketoenamines 2a–e were converted into different β-ketoenamides 3a–g by N-acylation with 2-pyridinecarboxylic acid derivatives. These β-ketoenamides were treated with a mixture of TMSOTf and Hünig’s base to promote the cyclocondensation to 4-hydroxypyridine derivatives. Their immediate O-nonaflation employing nonafluorobutanesulfonyl fluoride provided the expected 4-nonafloxy-substituted bipyridine derivatives 5a–g in moderate to good overall yields. The bipyridyl nonaflates are excellent precursors for palladium-catalyzed reactions as demonstrated by representative Suzuki and Sonogashira couplings. Thus, a library of specifically substituted bipyridine derivatives was generated, showing the versatility of the simple 1,3-diketone-based approach to this important class of ligands.

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

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    Vahid Amani


    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.

  3. Polymorphism of felodipine co-crystals with 4,4'-bipyridine

    DEFF Research Database (Denmark)

    Surov, Artem Olegovich; Solanko, Katarzyna A.; Bond, Andrew;


    The calcium-channel blocking agent felodipine (Fel) forms co-crystals with 4,4′-bipyridine (BP) with 1:1 and 2:1 molar ratios. The [Fel + BP] (1:1) co-crystal exists in two polymorphic forms. Differential scanning calorimetry and solution calorimetry show that form I of the [Fel + BP] (1:1) co......-crystal is the most thermodynamically stable phase. The difference in the crystal lattice energies between different polymorphs of the co-crystal is found to be comparable with that between the polymorphic forms of pure felodipine. The enthalpies of formation of the co-crystals are small, which indicates...

  4. catena-Poly[[diaqua-bis(diphenyl-acetato)-zinc(II)]-μ-4,4'-bipyridine]. (United States)

    Yu, Shan-Shan; Zhou, Hong; Xian, Hua; Tian, Zheng-Fang


    In the title compound, [Zn(C(14)H(11)O(2))(2)(C(10)H(8)N(2))(H(2)O)(2)](n), the Zn(II) 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 Zn(II) ions into a chain along the b-axis direction. In the crystal structure, these chains are linked by inter-molecular O-H⋯O hydrogen bonds to form a two-dimensional network parallel to the ab plane.

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

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    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.

  6. Synthesis and CD Spectra of Chiral Molybdenum-fullerenyl Complexes with Pineno-bipyridine Ligands

    Institute of Scientific and Technical Information of China (English)

    Hui ZHANG; Cai Fei ZHU; Li LI; Wei ZOU; Yong Qing HUANG; Jing Xing GAO


    The synthesis and characterization of two chiral fullerene complexes (+) CD430- [Mo(η2-C60)(CO)3(LRR)] 1 and (-)CD430-[Mo(η2-C60)(CO)3(LSS)] 2 were described. The CD spectra of 1 and 2 in the visible range show weak Cotton effects, which are approximately of mirror image, indicating that the appended pineno-groups with opposite chirality in bipyridines can perturb the fullerene chromophores through the molybdenum centers and lead to induced CD effects.

  7. The electronic spectrum of cryogenic ruthenium-tris-bipyridine dications in vacuo (United States)

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


    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.

  8. Activation of Aromatic C-C Bonds of 2,2'-Bipyridine Ligands. (United States)

    Fombona, Sergio; Espinal-Viguri, Maialen; Huertos, Miguel A; Díaz, Jesús; López, Ramón; Menéndez, M Isabel; Pérez, Julio; Riera, Lucía


    4,4'-Disubstituted-2,2'-bipyridine ligands coordinated to Mo(II) and Re(I) cationic fragments become dearomatized by an intramolecular nucleophilic attack from a deprotonated N-alkylimidazole ligand in cis disposition. The subsequent protonation of these neutral complexes takes place on a pyridine carbon atom rather than at nitrogen, weakening an aromatic C-C bond and affording a dihydropyridyl moiety. Computational calculations allowed for the rationalization of the formation of the experimentally obtained products over other plausible alternatives.

  9. 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


    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...... conductance than the Pt-BPD junction due to the smaller work function of Au as compared to Pt. On the other hand, coupling to the local d band is stronger in the case of Pt and this broadens the LUMO resonance. We find that these effects largely outbalance each other leading to conductances of 0.01G(0) and 0...

  10. 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


    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.

  11. Crystal Structure of Tris(2,2'-bipyridine)nickel (Ⅱ) Tetrachlorozincate

    Institute of Scientific and Technical Information of China (English)

    林善火; 王志奎; 张百合; 胡怀明; 黄锦顺


    A bimetallic complex Ni[C10H8N2]3[ZnCl4] has been synthesized and its crystal structure determined at room temperature. The complex crystallizes in the trigonal system, space group R3c, with a = 13.343(2), b = 13.343(2), c =58. 932(12) A, V= 9087(3) A 3, Z = 12, NiZnC30N6CI14H24, Mr=734.30, Dc=1.611 g/cm3, μ= 1. 799 mm-1, F(000)=4464. Least-squares refinement of the structure leads to the agreement factors R1=0. 0278 and wR2=0. 0741 for the observable reflections. The complex consists of discrete tris (2, 2'-bipyridine) nickel (Ⅱ)cation, [Ni-(bipy)3]2+, and tetrachlorozincate anion, [ZnCl4]2-. Each nickel (Ⅱ)atom is six coordinated in an octahedron with six nitrogen atoms of three 2,2'-bipyridine ligands. The mean Ni(Ⅱ)-N bond length is 2. 089(2) A. The zinc(Ⅱ) atom is coordinated with four chloride atoms in tetrahedral geometry. The mean Zn (Ⅱ)- Cl bond length is 2. 264(1) A.

  12. Crystal structure, physical, and photophysical properties of a ruthenium(II) bipyridine diazafluorenone complex

    Energy Technology Data Exchange (ETDEWEB)

    Wang, Y.; Jackman, D.C.; Rillema, D.P. [Univ. of North Carolina, Charlotte, NC (United States)] [and others


    The complex [Ru(bpy){sub 2}(dafo)](PF{sub 6}){sub 2}, where bpy is 2,2{prime}-bipyridine and dafo is diazafluorenone crystallizes in the space group P2{sub 1}/n with a = 9.5059(3){angstrom}, b = 14.002(2){angstrom} and c = 25.783(8){angstrom}. The coordination geometry of the Ru atom is that of a distorted octahedron with a RuN{sub 6} core. The two Ru-N bond distances to the dafo ligand are 2.13(1) and 2.15(1) {angstrom}; the four Ru-N bond distances to the bipyridine ligands are 2.03(1), 2.05(1), 2.06(1), and 2.07(1) {angstrom}. The three shortest Ru-N distances are trans to the three longest Ru-N distances. The complex is oxidized and reduced reversibly at 1.41 and -0.65 V vs. SSCE, respectively. It displays absorptions at 438 nm (1.6 x 10{sup 4}), 285 nm (6.2 x 10{sup 4}), and 240 nm (4.1 x 10{sup 4}) and a broad emission centered at 626 nm in water at room temperature. The emission lifetime is 420 ns and the emission quantum yield is 5.3 x 10{sup -4}.

  13. 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.


    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.

  14. 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.


    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.

  15. 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: [MacDiarmid Institute for Advanced Materials and Nanotechnology, Department of Chemistry, University of Canterbury, Private Bag 4800, Christchurch (New Zealand)


    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.

  16. 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


    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.

  17. Bipyridine, an iron chelator, does not lessen intracerebral iron-induced damage or improve outcome after intracerebral hemorrhagic stroke in rats. (United States)

    Caliaperumal, Jayalakshmi; Wowk, Shannon; Jones, Sarah; Ma, Yonglie; Colbourne, Frederick


    Iron chelators, such as the intracellular ferrous chelator 2,2'-bipyridine, are a potential means of ameliorating iron-induced injury after intracerebral hemorrhage (ICH). We evaluated bipyridine against the collagenase and whole-blood ICH models and a simplified model of iron-induced damage involving a striatal injection of FeCl2 in adult rats. First, we assessed whether bipyridine (25 mg/kg beginning 12 h post-ICH and every 12 h for 3 days) would attenuate non-heme iron levels in the brain and lessen behavioral impairments (neurological deficit scale, corner turn test, and horizontal ladder) 7 days after collagenase-induced ICH. Second, we evaluated bipyridine (20 mg/kg beginning 6 h post-ICH and then every 24 h) on edema 3 days after collagenase infusion. Body temperature was continually recorded in a subset of these rats beginning 24 h prior to ICH until euthanasia. Third, bipyridine was administered (as per experiment 2) after whole-blood infusion to examine tissue loss, neuronal degeneration, and behavioral impairments at 7 days post-stroke, as well as body temperature for 3 days post-stroke. Finally, we evaluated whether bipyridine (25 mg/kg given 2 h prior to surgery and then every 12 h for 3 days) lessens tissue loss, neuronal death, and behavioral deficits after striatal FeCl2 injection. Bipyridine caused a significant hypothermic effect (maximum drop to 34.6 °C for 2-5 h after each injection) in both ICH models; however, in all experiments bipyridine-treated rats were indistinguishable from vehicle controls on all other measures (e.g., tissue loss, behavioral impairments, etc.). These results do not support the use of bipyridine against ICH.

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

    Energy Technology Data Exchange (ETDEWEB)

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


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

  19. Ultrafast excited state dynamics of tris-(2,2'-bipyridine) Ruthenium (II)

    Energy Technology Data Exchange (ETDEWEB)

    Yeh, Alvin T.W. [Univ. of California, Berkeley, CA (United States)


    Time resolved anisotropy measurements and time dependent transient absorption measurements are used to study the evolution of the photoexcited Franck-Condon state to the formation of the long-lived triplet metal-to-ligand charge-transfer (3MLCT) state in tris-(2,2’-bipyridine) ruthenium. [Ru(bpy)3]2+ represents a large class of inorganic compounds with interesting and potentially applicable photophysical properties. These compounds have generated much interest in the inorganic chemistry community because their photophysical properties are easily manipulated by synthetic chemistry methods. However, little remains known about the processes which govern the evolution horn initial photoexcitation to the formation of the long-lived excited state.

  20. Synthesis, Characterization, Spectroscopic and Electrochemical Properties of New Mono-and Binuclear Copper(Ⅰ) Complexes with Substituted 2,2'-Bipyridine

    Institute of Scientific and Technical Information of China (English)

    CAO, Qian-Yong(曹迁永); GAN, Xin(甘欣); FU, Wen-Fu(傅文甫)


    The mono- and binuclear Cu(Ⅰ) complexes with substituted 2,2'-bipyridine and iodide ligands, [CuL2]BF4 (L=4-methoxycarbonyl-6-(4-methylphenyl)-2,2'-bipyridine (a), 6-(4-hydroxymethylphenyl)-2,2'-bipyridine (b) and 6-(4-methoxylphenyl)-2,2'-bipyridine (c)) and [Cu2(μ-I)2L2] were prepared, and the crystal structures of the complexes were obtained from signal-crystal X-ray diffractional analysis. The spectroscopic properties of the complexes in dichloromethane are dominated by low energy MLCT bands from 360 to 650 nm. The electrochemical studies of mononuclear complexes reveal that the complexes have stable copper(Ⅰ) state.

  1. 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


    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.

  2. Coordination polymers and metal-organic frameworks derived from 4,4'-dicarboxy-2,2'-bipyridine and 4,4',6,6'-tetracarboxy-2,2'-bipyridine ligands: a personal perspective. (United States)

    Kruger, Paul E


    Presented herein is a personal overview of some of the contributions we have made over recent years to coordination polymer chemistry employing 2,2'-bipyridine-polycarboxylic acid ligands in conjunction with first row transition, main group or lanthanide metal ions. Primarily the discussion is centred upon the two ligands with which we have enjoyed the most success: 4,4'-dicarboxy-2,2'-bipyridine (4,4'-H2dcbp) and 4,4',6,6'-tetracarboxy-2,2'-bipyridine (4,4',6,6'-H4tcbp). Initial discussion is focused upon the synthetic aspects of ligand formation and their structural characterisation and then moves on to the synthesis of metal complexes incorporating these ligands and the coordination polymers they form. Where possible the discussion is presented from a synthetic and structural perspective with highlight given to the pertinent properties of the coordination polymers formed e.g. thermal behaviour, magnetic, luminescent or small molecule sorption properties. We end the review with some conclusions and highlight some current work with a view to future research.

  3. Crystal Structure and Luminescence Property of Lanthanide Complexes with 2-Fluorobenzoic Acid and 2,2'-Bipyridine

    Institute of Scientific and Technical Information of China (English)

    Li Xia; Zhang Zhuoyong; Song Haibin


    The two compounds of [Ln(2-FBA)3·2,2'-bpy]2 (2-FBA=2-fluorobenzoato, 2,2'-bpy=2,2'-bipyridine, Ln=Eu(1), Dy(2)) were synthesized and their structures were determined by X-ray diffraction method. Crystallized complexes 1 and 2 are isomorphous, monoclinic system with P21/n space group. The two complexes are binuclear molecule with an inversion center. The two lanthanide ions are linked by four bridged 2-FBA ligands and each lanthanide ion is further bonded to one chelated bidentate 2-FBA ligand and one 2,2'-bipyridine molecule. The coordination number of metal ion is eight. The europium complex exhibits strong red fluorescence. 5D0→7Fj (j= 1~4) transition emission of Eu3+ ion was observed.

  4. Towards allosteric receptors – synthesis of β-cyclodextrin-functionalised 2,2’-bipyridines and their metal complexes

    Directory of Open Access Journals (Sweden)

    Christopher Kremer


    Full Text Available Herein, we present three new 2,2’-bipyridines that carry two β-cyclodextrin moieties in different substitution patterns. When coordinated by zinc(II or copper(I ions (or their complexes, these compounds undergo conformational changes and switch between “open” and “closed” forms and thereby bringing together or separating the cyclodextrin moieties from each other.

  5. Modulation of the conductance of a 2,2'-bipyridine-functionalized peptidic ion channel by Ni2+. (United States)

    Pilz, Claudia S; Steinem, Claudia


    An alpha-helical amphipathic peptide with the sequence H2N-(LSSLLSL)3-CONH2 was obtained by solid phase synthesis and a 2,2'-bipyridine was coupled to its N-terminus, which allows complexation of Ni2+. Complexation of the 2,2'-bipyridine residues was proven by UV/Vis spectroscopy. The peptide helices were inserted into lipid bilayers (nano black lipid membranes, nano-BLMs) that suspend the pores of porous alumina substrates with a pore diameter of 60 nm by applying a potential difference. From single channel recordings, we were able to distinguish four distinct conductance states, which we attribute to an increasing number of peptide helices participating in the conducting helix bundle. Addition of Ni2+ in micromolar concentrations altered the conductance behaviour of the formed ion channels in nano-BLMs considerably. The first two conductance states appear much more prominent demonstrating that the complexation of bipyridine by Ni2+ results in a considerable confinement of the observed multiple conductance states. However, the conductance levels were independent of the presence of Ni2+. Moreover, from a detailed analysis of the open lifetimes of the channels, we conclude that the complexation of Ni2+ diminishes the frequency of channel events with larger open times.

  6. A new ligand system based on a bipyridine-functionalized calix[4]arene backbone leading to mono- and bimetallic complexes. (United States)

    Dorta, Reto; Shimon, Linda J W; Rozenberg, Haim; Ben-David, Yehoshoa; Milstein, David


    The synthesis of a new ligand system for mono- and bimetallic complexes based on a calixarene is described. Ligand BBPC (3, bis(bipyridine)-calix[4]arene) is obtained in three steps in 40% overall yield by first brominating one of the methyl groups of the 4,4'-dimethyl-2,2'-bipyridine in two steps and subsequently reacting it with p-tert-butylcalix[4]arene under basic conditions. Reaction of BBPC (3) with 2 equiv of [Rh(NBD)(2)]BF(4) or [Rh(NBD)(CH(3)CN)(2)]BF(4) (NBD = norbornadiene) produces the bimetallic compound BBPC[Rh(NBD)BF(4)](2) (4). Treatment of the ligand with PdCl(2)(CH(3)CN)(2) leads to the isolation of the bimetallic complex BBPC[PdCl(2)](2) (5). When the nickel precursor NiBr(2)(DME) (DME = dimethoxyethane) is reacted with BBPC, the bimetallic complex BBPC[NiBr(2)](2) (6) is isolated which, upon crystallization from methanol, gives the mononuclear bis(bipyridine) complex BBPC[NiBr(OMe)] (7). Full characterization includes X-ray structural studies of complexes 4, 5, and 7. The bimetallic compounds 4 and 5 show metal to metal distances of 4.334 A (for 4) and 3.224 A (for 5). For all three complexes, unique molecular packing arrangements were found, based on hydrophobic/hydrophilic interactions.

  7. 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


    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.

  8. Molecular spectrum of lanthanide complexes with 2,3-dichlorobenzoic acid and 2,2-bipyridine. (United States)

    He, Shu-Mei; Sun, Shu-Jing; Zheng, Jun-Ru; Zhang, Jian-Jun


    With 2,3-dichlorobenzoic acid as the first ligands and 2,2'-bipyridine as the second ligands, the lanthanide complexes [Ln(2,3-DClBA)3bipy]2 [Ln=Nd(a), Sm(b), Eu(c), Tb(d), Dy(e), Ho(f)] have been synthesized. By using Infrared (IR) and Raman (R) spectra, the characteristics of the groups can be identified. The bands of lanthanide complexes have been analyzed and attributed, and clearly demonstrated with the use of the complementarity of IR and R. The experiment reveals that the bands of complexes are affected by lanthanide elements (Ln). The frequency of stretching vibration and breathing vibration of ring, together with the stretching vibration of the carbonyl group (νCO), tends to be rising as the atomic number of lanthanide increasing. Meanwhile, crystallography data demonstrate that the six carbonyl groups have different bond length and bond angle, which can lead to different vibration frequency. The second derivatives of IR show that there are multiple vibration frequencies existing in the symmetrical stretching vibration of the carbonyl group (νsCO). Therefore the second derivative of IR spectrum is a characteristic band of different coordination modes of carbonyl group.

  9. On the electronic structure of nitro-substituted bipyridines and their platinum complexes. (United States)

    Murray, Paul R; Crawford, Stephen; Dawson, Alice; Delf, Alexander; Findlay, Calum; Jack, Lorna; McInnes, Eric J L; Al-Musharafi, Salma; Nichol, Gary S; Oswald, Iain; Yellowlees, Lesley J


    We report the preparation and electrochemical studies of a systematic series of mono- and di-nitro-substituted 2,2'-bipyridine (bipy) compounds [x-NO(2)-bipy (x = 3,4) and x,x'-(NO(2))(2)-bipy (x,x' = 3, 4, 5)] and their complexes with platinum(II), [Pt(x-NO(2)-bipy)Cl(2)] and [Pt(x,x'-(NO(2))(2)-bipy)Cl(2)]. The effect of the number and substitution pattern of the nitro groups on the low-lying acceptor molecular orbitals (involved in charge transfer transitions) is probed by in situ UV/Vis/NIR and EPR spectroelectrochemical methods, supported by DFT calculations. The LUMOs of x-NO(2)-bipy (x = 3-5) are largely localised on the NO(2)-pyridyl moiety; this is also true of their {PtCl(2)} complexes but with a small but significant shift of electron density from the nitro groups. The LUMOs of x,x'-(NO(2))(2)-bipy with x = 3 and 5 are delocalised over both NO(2)-pyridyl rings, but for 4,4'-(NO(2))(2)-bipy is localised on a single NO(2)-pyridyl ring. In all cases the LUMO of the [Pt(x,x'-(NO(2))(2)-bipy)Cl(2)] complexes is delocalised over both nitro-pyridyl rings. For all complexes, the 4(4') derivatives allows greatest overlap with metal valence orbitals in the LUMO.

  10. Studies on the Dihedral Angle and Torsional Barriers for 4,4′-Bipyridine

    Institute of Scientific and Technical Information of China (English)

    CHEN Wen-kai; LU Chun-hai; XU Jiao; LI Jun-qian


    Using the Hartree-Fock, MP2, and the B3LYP, BLYP, mPW1PW91 density functional methods, each combined with the 6-31G(d), 6-311G(d), 6-311+(d), 6-311++G(d, p) cc-pvdz and cc-pvtz basis sets, the equilibrium geometry of 4,4′ -bipyridine was optimized and the internal rotational potential barriers heights at 0° (AE0), 90° (AE90) were obtained. For the best basis set (cc-pvtz) , the predicted dihedral angle e ranges from 37.0 to 37.8° for all methods except the Hartree-Fock method (43.7). This agreed with the estimation from the electron diffraction experimental measurement (37.2°). The inter-ring C-C distance, ranging from 147.2 to 148.7 pm ( 147 pm experimental), is intermediate between the typical aromatic C-C bond and the aliphatic C-C bond. The results show that the inter-ring o-conjugation between two pyridyl rings stabilizes the co-planar conformer and the steric repulsion between the ortho neighboring hydrogens belonging to different rings favors the non-planar orthogonal conformer.

  11. 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


    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.

  12. Bis(4,4′-bipyridinium dodecatungstosilicate 4,4′-bipyridine hexahydrate

    Directory of Open Access Journals (Sweden)

    Quan Zhao


    Full Text Available The title compound, (C10H10N22[SiW12O40]·C10H8N2·6H2O or (4,4′-bipyH22[SiW12O40].(4,4′-bipy·6H2O (4,4′-bipy is 4,4′-bipyridine, was prepared under hydrothermal conditions. The asymmetric unit contains a discrete Keggin-type [SiW12O40]4− anion (located on a twofold axis, one 4,4′-bipy (located on a twofold axis, two (4,4′-bipyH22+ cations and six uncoordinated water molecules. The polyoxoanion is constructed from a central SiO4 tetrahedron which shares its O atoms with four trinuclear W3O13 groups, each of which is made up of three edge-sharing WO6 octahedra. The water molecules and [SiW12O40]4− anions are linked through hydrogen bonds.

  13. 3-Aminobenzoic acid–4,4′-bipyridine (2/3

    Directory of Open Access Journals (Sweden)

    Pornsuda Lhengwan


    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.

  14. (2,2′-Bipyridine(2-formyl-6-methoxyphenolatonickel(II perchlorate

    Directory of Open Access Journals (Sweden)

    Cui-Juan Wang


    Full Text Available In the title compound, [Ni(C8H7O3(C10H8N2]ClO4, the NiII atom is in a slightly distorted square-planar coordination by two N atoms from the 2,2′-bipyridine (bipy ligand and two O atoms from the deprotonated 2-formyl-6-methoxyphenolate (mbd ligand. The bipy ligand is nearly coplanar with the NiII square plane, the Ni atom being only 0.042 (2 Å from the mean plane, whereas the benzaldehyde plane is folded with respect to the square plane, making a dihedral angle of 19.17 (8°. One of the O atoms of the perchlorate anion is involved in a weak interaction with the Ni atom, with an Ni—O distance of 2.5732 (18 Å. The packing is stabilized by weak C—H...O interactions.

  15. Ruthenium(II) alpha-Diimine Complexes with One, Two, and Three 4,4'-Bis(hydroxymethyl)-2,2'-bipyridine and 4,4'-Bis(chloromethyl)-2,2'-bipyridine Ligands: Useful Starting Materials for Further Derivatization. (United States)

    Collins, James E.; Lamba, Jaydeep J. S.; Love, J. Christopher; McAlvin, John E.; Ng, Christina; Peters, Benjamin P.; Wu, Xufeng; Fraser, Cassandra L.


    Although Ru(II) tris(bipyridine) complexes and related alpha-diimine analogues find wide use in chemistry, many common ligand and metal complex derivatives are difficult to synthesize. The halomethyl bpy ligands and their inert metal complexes are one such example. These compounds are desirable since they serve as useful starting materials for a variety of more elaborate derivatives. Although 4,4'-bis(halomethyl)-2,2'-bipyridine ligands readily chelate to labile metal ions, they are not compatible with the higher temperatures and polar solvents typically required to effect ligand substitution at more inert Ru centers. Alternate routes to these targets involving solvento and other substitution labile intermediates yield products, but yields are typically low due to difficulties in purification. This report describes a new route to Ru(II) halomethyl bpy complexes involving chelation of the more robust 4,4'-bis(hydroxymethyl)-2,2'-bipyridine, bpy(CH(2)OH)(2), followed by conversion to the corresponding chloromethyl species on the metal using oxalyl chloride and DMF in THF or CH(3)CN solution. This new "OH to Cl" methodology is demonstrated for Ru(II) complexes with two, four, and six functionalities with both bpy and phen ancillary ligands. Complexes of the general formula [L(n)()Ru{bpy(CH(2)X)(2)}(3)(-)(n)()](PF(6))(2) (L = bpy, phen; X = OH, Cl; n = 0-2) have been prepared in good yield and are conveniently purified by precipitation. These Ru alpha-diimine complexes have already been utilized as multifunctional metalloinitiators for controlled cationic and radical polymerizations. They promise to be valuable for bpy derivatization generally.

  16. Vanadium methyl-bipyridine organoligand and its influence on energy balance and organs mass. (United States)

    Krośniak, Mirosław; Francik, Renata; Wojtanowska-Krośniak, Agnieszka; Tedeschi, Cinzia; Krasoń-Nowak, Małgorzata; Chłopicka, Joanna; Gryboś, Ryszard


    In the treatment of lifestyle diseases, including metabolic syndrome and type 2 diabetes, it is important to lower body mass and fat tissue, and consequently, to increase insulin-sensitivity. Unfortunately, it often happens that low-energy diet which would lower overweight is not observed and, thus, it does not bring the expected effects. This paper discusses the influence of three diets-control, high-fructose, and high-fatty diet-on absorption of energy from food in order to transform it into body mass. The kJ/g ratio which describes this process has been calculated. In the tested diets, the addition of fructose (79.13 ± 2.47 kJ/g) or fat (82.48 ± 2.28 kJ/g) results in higher transformation of energy into body mass than in the case of control diet (89.60 ± 1.86 kJ/g). The addition of Na[VO(O2)2(4,4′-Me2-2,2′-bpy)]•8H2O (where 4,4′-Me2-2,2′-bpy = 4,4′-dimethyl-2,2′-bipyridine) results in statistical increase of that ratio: fructose diet (86.88 ± 0.44 kJ/g), fat diet (104.68 ± 3.01 kJ/g), and control diet (115.98 ± 0.56 kJ/g), respectively. Fat diet statistically influences the decrease of kidney mass in comparison to the other diets. The application of the tested vanadium compound results also in the statistical decrease of the fatty liver caused by fructose and fat diet.

  17. One-dimensional Polymers Constructed with Binuclear Copper(Ⅱ) α,β-Unsaturated Carboxylates Bridged by 4,4'-Bipyridine

    Institute of Scientific and Technical Information of China (English)

    刘萍; 王尧宇; 李东升; 栾新军; 高松; 史启祯


    A methanol solution of 4,4'-bipyridine reacts with Cu2A4(H2O)2 to yield coordination polymers of general formula: [Cu2A4(bipy)]n [A: CH2=C(Me)CO2- (1), CH2=CHCO2- (2); bipy: 4,4'-bipyridine]. They were characterized by elemental analyses, IR spectra and thermal analyses. The X-ray structure analyses of 1 show a one-dimensional chain structure where the binuclear structural units Cu2[CH2=C(Me)CO2]4 are bridged by 4,4'-bipyridine molecules. Furthermore, the binuclear units between adjacent layers can form micropores. The temperature-dependent magnetic susceptibility of 1 indicates that the strong antiferromagnetic interaction exists between copper(Ⅱ) atoms in the binuclear units.

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

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    Xuan Xu


    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.

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

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


    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].

  20. 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)


    [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.

  1. (Acetato-κO(2,2′-bipyridine-κ2N,N′trimethylplatinum(IV monohydrate

    Directory of Open Access Journals (Sweden)

    Dirk Steinborn


    Full Text Available In the title hydrate, [Pt(CH33(CH3COO(C10H8N2]·H2O, the PtIV atom exhibits a distorted octahedral coordination geometry built up by three methyl ligands in a facial arrangement, a bipyridine ligand and a monodentately bound acetate ligand. In the crystal structure, intermolecular O—H...O hydrogen bonds are observed between the water molecule and the platinum complex, which link the molecules into chains along the c axis.

  2. 4-{Phenyl[4-(6-phenyl-2,2′-bipyridin-4-ylphenyl]amino}benzaldehyde

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    Yu-yang Zhang


    Full Text Available The title molecule, C35H25N3O, is a triphenylamine derivative with the 4-position substituted by an aldehyde group, and the 4′-position substituted by a 6-phenyl-2,2′-bipyridine group. The whole molecule is non-planar and the dihedral angle between the core benzene and pyridine rings is 36.96 (5°. The dihedral angle between the phenyl and benzaldehyde groups bonded to the amine N atom is 70.86 (5°.

  3. Coordination chemistry for antibacterial materials: a monolayer of a Cu(2+) 2,2'-bipyridine complex grafted on a glass surface. (United States)

    Pallavicini, Piersandro; Dacarro, Giacomo; Grisoli, Pietro; Mangano, Carlo; Patrini, Maddalena; Rigoni, Federica; Sangaletti, Luigi; Taglietti, Angelo


    A propyltrimethoxysilane-modified 2,2'-bipyridine ligand is synthesized and its acetonitrile solutions are used to prepare monolayers of the molecule on glass surfaces. Absorption and X-ray photoelectron spectroscopy demonstrate that the modified glass surfaces bind Cu(2+) with a 1:1 ratio with respect to the 2,2'-bipyridine moieties under the chosen preparative conditions, producing materials bearing 0.016 μg cm(-2) of copper. Although in trace amounts, the bound Cu(2+) cations exert a significant microbicidal effect against Escherichia coli and Staphylococcus aureus.

  4. 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


    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.

  5. Metal dependent motif transition in a self-assembled monolayer of bipyridine derivatives via coordination: An STM study (United States)

    Wang, Yi; Yuan, Qunhui; Xu, Hongbo; Zhu, Xuefeng; Gan, Wei


    Low-dimensional molecular motifs with diversity developed via the on-surface chemistry are attracting growing interest for their potential in advanced nanofabrication. In this work, scanning tunneling microscopy was employed to investigate the in situ and ex situ metal coordinations between 4,4'-ditetradecyl-2,2'-bipyridine (bpy) and Zn(ii) or Cu(ii) ions at a highly oriented pyrolytic graphite (HOPG)/1-phenyloctane interface under ambient conditions. The results demonstrate that the bpy adopts a flat-lying orientation with its substituted alkyl chains in a tail-to-tail arrangement in a bpy monolayer. For the in situ coordination, the bpy/Zn(ii) and bpy/Cu(ii) complexes are aligned in edge-on fashions, wherein the bpy stands vertically on the HOPG surface and interdigitates at the alkyl chains. In the two-dimensional arrays of ex situ coordinated complexes, metal dependent motifs have been observed with Zn(ii) and Cu(ii), wherein the bipyridine moieties are parallel to the graphite surface. These results suggest that the desired on-surface coordination architectures may be achieved by the intentional selection of the metal centers.

  6. Structural, spectroscopic, magnetic and electrochemical studies of monomer N-substituted-sulfanilamide copper (II) complex with 2,2'-bipyridine. (United States)

    Öztürk, Filiz; Bulut, İclal; Bulut, Ahmet


    A novel copper (II) complex of sulfamethazine (4-amino-N-[4,6-dimethyl-2-pyrimidinyl] benzene sulfonamide, Hsmz) ([Cu(smz)2bipy]⋅0.8H2O; bipy: 2,2'-bipyridine) has been synthesized and characterized by single crystal X-ray diffraction, EPR, IR, UV-vis and electrochemical methods. The single crystal X-ray analysis indicated that the compound crystallizes in the monoclinic space group P21/c with Z=4. The central copper (II) ion is coordinated by two bidentate sulfamethazine anions through the nitrogen atoms together with one bidentate 2,2'-bipyridine ligand forming the octahedral geometry. The characteristic vibration bands support the X-ray analysis results. The EPR spectral analysis has led to that the ground state wave function of the unpaired electron of copper ion is [Formula: see text] ((2)B1g state) and also indicated that the metal ions are located in distorted octahedral sites (D4h) elongated along the z-axis. The electrochemical studies of the complex were also carried out to determine the active sites of the ligands. The cyclic and square wave voltammetric techniques have been used to determine the complex.

  7. Photocatalytic water decontamination by the zeolite-y entrapped ruthenium tris-2,2 bipyridine complex

    Energy Technology Data Exchange (ETDEWEB)

    Szulbinski, W.S.; Malato Rodirguez, S.; Gernjak, W.


    The zeolite-Y entrapped ruthenium tris-2,2-bipyridine complex externally loaded with platinum (Z-[Ru(bpp){sub 3}]''2+/Pt) has been examined as a novel photocatalyst for wastewater treatment in flow reactors of the pilot plant at the Plataforma Solar de Almeria, in Sapin. The catalyst generated by the template synthesis of [Ru(bpy){sub 3}]''2+ within the zeolite-Y supercharges (with the occupancy of one the [Ru(bpy){sub 3}]'' molecule per five the zeolite supercharges), and then platinized (1% wt) of the resulting Z-[Ru(bpy){sub 3}]''2+. The catalytic activity of Z-[u(bpy){sub 3}]''2+/Pt for waste-water treatment has been compared to that of TiO{sub 2} as the standard. For this phenol (PhOH) and pirimicarb ( a pesticide) have been used as models for water pollutants. By kinetics measurements, it has been documented that Z-[Ru(bpy){sub 3}]''2+/Pt decomposes PhOH with the relative photonic efficiency of {zeta}=0.37, assuming that{zeta}=1.0 for TiO{sub 2}, under the same experimental conditions. To improve the Z-[Ru(bpy){sub 3}]''2+/Pt photocatalytic activity, all the zeolite super cages have to be occupied with [Ru(bpy){sub 3}]''2+ modules, since this might increase the rate of the photoinduced electron transfer reaction. Moreover, it has been revealed that Z-[Ru(bpy){sub 3}]''2+/Pt is mostly active at the visible range of the solar radiation, at which TiO{sub 2} is inactive and unable to decompose organic pollutants. This has been supported by the diffuse reflectance spectroscopic measurement exhibiting the electronic absorption of Z-[Ru(bpy){sub 3}]''2*/pt at {lambda}{sub m}ax=454 nm. (Author) 15 refs.

  8. Design and Synthesis of 4,4'-Disubstituted-[2,2']-Bipyridines for Catalyzing CO/Styrene Copolymerization with Palladium(Ⅱ)

    Institute of Scientific and Technical Information of China (English)

    郭锦棠; 郁培云; 王海霞; 赵海洋


    A series of 4,4'-disubstituted-[2,2']-bipyridines, featuring electron withdrawing/donating functional groups such as amino, chloro, nitro, ethoxycarbonyl, carboxy, methyl, methoxy and hydroxymethyl, have been syn-thesized and employed in the copolymerization of carbon monoxide(CO)and styrene. The available bipyridine and its derivatives were coordinated with palladium(Ⅱ)acetate for catalyzing the copolymerization of CO and styrene, and the concomitant polyketone was characterized by means of 13C NMR, FTIR, differential scanning calo-rimetry(DSC)and element analysis techniques concerning its structure and thermal performance. The effect of dif-ferent electron-donating and electron-withdrawing groups on catalyst performance and molecular weight of co-polymer was studied under certain experimental condition. It has been proved that the enhancement of electron donating and conjugative effects on bipyridine ligand will not only improve the catalytic activity of the composi-tion, but also increase the molecular weight of the as-prepared polyketone. The catalytic activity is the highest in hydroxymethyl substituted 2,2'-bipyridine ligand(1 356 gSTCO/(gPd · h)), when the molecular weight and polydispersity index of the polyketone are Mn=8 502,Mw=1 3440 and Mw/Mn=1.581, respectively.

  9. Cocrystals of kaempferol, quercetin and myricetin with 4,4‧-bipyridine: Crystal structures, analyses of intermolecular interactions and antibacterial properties (United States)

    Zhang, Yu-Nan; Yin, He-Mei; Zhang, Yu; Zhang, Da-Jun; Su, Xin; Kuang, Hai-Xue


    With an aim to explore the interactions of Osbnd H⋯N between hydroxyl moiety of the flavonoids and the pyridyl ring of N-containing aromatic amines, three flavonols with varying B-ring-hydroxyl groups (kaempferol, quercetin, and myricetin) were selected to combine with 4,4‧-bipyridine. As a result, three new cocrystals of flavonols were obtained with a solution evaporation approach. These three cocrystals were characterized by single crystal X-ray diffraction, XPRD, IR and NMR methods. The resulting cocrystals were kaempferol: 4,4‧-bipyridine (2:1) (KAE·BPY·2H2O), quercetin: 4,4‧-bipyridine (1:1.5) (QUE·BPY), and myricetin: 4,4‧-bipyridine (1:2) (MYR·BPY·H2O). Structural analyses show that an array of hydrogen bonds and π-π stacking interactions interconnect the molecules to form a two-dimensional (2D) supramolecular layer in KAE·BPY·2H2O, QUE·BPY, and MYR·BPY·H2O. In the three cocrystals, they present as three different synthons-ⅠR88(58), Ⅳ R44(42) and, Ⅶ R66(29) with 4,4‧-bipyridine, respectively-which may yield a strategy for constructing the supramolecule. Cocrystals of flavonols combined with N-containing aromatic amines, 7-OH, B-ring-hydroxyl number and/or the location of the flavonols to play a significant part in extending the dimensionality of the cocrystals. The resulting motif formation and crystal packing in these flavonols cocrystals has combined with N-containing aromatic amines. Additionally, the antibacterial properties of the three cocrystals against Staphylococcus aureus (S. aureus) and Escherichia coli (E. coli) have been investigated.

  10. (2,2′-Bipyridine-κ2N,N′dichloridopalladium(II 1,4-dioxane hemisolvate

    Directory of Open Access Journals (Sweden)

    Ricardo Alfredo Gutiérrez Márquez


    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.

  11. Synthesis and Crystal Structure of Palladium(Ⅱ) Complex with 2,2'-Bipyridine-3,3'-dicarboxylic Acid

    Institute of Scientific and Technical Information of China (English)


    The title complex Pd(H2BDA)Cl2(2DMSO (C16H14Cl2N2O6PdS2, H2BDA = 2,2'- bipyridine-3,3'-dicarboxylic acid) has been synthesized and characterized by IR spectra, elemental analysis and 1H NMR spectra. Its structure was determined by single-crystal X-ray diffraction analysis. The complex crystallizes in the monoclinic system, space group P21/c with a = 1.3604(6), b = 1.2606(6), c = 1.3521(6) nm, β = 103.677(7)°, V = 2.2530(17) nm3, Mr = 571.75, Z = 4, Dc = 1.686 g/cm3, μ = 1.280 mm-1, F(000) = 1136, R = 0.0405 and wR = 0.0908. The complex presents a planar quadrangle arrangement and is assembled via hydrogen bonds.

  12. 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


    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.

  13. 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


    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...

  14. Liquid chromatography of antihistamines using post-column tris(2,2'-bipyridine) ruthenium(III) chemiluminescence detection. (United States)

    Holeman, J A; Danielson, N D


    The separation and detection of five antihistamine drugs commonly found within over-the-counter allergy and cold pharmaceutical products was performed by HPLC with chemiluminescence (CL) detection. Comparable detection limits at 5-10 pmol were found for the antihistamines by both UV at 214 nm and tris(2,2'-bipyridine) ruthenium(III) CL. However, urine samples were found not to generate as large an unretained peak by CL detection as compared to those peaks by UV detection at 214 and 254 nm. For example, the pheniramine peak representing 0.15 microgram/ml was almost totally obscured at 214 nm. Quantitative results received for three antihistamine commercial samples ranged from 4 to 8% error in accuracy when an internal standard was used to compensate for short term detector drift.

  15. A Molybdenum(0) Isocyanide Analogue of Ru(2,2'-Bipyridine)3 (2+) : A Strong Reductant for Photoredox Catalysis. (United States)

    Büldt, Laura A; Guo, Xingwei; Prescimone, Alessandro; Wenger, Oliver S


    We report the first homoleptic Mo(0) complex with bidentate isocyanide ligands, which exhibits metal-to-ligand charge transfer ((3) MLCT) luminescence with quantum yields and lifetimes similar to Ru(bpy)3 (2+) (bpy=2,2'-bipyridine). This Mo(0) complex is a very strong photoreductant, which manifests in its capability to reduce acetophenone with essentially diffusion-limited kinetics as shown by time-resolved laser spectroscopy. The application potential of this complex for photoredox catalysis was demonstrated by the rearrangement of an acyl cyclopropane to a 2,3-dihydrofuran, which is a reaction that requires a reduction potential so negative that even the well-known and strongly reducing Ir(2-phenylpyridine)3 photosensitizer cannot catalyze it. Our study thus provides the proof-of-concept for the use of chelating isocyanides to obtain Mo(0) complexes with long-lived (3) MLCT excited states that are applicable to unusually challenging photoredox chemistry.

  16. Copper (II) and 2,2′-Bipyridine Complexation Improves Chemopreventive Effects of Naringenin against Breast Tumor Cells (United States)

    Filho, Júlio César Conceição; Sarria, André Lúcio Franceschini; Becceneri, Amanda Blanque; Fuzer, Angelina Maria; Batalhão, Jaqueline Raquel; da Silva, Caio Marcio Paranhos; Carlos, Rose Maria; Vieira, Paulo Cezar; Fernandes, João Batista; Cominetti, Márcia Regina


    Cancer is the second leading cause of death worldwide and there is epidemiological evidence that demonstrates this tendency is emerging. Naringenin (NGEN) is a trihydroxyflavanone that shows various biological effects such as antioxidant, anticancer, anti-inflammatory, and antiviral activities. It belongs to flavanone class, which represents flavonoids with a C6-C3-C6 skeleton. Flavonoids do not exhibit sufficient activity to be used for chemotherapy, however they can be chemically modified by complexation with metals such as copper (Cu) (II) for instance, in order to be applied for adjuvant therapy. This study investigated the effects of Cu(II) and 2,2′-bipyridine complexation with naringenin on MDA-MB-231 cells. We demonstrated that naringenin complexed with Cu(II) and 2,2′-bipyridine (NGENCuB) was more efficient inhibiting colony formation, proliferation and migration of MDA-MB-231 tumor cells, than naringenin (NGEN) itself. Furthermore, we verified that NGENCuB was more effective than NGEN inhibiting pro-MMP9 activity by zymography assays. Finally, through flow cytometry, we showed that NGENCuB is more efficient than NGEN inducing apoptosis in MDA-MB-231 cells. These results were confirmed by gene expression analysis in real time PCR. We observed that NGENCuB upregulated the expression of pro-apoptotic gene caspase-9, but did not change the expression of caspase-8 or anti-apoptotic gene Bcl-2. There are only few works investigating the effects of Cu(II) complexation with naringenin on tumor cells. To the best of our knowledge, this is the first work describing the effects of Cu(II) complexation of a flavonoid on MDA-MB-231 breast tumor cells. PMID:25192075

  17. Copper (II and 2,2'-bipyridine complexation improves chemopreventive effects of naringenin against breast tumor cells.

    Directory of Open Access Journals (Sweden)

    Júlio César Conceição Filho

    Full Text Available Cancer is the second leading cause of death worldwide and there is epidemiological evidence that demonstrates this tendency is emerging. Naringenin (NGEN is a trihydroxyflavanone that shows various biological effects such as antioxidant, anticancer, anti-inflammatory, and antiviral activities. It belongs to flavanone class, which represents flavonoids with a C6-C3-C6 skeleton. Flavonoids do not exhibit sufficient activity to be used for chemotherapy, however they can be chemically modified by complexation with metals such as copper (Cu (II for instance, in order to be applied for adjuvant therapy. This study investigated the effects of Cu(II and 2,2'-bipyridine complexation with naringenin on MDA-MB-231 cells. We demonstrated that naringenin complexed with Cu(II and 2,2'-bipyridine (NGENCuB was more efficient inhibiting colony formation, proliferation and migration of MDA-MB-231 tumor cells, than naringenin (NGEN itself. Furthermore, we verified that NGENCuB was more effective than NGEN inhibiting pro-MMP9 activity by zymography assays. Finally, through flow cytometry, we showed that NGENCuB is more efficient than NGEN inducing apoptosis in MDA-MB-231 cells. These results were confirmed by gene expression analysis in real time PCR. We observed that NGENCuB upregulated the expression of pro-apoptotic gene caspase-9, but did not change the expression of caspase-8 or anti-apoptotic gene Bcl-2. There are only few works investigating the effects of Cu(II complexation with naringenin on tumor cells. To the best of our knowledge, this is the first work describing the effects of Cu(II complexation of a flavonoid on MDA-MB-231 breast tumor cells.

  18. 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: [ECsens, Department of Analytical Chemistry, Campus Fuentenueva, Faculty of Sciences, University of Granada, E-18071 Granada (Spain)


    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.

  19. Mn(II) complexes containing the polypyridylic chiral ligand (-)-pinene[5,6]bipyridine. Catalysts for oxidation reactions. (United States)

    Rich, Jordi; Rodríguez, Montserrat; Romero, Isabel; Vaquer, Lydia; Sala, Xavier; Llobet, Antoni; Corbella, Montserrat; Collomb, Marie-Noëlle; Fontrodona, Xavier


    A series of mononuclear and dinuclear chiral manganese(II) complexes containing the neutral bidentate chiral nitrogen ligand (-)-pinene[5,6]bipyridine, (-)-L, were prepared from different manganese salts. The chirality in these complexes arises from the pinene ring that has been fused to the 5,6 positions of one pyridine group of the bipyridine ligand. These complexes have been characterized through analytical, spectroscopic (IR, UV/Vis, ESI-MS) and electrochemical techniques (cyclic voltammetry). Single X-ray structure analysis revealed a five-coordinated Mn(II) ion in [{MnCl((-)-L)}2(mu-Cl)2] (2), [{Mn((-)-L)}2(mu-OAc)3](PF6) (3) and [MnCl2(H2O)((-)-L)] (4) and a six-coordinated one in [MnCl2((-)-L)2] (5), [Mn(CF3SO3)2((-)-L)2] (6) and [Mn(NO3)(H2O)((-)-L)2)](NO3) (7). The magnetic properties of the binuclear compounds 2 and 3 have been studied. Both compounds show a weak antiferromagnetic coupling (2, J = -0.22 cm(-1); 3, J = -0.85 cm(-1)). The catalytic activity of the whole set of complexes has been tested with regard to the epoxidation of aromatic alkenes with peracetic acid. In the particular case of styrene, good selectivities and moderate enantioselectivities were obtained. Furthermore, total retention of the initial cis configuration was achieved when epoxidizing cis-beta-methylstyrene with the chloride complexes. In general, the epoxidation activity of these manganese complexes is strongly dependent on the steric encumbrance of the substrates employed.

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

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    Xi-Fang Wang


    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.

  1. 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)


    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}.

  2. Crystal structure of catena-poly[[[triaqua(4-cyanobenzoato-κOnickel(II]-μ-4,4′-bipyridine-κ2N:N′] 4-cyanobenzoate

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    Alfredo A. Morales-Tapia


    Full Text Available In the title polymeric complex salt, {[Ni(C8H4NO2(C10H8N2(H2O3](C8H4NO2}n, the NiII cation is coordinated by a 4-cyanobenzoate anion, two 4,4′-bipyridine ligands and three water molecules in a distorted N2O4 octahedral geometry. The 4,4′-bipyridine ligands bridge the NiII cations to form polymeric chains of the title complex cations, propagating along the c-axis direction. The dihedral angle between the pyridine rings of the 4,4′-bipyridine ligand is 24.9 (6°. In the crystal, the uncoordinating 4-cyanobenzoate anions link with the complex cations via O—H...O hydrogen bonds into a three-dimensional supramolecular architecture. Weak C—H...O, C—H...N interactions and π–π stacking [centroid-to-centroid distances = 3.566 (4 and 3.885 (4 Å] are also observed in the crystal.

  3. On the Innocence of Bipyridine Ligands: How Well Do DFT Functionals Fare for These Challenging Spin Systems? (United States)

    Milko, Petr; Iron, Mark A


    The electronic structures of a number of iron, cobalt, vanadium, and titanium complexes with the 2,2'-bipyridine (bpy) ligand were considered using the multireference CASSCF and NEVPT2 methods. Many of these systems have been studied in the past using B3LYP and were then found to contain the bpy ligand as a radical anion. For many of the cases, this is contradicted by our multireference calculations. While there are instances where the ligand is indeed a radical anion, in many cases it remains neutral and is involved in backbonding from the metal center. For those cases where CASSCF is too costly, a number of DFT functionals, including the newer double-hybrid functionals, were evaluated against the CASSCF data. It was found that nonhybrid functionals, especially those containing the kinetic energy density τ, were the best at predicting the electronic nature of the complexes. The τ-HCTH and HCTH functionals were the top performers, correctly predicting eleven out of eleven test cases and with the lowest mean unsigned errors (MUE, 7.6 and 7.8 kcal·mol(-1), respectively); the M06-L, N12, BLYP, PBE, and TPSS functionals also did well, while B3LYP had significant problems.

  4. Synthesis and Crystal Structure of Copper(II) Complex with Mixed Bipyridine and 2-Hydroxy-1-naphthaldehyde Ligands

    Institute of Scientific and Technical Information of China (English)

    卜平宇; 程鹏; 赵斌; 阎世平; 瘳代正; 姜宗慧; 刘松岩; 姚心侃; 王宏根


    A mononuclear copper(II) complex, [Cu(bipy)(naph)(ClO4)] (where bipy is bipyridine and naph is 2-hydroxy-1-naphthaldehyde), was synthesized and characterized by X-ray single-crystal structure analysis. The crystal is triclinic, space group P ī with a = 9.245(4), b = 9.962(4), c = 10.809(7) A, α = 84.83(5), β =82.35(4), γ = 81.02(4)°, V = 972.1 >3, C21H15ClCuN2O6 Mr = 490.36, Z = 2, F(000) = 498, Dx = 1.68 g/cm3, μ = 13.05 cm-1, R = 0.078, Rw = 0.081 for 2295 observed reflections with I > 3σ(I). The copper(II) ion is coordinated by two nitrogen atoms of bipy and two oxygen atoms of naph in the equatorial plane, with an axial perchlorate oxygen-copper(II) bond to copper(II) ion to form square-pyramidal coordination geometry. The coordination environment of copper(II) is similar to the active site of galactose oxidase and this compound may also be considered as the structural model of galactose oxidase.

  5. Multispectroscopic DNA-binding studies of a terbium(III) complex containing 2,2'-bipyridine ligand. (United States)

    Aramesh-Boroujeni, Zahra; Khorasani-Motlagh, Mozhgan; Noroozifar, Meissam


    Agarose gel electrophoresis, absorption, fluorescence, viscosity, and circular dichroism (CD) have been used in exploring the interaction of terbium(III) complex, [Tb(bpy)2Cl3(OH2)] where bipy is 2,2'-bipyridine, with Fish salmon DNA. Agarose gel electrophoresis assay, along with absorption and fluorescence studies, reveal interaction between the corresponding complex and FS-DNA. Also, the binding constants (Kb) and the Stern-Volmer quenching constants (Ksv) of Tb(III) complex with FS-DNA were determined. The calculated thermodynamic parameters suggested that the binding of mentioned complex to FS-DNA was driven mainly by hydrophobic interactions. A comparative study of this complex with respect to the effect of iodide-induced quenching, ionic strength effect, and ethidium bromide exclusion assay reflects binding of explicit to the FS-DNA primarily in a groove fashion. CD and viscosity data also support the groove binding mode. Furthermore, Tb(III) complex have been simultaneously screened for their antibacterial and antifungal activities.

  6. Supramolecular Assemblies of(±)-2,2'-Dihydroxy-1,1'-binaphthyl with 2,2'-Bipyridine and Naphthodiazine

    Institute of Scientific and Technical Information of China (English)

    JI Bao-Ming吉保明; CHEN Hua-Ting陈花婷; DU Chen-Xia杜晨霞; DING Kui-Ling丁奎岭


    Supramolecular assemblies of (±)-2,2'-dihydroxy-l,l'-binaphthyl (BINOL, A), with aza donor molecules including 2,2'-bipyridine (B) and naphthodiazine (C), have been synthesized and characterized by single-crystal X-ray diffraction methods. Two inclusion complexes crystallize in the triclinic system with P-1 space group. In the inclusion complex between A and B, two molecules of A and two molecules of B are linked each other by intermolecular hydrogen bonds with two molecules of water as the bridges, forming a centrosymmetric dimer with formula of A2(H2O)2B2; while in the inclusion complex between A and C, the molecule C virtually acts as a bridge to link molecules A through intermolecular O-H...N hydrogen bonds, forming a short-chain supramolecular block with interactions also play an important role in the solid-state packing of these two inclusion complexes. The structural information disclosed on the complex between dihydroxy compound and aza hydrogen bond acceptors in this work would be particularly important for the rational design of supramolecular organic functional materials.

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

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    Nam-Ho Kim


    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.

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

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


    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.

  9. Microbore liquid chromatography of tertiary amine anticholinergic pharmaceuticals with tris(2,2'-bipyridine)ruthenium(III) chemiluminescence detection. (United States)

    Holeman, J A; Danielson, N D


    The post-column chemiluminescent reaction of six anticholinergic alkaloid compounds with tris(2,2'-bipyridine)ruthenium(III) (Ru(bpy)3(3+)) is applied to microbore high-performance liquid chromatography (HPLC). At flow rates less than 200 microL/min, the capillary mixing cell in which Ru(bpy)3(3+) and the analyte are mixed directly allows for good light detection. In contrast, a diminished signal occurs at these low flow rates with conventional post-column mixing in a tee. Optimal chemiluminescent pH conditions for atropine, scopolamine, dicyclomine, cyclopentolate, cyclobenzaprine, and procyclidine are determined at moderately basic conditions (pH 7 to 9). 2-Butanone is found to be compatible with the chemiluminescent reaction, whereas tetrahydrofuran and propionitrile cause an increase in background noise and a chemiluminescent signal loss. As 2-butanone is more nonpolar than acetonitrile, it assists in the elution of these hydrophobic anticholinergic compounds. Five anticholinergic compounds are resolved successfully with a PRP-1 polymeric column and a slightly basic mobile phase, but a C8 silica column is better suited for the more hydrophobic compounds (cyclobenzaprine, procyclidine, and dicyclomine).

  10. Five-coordinate [Pt(II)(bipyridine)2(phosphine)](n+) complexes: long-lived intermediates in ligand substitution reactions of [Pt(bipyridine)2](2+) with phosphine ligands. (United States)

    Lo, Warrick K C; Cavigliasso, Germán; Stranger, Robert; Crowley, James D; Blackman, Allan G


    The reaction of [Pt(N-N)2](2+) [N-N = 2,2'-bipyridine (bpy) or 4,4'-dimethyl-2,2'-bipyridine (4,4'-Me2bpy)] with phosphine ligands [PPh3 or PPh(PhSO3)2(2-)] in aqueous or methanolic solutions was studied by multinuclear ((1)H, (13)C, (31)P, and (195)Pt) NMR spectroscopy, X-ray crystallography, UV-visible spectroscopy, and high-resolution mass spectrometry. NMR spectra of solutions containing equimolar amounts of [Pt(N-N)2](2+) and phosphine ligand give evidence for rapid formation of long-lived, 5-coordinate [Pt(II)(N-N)2(phosphine)](n+) complexes. In the presence of excess phosphine ligand, these intermediates undergo much slower entry of a second phosphine ligand and loss of a bpy ligand to give [Pt(II)(N-N)(phosphine)2](n+) as the final product. The coordination of a phosphine ligand to the Pt(II) ion in the intermediate [Pt(N-N)2(phosphine)](n+) complexes is supported by the observation of (31)P-(195)Pt coupling in the (31)P NMR spectra. The 5-coordinate nature of [Pt(bpy)2{PPh(PhSO3)2}] is confirmed by X-ray crystallography. X-ray crystal structural analysis shows that the Pt(II) ion in [Pt(bpy)2{PPh(PhSO3)2}]·5.5H2O displays a distorted square pyramidal geometry, with one bpy ligand bound asymmetrically. These results provide strong support for the widely accepted associative ligand substitution mechanism for square planar Pt(II) complexes. X-ray structural characterization of the distorted square planar complex [Pt(bpy)(PPh3)2](ClO4)2 confirms this as the final product of the reaction of [Pt(bpy)2](2+) with PPh3 in CD3OD. The results of density functional calculations on [Pt(bpy)2](2+), [Pt(bpy)2(phosphine)](n+), and [Pt(bpy)(phosphine)2](n+) indicate that the bonding energy follows the trend of [Pt(bpy)(phosphine)2](n+) > [Pt(bpy)2(phosphine)](n+) > [Pt(bpy)2](2+) for stability and that the formation reactions of [Pt(bpy)2(phosphine)](n+) from [Pt(bpy)2](2+) and [Pt(bpy)(phosphine)2](n+) from [Pt(bpy)2(phosphine)](n+) are energetically favorable. These

  11. Reaction of tris(bipyridine)ruthenium(III) with hydroxide and its application in a solar energy storage system. (United States)

    Creutz, C; Sutin, N


    Irradiation of Ru(bipy)(3) (2+) (bipy = 2,2'-bipyridine) with light below 560 nm results in the formation of a charge-transfer excited state potentially capable of reducing water to dihydrogen with concomitant production of Ru(bipy)(3) (3+). The latter may be reduced by hydroxide [Formula: see text] to form dioxygen and regenerate the starting complex. The use of these reactions in a cell designed to bring about the photochemical decomposition of water is proposed.The stoichiometry, kinetics, and mechanism of the Ru(bipy)(3) (3+)-hydroxide reaction have been investigated by conventional and stopped-flow spectrophotometry. The dioxygen yield is a sharp function of pH, attaining its maximum value (about 80%) at pH 9. At low pH (3 and 4.8) the production of ruthenium(II) is first order with k(obsd) = (1.41 +/- 0.04) x 10(-4) sec(-1) (25 degrees , ionic strength mu = 1.00 M with sodium sulfate). In the intermediate pH range (7.9-10.0) complex kinetics are observed. In the hydroxide range 0.01-0.50 M, ruthenium(II) production is predominantly first order with k(obsd) = k(a)[OH(-)] + k(b)[OH(-)](2) sec(-1); k(a) = 148 M(-1) sec(-1) and k(b) = 138 M(-2) sec(-1) (25 degrees , mu = 1.00 M, sodium sulfate). For the k(a) term, the activation parameters are DeltaH(double dagger) = 15.3 +/- 1.0 kcal mol(-1) and DeltaS(double dagger) = 7 +/- 3 cal deg(-1) mol(-1) (1 cal = 4.184 J). An intermediate species (lambda(max) 800 nm) forms at the same rate as ruthenium(II) in this hydroxide range. It disappears with k(obsd) = 1.2 + 1.1 x 10(2) [OH(-)] sec(-1) at 25 degrees . Similarly absorbing (lambda(max) 750 to 800 nm) species are generated by the addition of hydroxyl radical to M(bipy)(3) (2+/3+) [M = Fe(II), Os(II), Ru(II), Cr(III), Ru(III)] in pulse radiolysis experiments. The kinetics above pH 7 are described in terms of rate-determining nucleophilic attack by hydroxide on the bound bipyridine ring. The hydroxide adduct so generated is tentatively identified with that observed in

  12. 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:


    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.

  13. Investigation of torsional potentials, molecular structure, vibrational properties, molecular characteristics and NBO analysis of some bipyridines using experimental and theoretical tools (United States)

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


    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.

  14. “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.


    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.

  15. 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


    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.

  16. (2,2′-Bipyridine-κ2N,N′bis(N-ethyl-N-methyldithiocarbamato-κ2S,S′zinc(II

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    Noorul Aisyah Abdul Ghafar


    Full Text Available The complete molecule of the title compound, [Zn(C4H8NS22(C10H8N2], is generated by crystallographic twofold symmetry, with the Zn atom lying on the rotation axis; the axis also bisects the central C—C bond of the 2,2′-bipyridine molecule. The metal atom is chelated by two S,S′-bidentate dithiocarbamate anions and the N,N′-bidentate heterocycle, resulting in a distorted cis-ZnN2S4 octahedral geometry. The methyl and ethyl groups of the anion are statistically disordered.

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

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    Hamid Reza Khavasi


    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].

  18. catena-Poly[[(5,5′-dimethyl-2,2′-bipyridine-κ2N,N′cadmium]-di-μ-bromido

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    Sadif A. Shirvan


    Full Text Available In the crystal of the title polymeric compound, [CdBr2(C12H12N2]n, the CdII cation is located on a twofold rotation axis. The CdII cation is six-coordinated in a distorted octahedral geometry formed by two N atoms from the 5,5′-dimethyl-2,2′-bipyridine ligand and four bridging Br− anions. The bridging function of the Br− anions leads to a polymeric chain running along the c axis.

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

    Directory of Open Access Journals (Sweden)

    Ming-Bo Ruan


    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.

  20. 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


    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.

  1. Supramolecular interactions in the 1:2 co-crystal of 4,4′-bipyridine and 3-chlorothiophene-2-carboxylic acid

    Directory of Open Access Journals (Sweden)

    Olakkandiyil Prajina


    Full Text Available The asymmetric unit of the title compound, 2C5H3ClO2S·C10H8N2, is comprised of a molecule of 3-chlorothiophene-2-carboxylic acid (3TPC and half of a molecule of 4,4′-bipyridine (BPY. A distinctive O—H...N-based synthon is present. Cl...Cl and π–π stacking interactions further stabilize the crystal structure, forming a two-dimensional network parallel to the bc plane.

  2. Di-μ-bromido-bis[bromido(4,4′-dimethyl-2,2′-bipyridine-κ2N,N′mercury(II

    Directory of Open Access Journals (Sweden)

    Amin Ebadi


    Full Text Available The asymmetric unit of the title compound, [Hg2Br4(C12H12N22], contains one half-molecule. The HgII atom is five-coordinated in a trigonal–bipyramidal configuration by two N atoms from the chelating 4,4′-dimethyl-2,2′-bipyridine ligand, two bridging Br and one terminal Br atom, leading to a centrosymmetric dimeric molecule. There is a π–π contact between the pyridine rings [centroid-to-centroid distance = 3.756 (5 Å].

  3. Electronic optimization of heteroleptic Ru(II) bipyridine complexes by remote substituents: synthesis, characterization, and application to dye-sensitized solar cells. (United States)

    Han, Won-Sik; Han, Jung-Kyu; Kim, Hyun-Young; Choi, Mi Jin; Kang, Yong-Soo; Pac, Chyongjin; Kang, Sang Ook


    We prepared a series of new heteroleptic ruthenium(II) complexes, Ru(NCS)(2)LL' (3a-3e), where L is 4,4'-di(hydroxycarbonyl)-2,2'-bipyridine and L' is 4,4'-di(p-X-phenyl)-2,2'-pyridine (X = CN (a), F (b), H (c), OMe (d), and NMe(2) (e)), in an attempt to explore the structure-activity relationships in their photophysical and electrochemical behavior and in their performance in dye-sensitized solar cells (DSSCs). When substituent X is changed from electron-donating NMe(2) to electron-withdrawing CN, the absorption and emission maxima reveal systematic bathochromic shifts. The redox potentials of these dyes are also significantly influenced by X. The electronic properties of the dyes were theoretically analyzed using density functional theory calculations; the results show good correlations with the experimental results. The solar-cell performance of DSSCs based on dye-grafted nanocrystalline TiO(2) using 3a-3e and standard N3 (bis[(4,4'-carboxy-2,2'-bipyridine)(thiocyanato)]ruthenium(II)) were compared, revealing substantial dependences on the dye structures, particularly on the remote substituent X. The 3d-based device showed the best performance: η = 8.30%, J(SC) = 16.0 mA·cm(-2), V(OC) = 717 mV, and ff = 0.72. These values are better than N3-based device.

  4. 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


    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.

  5. Structural, spectroscopic, magnetic and electrochemical studies of monomer N-substituted-sulfanilamide copper (II) complex with 2,2‧-bipyridine (United States)

    Öztürk, Filiz; Bulut, İclal; Bulut, Ahmet


    A novel copper (II) complex of sulfamethazine (4-amino-N-[4,6-dimethyl-2-pyrimidinyl] benzene sulfonamide, Hsmz) ([Cu(smz)2bipy]ṡ0.8H2O; bipy: 2,2‧-bipyridine) has been synthesized and characterized by single crystal X-ray diffraction, EPR, IR, UV-vis and electrochemical methods. The single crystal X-ray analysis indicated that the compound crystallizes in the monoclinic space group P21/c with Z = 4. The central copper (II) ion is coordinated by two bidentate sulfamethazine anions through the nitrogen atoms together with one bidentate 2,2‧-bipyridine ligand forming the octahedral geometry. The characteristic vibration bands support the X-ray analysis results. The EPR spectral analysis has led to that the ground state wave function of the unpaired electron of copper ion is dx2-y2 (2B1g state) and also indicated that the metal ions are located in distorted octahedral sites (D4h) elongated along the z-axis. The electrochemical studies of the complex were also carried out to determine the active sites of the ligands. The cyclic and square wave voltammetric techniques have been used to determine the complex.

  6. Photophysical Studies of Ru(II)tris(2,2`-bipyridine) Confined within a Zn(II)-Trimesic Acid Polyhedral Metal-Organic Framework

    Energy Technology Data Exchange (ETDEWEB)

    Larsen, Randy W; Wojtas, Lukasz [USF


    The ability to confine photoactive catalysts within metal-organic framework (MOF) materials affords the opportunity to expand the functional diversity of these materials into solar based applications. Here, the confinement of Ru(II)tris(2,2'-bipyridine) (RuBpy) by a MOF material derived from Zn(II) ions and trimesic acid (hereafter, USF2) is examined. Although the encapsulated RuBpy could not be crystallographically resolved within the MOF framework, the photophysical properties of the complex are characteristic of confinement including extended triplet metal-to-ligand (3MLCT) lifetime (τethanol = 614 ns and {τUSF2 = 1.2 μs at 25 °C) and a slight hypsochromic shift in the steady-state emission spectrum relative to RuBpy in ethanol. The extended lifetime is attributed to a deactivation of a nonradiative 3dd that is antibonding with respect to the Ru(II)-bipyridine due to a confined molecular environment. These results represent one of the first examples of RuBpy encapsulation and photophysical characterization within a polyhedral MOF material.

  7. Luminescent cyclometalated alkynylgold(III) complexes with 6-phenyl-2,2'-bipyridine derivatives: synthesis, characterization, electrochemistry, photophysics, and computational studies. (United States)

    Au, Vonika Ka-Man; Lam, Wai Han; Wong, Wing-Tak; Yam, Vivian Wing-Wah


    A novel class of luminescent gold(III) complexes containing various tridentate cyclometalating ligands derived from 6-phenyl-2,2'-bipyridine and alkynyl ligands, [Au(RC^N^N)(C≡C-R')]PF(6), has been successfully synthesized and characterized. One of the complexes has also been determined by X-ray crystallography. Electrochemical studies show a ligand-centered reduction originated from the cyclometalating RC^N^N ligands as well as an alkynyl-centered oxidation. The electronic absorption and photoluminescence properties of the complexes have also been investigated. In acetonitrile at room temperature, the complexes show intense absorption at higher energy region with wavelength shorter than 320 nm, and a moderately intense broad absorption band at 374-406 nm, assigned as the metal-perturbed intraligand π-π* transition of the cyclometalating RC(∧)N(∧)N ligand, with some charge transfer character from the aryl ring to the bipyridine moiety. Most of the complexes have been observed to show vibronic-structured emission bands at 469-550 nm in butyronitile glass at 77 K, assigned to an intraligand excited state of the RC^N^N ligand, with some charge transfer character from the aryl to the bipyridyine moiety. Insights into the origin of the absorption and emission have also been provided by density functional theory (DFT) and time-dependent density functional theory (TDDFT) calculations.

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

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


    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 a peak was observed at 0.34 V. The calibration curve was linear in the concentration range from 0.05 μM to 1 μM Ag(I) with a detection limit of 0.025 μM and RSD = 3.6%, for 0.4 μM Ag(I). The presence of several common ions in more than 125-fold excess had no effect on the determination of Ag(I). The developed sensor was applied to the determination of Ag(I) in water samples using a standard addition method. PMID:22163530

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

    Directory of Open Access Journals (Sweden)

    Gabriel Lucian Radu


    Full Text Available 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 a peak was observed at 0.34 V. The calibration curve was linear in the concentration range from 0.05 μM to 1 μM Ag(I with a detection limit of 0.025 μM and RSD = 3.6%, for 0.4 μM Ag(I. The presence of several common ions in more than 125-fold excess had no effect on the determination of Ag(I. The developed sensor was applied to the determination of Ag(I in water samples using a standard addition method.

  10. Crystal Structure and Magnetic Property of a Two-dimensional Manganese Compound [Mn(PhCOO)2(4,4'-bipyridine)]n

    Institute of Scientific and Technical Information of China (English)

    CHEN Hui; WANG Wen-Guo; MA Cheng-Bing; CHEN Chang-Neng; LIU Qiu-Tian; LIAO Dai-Zheng; LI Li-Cun


    A new two-dimensional polymeric manganese compound [Mn(PhCOO)2(4,4'-bipyridine)]n 1 has been prepared and structurally characterized by X-ray diffraction. The complex crystallizes in space group Pbcn with a = 18.7158(2), b = 11.6919(3), c = 9.4799(2)(A), V = 2074.42(7)(A)3, Z = 4, Mr = 453.34, Dc = 1.452 g/cm3, μ = 0.670 mm-1 and F(000) = 932. The final refinement gave R = 0.0458 and wR = 0.1439 for 1358 observed reflections with Ⅰ> 2σ(Ⅰ). The complex consists of repeating units of Mn(PhCOO)2(4,4'-bipyridine). Each Mn center is sixcoordinated by four carboxylate O atoms of four benzoate anions and two pyridyl N atoms from bipy ligands to furnish a slightly distorted octahedral geometry. The two adjacent Mn atoms are connected by a pair of μ1,3-carboxylate groups to form infinite chains, which are further interlinked by bipy to complete a 2D grid network. The magnetic property of the polymeric complex has also been investigated.

  11. Crystal Structure and Catalytic Behavior in Olefin Epoxidation of a One-Dimensional Tungsten Oxide/Bipyridine Hybrid. (United States)

    Amarante, Tatiana R; Antunes, Margarida M; Valente, Anabela A; Paz, Filipe A Almeida; Pillinger, Martyn; Gonçalves, Isabel S


    The tungsten oxide/2,2'-bipyridine hybrid material [WO3(2,2'-bpy)]·nH2O (n = 1-2) (1) has been prepared in near quantitative yield by the reaction of H2WO4, 2,2'-bpy, and H2O in the mole ratio of ca. 1:2:700 at 160 °C for 98 h in a rotating Teflon-lined digestion bomb. The solid-state structure of 1 was solved and refined through Rietveld analysis of high-resolution synchrotron X-ray diffraction data collected for the microcrystalline powder. The material, crystallizing in the orthorhombic space group Iba2, is composed of a one-dimensional organic-inorganic hybrid polymer, ∞(1)[WO3(2,2'-bpy)], topologically identical to that found in the previously reported anhydrous phases [MO3(2,2'-bpy)] (M = Mo, W). While in the latter the N,N'-chelated 2,2'-bpy ligands of adjacent corner-shared {MO4N2} octahedra are positioned on the same side of the 1D chain, in 1 the 2,2'-bpy ligands alternate above and below the chain. The catalytic behavior of compound 1 for the epoxidation of cis-cyclooctene was compared with that for several other tungsten- or molybdenum-based (pre)catalysts, including the hybrid polymer [MoO3(2,2'-bpy)]. While the latter exhibits superior performance when tert-butyl hydroperoxide (TBHP) is used as the oxidant, compound 1 is superior when aqueous hydrogen peroxide is used, allowing near-quantitative conversion of the olefin to the epoxide. With H2O2, compounds 1 and [MoO3(2,2'-bpy)] act as sources of soluble active species, namely, the oxodiperoxo complex [MO(O2)2(2,2'-bpy)], which is formed in situ. Compounds 1 and [WO(O2)2(2,2'-bpy)] (2) were further tested in the epoxidation of cyclododecene, trans-2-octene, 1-octene, (R)-limonene, and styrene. The structure of 2 was determined by single-crystal X-ray diffraction and found to be isotypical with the molybdenum analogue.

  12. Crystal structure of bis-(2,2'-bi-pyridine-κ(2) N,N')bis-(thio-cyanato-κN)mang-anese(II) 2,2'-bi-pyridine monosolvate. (United States)

    Suckert, Stefan; Jess, Inke; Näther, Christian


    In the crystal structure of the mononuclear title compound, [Mn(NCS)2(C10H8N2)2]·C10H8N2, the Mn(II) cation is coordin-ated in an all-cis configuration by two N-bound thio-cyanate anions and two 2,2'-bi-pyridine ligands within a slightly distorted octa-hedral environment. The asymmetric unit consists of one Mn(II) cation, two thio-cyanate anions and two 2,2'-bi-pyridine ligands, as well as two non-coordinating 2,2'-bi-pyridine ligands that are each located on centres of inversion. In the crystal structure, the discrete [Mn(NCS)2(C10H8N2)2] complex mol-ecules are arranged in such a way that cavities are formed, in which the solvent 2,2'-bi-pyridine mol-ecules are located. Apart from van der Waals forces, there are no remarkable inter-molecular inter-actions present in the crystal structure.

  13. Homoleptic 2,2'-bipyridine metalates(-I) of iron and cobalt, one cocrystallized with an anthracene radical anion and the other with neutral anthracene. (United States)

    Brennessel, William W; Ellis, John E


    Homoleptic 2,2'-bipyridine (bipy) metalates of iron and cobalt have been synthesized directly from the corresponding homoleptic anthracene metalates. In the iron structure, bis[([2.2.2]cryptand)potassium(I)] tris(2,2'-bipyridine)ferrate(-I) anthracene(-I), [K(C18H36N2O6)]2[Fe(C10H8N2)3](C14H10), the asymmetric unit contains one potassium complex cation in a general position, the Fe center and one and a half bipy ligands of the ferrate complex on a crystallographic twofold axis that includes the Fe atom, and one half of an anthracene radical anion whose other half is generated by a crystallographic inversion center. The cations and anions are well separated and the geometry about the Fe center is essentially octahedral. In the cobalt structure, ([2.2.2]cryptand)potassium(I) bis(2,2'-bipyridine)cobaltate(-I) anthracene hemisolvate tetrahydrofuran (THF) disolvate, [K(C18H36N2O6)][Co(C10H8N2)2]·0.5C14H10·2C4H8O, the asymmetric unit contains the cation, anion, and both cocrystallized THF solvent molecules in general positions, and one half of a cocrystallized anthracene molecule whose other half is generated by a crystallographic inversion center. The cation and anion are well separated and the ligand planes in the cobaltate anion are periplanar. Each anthracene molecule is midway between and is oriented perpendicular to a pair of symmetry-related bipy ligands such that aromatic donor-acceptor interactions may play a role in the packing arrangement. The lengths of the bonds that connect the bipy rings support the assertion that the ligands are bipy radical anions in the iron structure. However, in the case of cobalt, these lengths are between the known ranges for a bipy radical anion and a bipy dianion, and therefore no conclusion can be made from the crystallography alone. One cocrystallized THF solvent molecule in the cobalt structure was modeled as disordered over three positions with appropriate geometric and thermal restraints, which resulted in a refined

  14. 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)



    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。

  15. (2,2′-Bipyridine-κ2N,N′bis(N-isopropyl-N-methyldithiocarbamato-κ2S,S′cadmium

    Directory of Open Access Journals (Sweden)

    Nor Asiken Abdul Wahab


    Full Text Available The CdII atom in the title compound, [Cd(C5H10NS22(C10H8N2], exists in an N2S4 donor set defined by two chelating dithiocarbamate anions as well as a 2,2′-bipyridine ligand. The coordination geometry approximates a trigonal prism. The crystal packing features weak C—H...S interactions, leading to linear supramolecular chains along the a axis. The primary connections between these are by π–π stacking interactions [ring centroid distance between centrosymmetrically related pyridyl rings = 3.7455 (10 Å]. Overall, the crystal structure may be described as comprising double layers of molecules that stack along the b axis.

  16. 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


    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.

  17. A new copper(II) complex with 2-thenoyltrifluoroacetone and 2,2-bipyridine: Crystal structure, spectral properties and cytotoxic activity (United States)

    Lopes, P. S.; Paixão, D. A.; de Paula, F. C. S.; Ferreira, A. M. D. C.; Ellena, J.; Guilardi, S.; Pereira-Maia, E. C.; Guerra, W.


    This work reports the synthesis and characterization of a new copper(II) complex with 2-thenoyltrifluoroacetone (HTTA) and 2,2-bipyridine (bipy). The complex was characterized by elemental analysis, UV-Vis, IR and EPR. The crystal structure was determined by single-crystal X-ray diffraction. The copper ion has a distorted square-pyramidal geometry and is coordinated to two bidentate ligands (HTTA and bipy) and a perchlorate ion weakly bonded in the apical position. The crystal packing is stabilized by non-classical hydrogen bonds and weak interactions π-π stacking. In the copper complex, the metal ion binds to HTTA via the oxygen atoms of the β-diketone group and to bipy via its two heterocyclic nitrogens. The title compound inhibits the growth of K562 cells with an IC50 value equal to 28.2 μmol L-1.

  18. Electrogenerated chemiluminescence of tris(2,2' bipyridine)ruthenium(II) using common biological buffers as co-reactant, pH buffer and supporting electrolyte. (United States)

    Kebede, Noah; Francis, Paul S; Barbante, Gregory J; Hogan, Conor F


    A series of aliphatic tertiary amines (HEPES, POPSO, EPPS and BIS-TRIS) commonly used to buffer the pH in biological experiments, were examined as alternative, non-toxic co-reactants for the electrogenerated chemiluminescence (ECL) of tris(2,2'-bipyridine)ruthenium(ii) ([Ru(bpy)3](2+)). These were found to be very attractive as "multi-tasking" reagents, serving not only as co-reactants, but also fulfiling the roles of pH buffer and supporting electrolyte within an aqueous environment; thus significantly simplifying the overall ECL analysis. Sub-nanomolar detection limits were obtained for [Ru(bpy)3](2+) in the presence of BIS-TRIS, making this species an valuable option for co-reactant ECL-based bioanalytical applications.

  19. 4-(2,4-Dichlorophenyl-6-(1H-indol-3-yl-2,2′-bipyridine-5-carbonitrile

    Directory of Open Access Journals (Sweden)

    M. N. Ponnuswamy


    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.

  20. Cyanoacetanilides intermediates in heterocyclic synthesis. Part 6: Preparation of some hitherto unknown 2-oxopyridine, bipyridine, isoquinoline and chromeno[3,4-c]pyridine containing sulfonamide moiety

    Directory of Open Access Journals (Sweden)

    Yousry A. Ammar


    Full Text Available Treatment of cyanoacetanilide derivative 1 with tetracyanoethylene (2 in dioxane/triethylamine furnished 2-pyridone derivative 6. Aminopyridine 9 was obtained by cyclization of compound 1 with ketene dithioacetal 7/EtONa. Cyclocondensation of 1 with malononitrile and/or acetylacetone (1:1 M ratio gave pyridine derivatives 11 and 13. Ternary condensation of compound 1, aliphatic aldehydes and malononitrile (1:1:1 M ratio yielded the 2-pyridones 20a and b. Bipyridines 22a–c were prepared by refluxing of compound 21 with active methylene reagents. Cyclization of chromene derivatives 24 and 28 with malononitrile produced the novel chromeno[3,4-c]pyridine 26 and pyrano[3′,2′:6,7]chromeno[3,4-c]pyridine 29.

  1. Structure of Coordination Polymer,[Zn (bipy) (H2O) 3SO4] · 2H2O (bipy = 4,4'-bipyridine)

    Institute of Scientific and Technical Information of China (English)

    马建方; 刘景福; 邢彦; 贾恒庆; 林永华


    The crystal of the title compound (C10H18N2O9SZn Mr= 407. 69) belongs to the hexagonal system, space group P65 with cell parameters: a= 11. 411(2), c=20. 908(4) A, V=2357.7(7)A 3, Z=6, Dc=1. 723g/cm3, F(000)=1260,μ(MoKα) =1. 743mm-1. The final R and wR factors are 0. 072 and 0. 178 respectively for 1335 observed reflections. In the structure, zinc ions are bridged by 4,4'-bipyridine to form infinite chains. The sheets containing parallel chains stack along a 65 screw axis to give a helical staircase motif. The helical structure is mainly controlled by the hydrogen bonds.

  2. (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


    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...

  3. Aqua-(2,2'-bipyridine-κN,N')[2-(3-thien-yl)malonato-κO,O']zinc(II) dihydrate. (United States)

    Meng, Cai-Xia; Zheng, Xue-Gang; Fu, Feng; Zhang, Xiao-Ning; Zhang, Peng


    In the crystal structure of the title compound, [Zn(C(7)H(4)O(4)S)(C(10)H(8)N(2))(H(2)O)]·2H(2)O, the Zn(II) ion assumes a trigonal-bipyramidal coordination geometry completed by two N atoms from a 2,2'-bipyridine ligand, two O atoms from a 2-(3-thien-yl)malonate anion and a water mol-ecule. The S atom of the 2-(3-thien-yl)malonate ligand is disordered over two sites with an occupancy ratio of 0.701 (5):0.299 (5). Inter-molecular O-H⋯O hydrogen bonding is present in the crystal structure.

  4. Aqua(2,2′-bipyridine-κ2N,N′[2-(3-thienylmalonato-κ2O,O′]zinc(II dihydrate

    Directory of Open Access Journals (Sweden)

    Peng Zhang


    Full Text Available In the crystal structure of the title compound, [Zn(C7H4O4S(C10H8N2(H2O]·2H2O, the ZnII ion assumes a trigonal–bipyramidal coordination geometry completed by two N atoms from a 2,2′-bipyridine ligand, two O atoms from a 2-(3-thienylmalonate anion and a water molecule. The S atom of the 2-(3-thienylmalonate ligand is disordered over two sites with an occupancy ratio of 0.701 (5:0.299 (5. Intermolecular O—H...O hydrogen bonding is present in the crystal structure.

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

    Institute of Scientific and Technical Information of China (English)

    Li Chun Xuan; Qing Jiang Pan


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

  6. Chain folding controlled by an isomeric repeat unit: helix formation versus random aggregation in acetylene-bridged carbazole-bipyridine co-oligomers. (United States)

    Divya, Kizhmuri P; Sreejith, Sivaramapanicker; Suresh, Cherumuttathu H; Philips, Divya S; Ajayaghosh, Ayyappanpillai


    An unprecedented, positional effect of the isomeric repeat unit on chain folding in donor–acceptor-linked oligomers, which contain alternating bipyridine and carbazole moieties that are connected through an acetylinic linkage, is reported. 4,4′-Linked oligomer 1 adopts an intrachain helical conformation (CD-active) in CHCl3/MeCN (20:80 v/v), whereas oligomer 2, which contains an isomeric 6,6′-linkage, forms interchain randomly coiled aggregates (CD-inactive). The substitution position plays a significant role in controlling the variations in electronic effects and dipole moments around the bipyridyl moiety, which are responsible for this observed phenomenon. Two model compounds of oligomers 1 and 2 (3 and 4, respectively) were prepared and their properties were compared. A systematic investigation of the photophysical and CD properties of these structures, as well as theoretical studies, support our conclusions.

  7. Microwave-assisted synthesis and crystal structure of oxo(diperoxo)(4,4'-di-tert-butyl-2,2'-bipyridine)-molybdenum(VI). (United States)

    Amarante, Tatiana R; Almeida Paz, Filipe A; Gago, Sandra; Gonçalves, Isabel S; Pillinger, Martyn; Rodrigues, Alírio E; Abrantes, Marta


    The oxodiperoxo complex MoO(O2)(2)(tbbpy) (tbbpy = 4,4'-di-tert-butyl-2,2'- bipyridine) was isolated from the reaction of MoO2Cl(2)(tbbpy) in water under microwaveassisted heating at 120 masculineC for 4 h. The structure of the oxodiperoxo complex was determined by single crystal X-ray diffraction. The Mo(VI) centre is seven-coordinated with a geometry which strongly resembles a highly distorted bipyramid. Individual MoO(O2)(2)(tbbpy) complexes are interdigitated along the [010] direction to form a column. The crystal structure is formed by the close packing of the columnar-stacked complexes. Interactions between neighbouring columns are essentially of van der Waals type mediated by the need to effectively fill the available space.

  8. Microwave-Assisted Synthesis and Crystal Structure of Oxo(diperoxo(4,4'-di-tert-butyl-2,2'-bipyridine-molybdenum(VI

    Directory of Open Access Journals (Sweden)

    Alírio E. Rodrigues


    Full Text Available The oxodiperoxo complex MoO(O22(tbbpy (tbbpy = 4,4'-di-tert-butyl-2,2'- bipyridine was isolated from the reaction of MoO2Cl2(tbbpy in water under microwaveassisted heating at 120 ºC for 4 h. The structure of the oxodiperoxo complex was determined by single crystal X-ray diffraction. The MoVI centre is seven-coordinated with a geometry which strongly resembles a highly distorted bipyramid. Individual MoO(O22(tbbpy complexes are interdigitated along the [010] direction to form a column. The crystal structure is formed by the close packing of the columnar-stacked complexes. Interactions between neighbouring columns are essentially of van der Waals type mediated by the need to effectively fill the available space.

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

    Shi, Fa-Nian; Silva, Ana Rosa; Rocha, João


    The hydrothermal synthesis of a new metal-organic framework (MOF) formulated as Cu 2(4,4'-bpy) 2SO 4·6(H 2O), [abbreviation: (1); bpy or 4,4'-bpy=4,4'-bipyridine; SO 42-=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 SO 42-, 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.

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

    Directory of Open Access Journals (Sweden)

    Fatin Allia Mohamad


    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.

  11. 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.


    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.

  12. Cyclometalated Iridium(III) Complexes Containing 4,4'-π-Conjugated 2,2'-Bipyridine Derivatives as the Ancillary Ligands: Synthesis, Photophysics, and Computational Studies. (United States)

    Sarma, Monima; Chatterjee, Tanmay; Bodapati, Ramakrishna; Krishnakanth, Katturi Naga; Hamad, Syed; Rao, S Venugopal; Das, Samar K


    This article demonstrates a series of cyclometalated Ir(III) complexes of the type [Ir(III)(C^N)2(N^N)](PF6), where C^N is 2-phenylpyridine, and N^N corresponds to the 4,4'-π-conjugated 2,2'-bipyridine ancillary ligands. All these compounds were synthesized through splitting of the binuclear dichloro-bridged complex precursor, [Ir(C^N)2(μ-Cl)]2, with the appropriate bipyridine ligands followed by the anion exchange reaction. The linear and nonlinear absorption properties of the synthesized complexes were investigated. The absorption spectra of all the title complexes exhibit a broad structureless feature in the spectral region of 350-700 nm with two bands being well-resolved in most of the cases. The structures of all the compounds were modeled in dichloromethane using the density functional theory (DFT) algorithm. The nature of electronic transitions was further comprehended on the basis of time-dependent DFT analysis, which indicates that the origins of various bands are primarily due to intraligand charge transfer transitions along with mixed-metal and ligand-centered transitions. The synthesized compounds are found to be nonemissive at room temperature because of probable nonradiative deactivation pathways of the T1 state that compete with the radiative (phosphorescence) decay modes. However, the frozen solutions of compounds Ir(MS 3) and Ir(MS 5) phosphoresce at the near-IR region, the other complexes remaining nonemissive up to 800 nm wavelength window. The two-photon absorption studies on the synthesized complexes reveal that values of the absorption cross-section are quite notable and lie in the range of 300-1000 GM in the picosecond case and 45-186 GM in the femtosecond case.

  13. Quantum chemical interpretation of ultrafast luminescence decay and intersystem crossings in rhenium(I) carbonyl bipyridine complexes. (United States)

    Gourlaouen, Christophe; Eng, Julien; Otsuka, Miho; Gindensperger, Etienne; Daniel, Chantal


    Ultrafast luminescence decay and intersystem crossing processes through the seven low-lying singlet and triplet excited states of [Re (X)(CO)3(bpy)] (X = Cl, Br, I; bpy = 2,2'-bipyridine) are interpreted on the basis of time-dependent density functional theory (TD-DFT) electronic structure calculations performed in acetonitrile and including spin-orbit coupling (SOC) effects within the zeroth-order approximation. It is shown that the red shift of the lowest part of the spectra by SOC increases from X = Cl (0.06 eV) to X = Br (0.09 eV) and X = I (0.18 eV) due to the participation of the triplet sublevels to the absorption. The six lowest "spin-orbit" states remain largely triplet in character and the maximum of absorption is not drastically affected by SOC. While the energy of the excited states is affected by SOC, the character of these states is not significantly modified: SOC mixes states of the same nature, namely metal-to-ligand-charge-transfer/halide-to-ligand-charge-transfer (MLCT/XLCT). This mixing can be large, however, as illustrated by the S1/T2 (a(1)A″/a(3)A') mixing that amounts to about 50:50 within the series Cl > Br > I. On the basis of the optimized structures of the six lowest excited states an interpretation of the emission signals detected by ultrafast luminescence spectroscopy is proposed. It is shown that whereas the experimental Stokes shift of 6000 cm(-1) observed for the three complexes is well reproduced without SOC correction for the Cl and Br complexes, SOC effects have to be taken into account for the iodide complex. The early signal of ultrafast luminescence detected immediately after absorption at 400 nm to the S2 state, covering the 500-550 nm energy domain and characterized by a decay τ1 = 85 fs (X = Cl) and 128 fs (X = Br), is attributed to S2 calculated at 505 and 522 nm, respectively, and to some extend to T3 by SOC. The intermediate band observed at longer time-scale between 550 and 600 nm with emissive decay time τ2 = 340 fs

  14. Preparation of 2, 2'-bipyridine-4, 4'-dicarbaldehyde Treated with Iodine%碘法制备2,2'-联吡啶-4,4'-二甲醛

    Institute of Scientific and Technical Information of China (English)

    张立攀; 翟凤英; 左超凡


    2,2'-bipyridine-4,4'-dicarbaldehyde was synthesized from 4,4'-dimethyl-2,2'-bipyridine by treated with iodine and dimethylsulfoxide as oxidation system. The characterization of structure was confirmed by melt point and mass spectrometry,and the optimum conditions were obtained through the improvement.%以4,4’-二甲基-2,2’-联吡啶为原料,以单质碘和二甲亚砜混合体系,直接处理得到了2,2'-联吡啶-4,4'-二甲醛,通过熔点和质谱对产物结构进行了表征,并进一步优化,得到最佳工艺条件.

  15. Crystal structures of [Ln(NO33(μ2-bpydo2], where Ln = Ce, Pr or Nd, and bpydo = 4,4′-bipyridine N,N′-dioxide: layered coordination networks containing 44 grids

    Directory of Open Access Journals (Sweden)

    Michael L. Stromyer


    Full Text Available Three isostructural coordination networks of Ce, Pr, and Nd nitrate with 4,4′-bipyridine N,N′-dioxide (bpydo are reported, namely poly[[tris(nitrato-κ2O,O′cerium(III]-bis(μ2-4,4′-bipyridine N,N′-dioxide-κ2N:N′], [Ce(NO33(C10H8N2O22], poly[[tris(nitrato-κ2O,O′praeseodymium(III]-bis(μ2-4,4′-bipyridine N,N′-dioxide-κ2N:N′], [Pr(NO33(C10H8N2O22], and poly[[tris(nitrato-κ2O,O′neodymium(III]-bis(μ2-4,4′-bipyridine N,N′-dioxide-κ2N:N′], [Nd(NO33(C10H8N2O22]. All three compounds are isostructural to the previously reported La analogue. The asymmetric unit of [Ln(NO33(μ2-bpydo2] contains one lanthanide cation, two bpydo ligands, and three nitrate anions. Both bpydo ligands act as end-to-end μ2-bridges and display nearly ideal cis and gauche conformations, respectively. The bpydo ligands link the ten-coordinate LnIII cations, forming interdigitating 44 grid-like layers extending parallel to (-101, where interdigitation of layers is promoted by C—H...O interactions between nitrate anions and bpydo ligands. The interdigitated layers are linked to sets of neighboring layers via further C—H...O and π–π interactions.

  16. Ion-pair triple helicates and mesocates self-assembled from ditopic 2,2 -bipyridine-bis(urea) ligands and Ni(II) and Fe(II) sulfate salts

    Energy Technology Data Exchange (ETDEWEB)

    Custelcean, Radu [ORNL; Bonnesen, Peter V [ORNL; Roach, Benjamin D [ORNL; Duncan, Nathan C [ORNL


    NiSO{sub 4} and FeSO{sub 4} self-assemble with heteroditopic ligands (L) comprising 2,2{prime}-bipyridine and o-phenylene-(bis)urea cation- and anion-binding sites, respectively, into [ML{sub 3}SO{sub 4}] (M = Ni{sup 2+}, Fe{sup 2+}) triple-stranded ion-pair helicates and mesocates.

  17. Correlation of the solid-state reactivities of racemic 2,4(6)-di-O-benzoyl-myo-inositol 1,3,5-orthoformate and its 4,4'-bipyridine cocrystal with their crystal structures. (United States)

    Tamboli, Majid I; Bahadur, Vir; Gonnade, Rajesh G; Shashidhar, Mysore S


    Racemic 2,4(6)-di-O-benzoyl-myo-inositol 1,3,5-orthoformate, C21H18O8, (1), shows a very efficient intermolecular benzoyl-group migration reaction in its crystals. However, the presence of 4,4'-bipyridine molecules in its cocrystal, C21H18O8·C10H8N2, (1)·BP, inhibits the intermolecular benzoyl-group transfer reaction. In (1), molecules are assembled around the crystallographic twofold screw axis (b axis) to form a helical self-assembly through conventional O-H···O hydrogen-bonding interactions. This helical association places the reactive C6-O-benzoyl group (electrophile, El) and the C4-hydroxy group (nucleophile, Nu) in proximity, with a preorganized El···Nu geometry favourable for the acyl transfer reaction. In the cocrystal (1)·BP, the dibenzoate and bipyridine molecules are arranged alternately through O-H···N interactions. The presence of the bipyridine molecules perturbs the regular helical assembly of the dibenzoate molecules and thus restricts the solid-state reactivity. Hence, unlike the parent dibenzoate crystals, the cocrystals do not exhibit benzoyl-transfer reactions. This approach is useful for increasing the stability of small molecules in the crystalline state and could find application in the design of functional solids.

  18. 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


    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.

  19. 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


    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.

  20. Catena-dichloro(4,4?-dimethyl-2,2?-bipyridine) Cadmium(II), a New One-dimensional Chain with Blue Fluorescent Emission

    Institute of Scientific and Technical Information of China (English)

    ZHANG Gui-Ling; LI Yan-Tuan; LUO Xu-Qiang; WU Zhi-Yong


    A new μ-chloro-bridged one-dimensional coordination polymer [Cd(dmbpy)Cl2]n (dmbpy = 4,4?-dimethyl-2,2?-bipyridine) has been synthesized and structurally characterized by elemental analyses, IR, UV spectra and single-crystal X-ray diffraction. The complex crystallizes in the monoclinic system, space group C2/c with a = 17.745(4), b = 10.326(2), c = 7.3382(15) ?, β = 106.85(3)o, V = 1286.9(4) ?3, Z = 4, C12H12N2Cl2Cd, Mr = 367.54, Dc = 1.897 g/cm3, F(000) = 720, λ(MoK() = 0.71073 ?, ( = 2.089 mm-1, R = 0.0368 and wR = 0.1048 for 1041 observed reflections (I > 2σ(I)). Cadmium(II) adopts a distorted octahedral coordination geometry and adjacent coordination chains are intercalated in a zipper-like fashion into 2D layers through the π-π stacking interactions between dmbpy. Fluorescent analyses show that it exhibits intense blue photoluminescence in both DMF and DMSO solutions at room temperature.

  1. Synthesis and Crystal Structure of a Novel Layered Lead(Ⅱ) Carboxylate-sulfonate Compound Templated by 4,4'-Bipyridine

    Institute of Scientific and Technical Information of China (English)

    YING Shao-Ming; LUO Qiu-Yan; XU Ya-Ping; LIN Jun-Yue; HUANG Gan-Sheng


    A new lead(Ⅱ) carboxylate-sulfonate has been hydrothermally synthesized and characterized by X-ray single-crystal and elemental analyses. It crystallizes in triclinic, space group P,(1) with a=8.1573(6), b=9.4663(7), c=12.7488(9) (A), α=89.2320(10), β=80.7380(10), γ=77.9760(10)°, Z=2, V=950.10(12) (A)3, Mr=599.57, Dc=2.096 g/cm3, μ=9.032 mm-1, F(000)=572, the final R=0.0412 and wR=0.1035. It has a 1D chain structure, and the Pb(Ⅱ) is six-coordinated. Two PbO6 polyhedra are interconnected via edge-sharing into a two-core unit. Such units are further interconnected by 3-sulfonato-benzoic acids into 1D chains which are linked by hydrogen bonds into a layer structure. The 4,4'-bipyridines are located at the interlayer space and link the layers into a supramolecular structure by π-π stacking interactions.

  2. Spectrophotometric Determination of Iron(II after Solid Phase Extraction of Its 2,2′ Bipyridine Complex on Silica Gel-Polyethylene Glycol

    Directory of Open Access Journals (Sweden)

    Nahid Pourreza


    Full Text Available A new solid phase extraction procedure was developed for preconcentration of iron(II using silica gel-polyethylene glycol (silica-PEG as an adsorbent. The method is based on retention of iron(II as 2,2′ bipyridine complex on silica-PEG. The retained complex is eluted by 1.0 mol L−1 of sulfuric acid-acetone mixture (1:2 and its absorbance is measured at 518 nm, spectrophotometrically. The effects of different parameters such as pH, concentration of the reagent, eluting reagent, sample volume, amount of adsorbent, and interfering ions were investigated. The calibration graph was linear in the range of 1–60 ng mL−1 of iron(II. The limit of detection based on 3Sb was 0.57 ng mL−1 and relative standard deviations (R.S.D for ten replicate measurements of 12 and 42 ng mL−1 of iron(II were 2.4 and 1.7%, respectively. The method was applied to the determination of of iron(II in water, multivitamin tablet, and spinach samples.

  3. Synthesis, crystal structure and photoelectric property of two new coordination polymers constructed by longer-spanning suberic acid and 4,4'-bipyridine ligands. (United States)

    Xie, Yan; Bai, Feng Ying; Li, Jing; Xing, Yong Heng; Wang, Zhuo; Zhao, Hai Yan; Pu, Zhi Feng; Ge, Mao Fa; Shi, Zhan


    Two-dimensional coordination polymers, [M(C₈H₁₂O₄)(C₁₀H₈N₂)]·H₂O [M=Co (1), Cd (2); C₁₀H₈N₂ = 4,4-bipyridine, C₈H₁₄O₄=subaric acid] were obtained from the reaction of the metal salts, bipy and subaric acid at 180°C and characterized by elemental analysis, infrared spectrum, and single-crystal X-ray diffraction and surface photovoltage spectrum (SPS). The single-crystal X-ray diffraction showed that the subaric ligand in the two complexes exhibits two types of modes coordinating to transition metal ions, resulting in the formation of a 1D infinite chain along the c-axis. In addition, the results of SPS for complexes 1 and 2 indicate that these two complexes exhibit positive surface photovoltage responses in the range of 300-800 nm, which can be assigned to LMCT and MLCT, respectively. And the SPS of complex 1 also can be assigned to the d→d* electronic transition. The SPS spectra of the two complexes are consistent with their UV-vis spectra.

  4. 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


    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.

  5. Synthesis and Crystal Structure of a New Mononuclear Cu(II) Complex with 4,4'-Dimethyl-2,2'-bipyridine

    Institute of Scientific and Technical Information of China (English)

    李风华; 高东昭; 吴红星; 林华宽; 朱守荣


    A new mononuclear copper (II) complex,[Cu(dbpy)2Cl]·OH·0.5CH3OH·2H2O (dbpy = 4,4'-dimethyl-2,2'-bipyridine) (C24.50H31ClCuN4O3.50,Mr = 536.52) has been synthesized and its crystal structure was determined by X-ray diffraction method.It crystallizes in monoclinic,space group P2/c with a = 13.383(6),b = 7.653(3),c = 14.164(6)(A),β= 105.395(8)o,V = 1398.7(10)(A)3,Z = 2,Dc = 1.274 g/cm3,(=0.908 mm-1,F(000) = 560 and R = 0.0773 for 1467 observed reflections with I>2б(I).Each copper(II) ion is coordinated by two dbpy and one Cl-ion and the coordination geometry can be described as a distorted trigonal bipyramidal arrangement.

  6. A Microcalorimetry and Spectroscopy Study on the Interaction of BSA with 2,2′-Bipyridine Octylglycinato Palladium(II) Nitrate

    Institute of Scientific and Technical Information of China (English)



    The interaction of bovine serum albumin (BSA) with a new palladium(II) complex [Pd(bpy)(Oct-Gly)]NO3 (bpy, 2,2′-bipyridine; Oct-Gly, octyl-glycine) was studied by isothermal titration UV-visible spectrophotometry and microcalorimetry in 30 mmol/L Tris buffer, pH 7.0. There is a set of 18 binding sites for this complex on BSA at 300 and 310 K with positive cooperativity in the binding process. The Hill coefficients at 300 and 310 K are 2.2 and 2.4, respectively. The binding of this palladium complex on BSA is endothermic with mean association binding constant of 21.0 and 16.4 (mmol/L)-1 at 300 and 310 K, respectively. The complex can denature the protein as surfactants. The stability of BSA in the interaction study with the complex is 84 and 58 kJ/mol at 300 and 310 K, respectively. Also, the enthalpy of BSA denaturation due to the interaction with the complex is 842 kJ/mol.

  7. Synthesis, characterization, and DNA binding and cleavage properties of copper(II)-tryptophanphenyl-alanine-1,10-phenanthroline/2,2'-bipyridine complexes. (United States)

    Reddy, Pulimamidi R; Raju, Nomula; Satyanarayana, Battu


    The mononuclear dipeptide-based Cu(II) complexes [Cu(II) (trp-phe)(phen)(H₂O)] ⋅ ClO₄ (1) and [Cu(II) (trp-phe)(bpy)(H₂O)] ⋅ ClO₄ (2) (trp-phe=tryptophanphenylalanine, phen=1,10-phenanthroline, bpy=2,2'-bipyridine) were isolated, and their interaction with DNA was studied. They exhibit intercalative mode of interaction with DNA. The intercalative interaction was quantified by Stern-Volmer quenching constant (K(sq) =0.14 for 1 and 0.08 for 2). The Cu(II) complexes convert supercoiled plasmid DNA into its nicked circular form hydrolytically at physiological conditions at a concentration as low as 5 μM (for 1) and 10 μM (for 2). The DNA hydrolysis rates at a complex concentration of 50 μM were determined as 1.74 h(-1) (R=0.985) for 1 and 0.65 h(-1) (R=0.965) for 2. The rate enhancement in the range of 2.40-4.10×10⁷-fold compared to non-catalyzed double-stranded DNA is significant. This was attributed to the presence of a H(2) O molecule in the axial position of the Cu complexes.

  8. Molecular structure identification and position of a dopant ion in diaqua(2,2‧-bipyridine)malonatozinc(II) by spectroscopic studies - II: VO(II) (United States)

    Parthipan, Krishnan; Ramesh, Hema; Sambasiva Rao, P.


    Single crystal EPR, optical, FT-IR and powder XRD studies of VO(II) ion doped diaqua(2,2'-bipyridine) malonato zinc complex were carried out at room temperature to ascertain the structural properties. In EPR, the angular variation of vanadium hyperfine lines indicated a single site, with spin Hamiltonian parameters as: g xx = 1.968, g yy = 1.964, g zz = 1.928, A xx = 7.54 mT, A yy = 6.36 mT and A zz = 18.81 mT. In addition, the dopant had entered the lattice in an interstitial position and the position had been identified with the help of atom positions of the host lattice. The EPR and optical data was corroborated to obtain various bonding parameters, from which the nature of the bonding in the complex was discussed. FT-IR and powder XRD studies were used to observe the effect of dopant on structural parameters of the host lattice.

  9. Aqua-(2,2'-bipyridine-κ²N,N')(2-methyl-malonato-κ²O¹,O³)copper(II) dihydrate. (United States)

    Manochitra, P; Manikandan, N; Murugavel, S; Sreeshailam, R; Sambasiva Rao, P


    In the title compound, [Cu(C₄H₄O₄)(C₁₀H₈N₂)(H₂O)]·2H₂O, the Cu(II) ion displays a slightly distorted square-pyramidal coordination. The water mol-ecule at the apical position shows a long bond [Cu-O = 2.276 (2) Å]. The basal plane is formed by two N atoms of the 2,2'-bipyridine ligand and two carboxyl-ate O atoms from a malonate group. The five-membered chelate ring is almost planar [maximum deviation = -0.006 (2) Å], while the six-membered chelate ring defined by the malonate ligand adopts a distorted boat conformation. In the crystal, Cu(II) complex mol-ecules and lattice water mol-ecules are connected by O-H⋯O and C-H⋯O hydrogen bonds. The crystal packing is further stabilized by π-π inter-actions [centroid-centroid distances = 3.563 (2)-3.828 (2) Å].

  10. Hydrothermal Synthesis, Crystal Structure and Photoluminescent Property of a Zinc(II) Coordination Polymer Assembled by Phthalate and 4,4'-Bipyridine

    Institute of Scientific and Technical Information of China (English)

    LI Xiu-Mei; WANG Qing-Wei; CUI Yun-Cheng; LI Chuan-Bi; WANG Ren-Zhang; LIU Bo


    A metal-organic coordination polymer {[Zn(Pht)(4,4′-bipy)(H2O)2]·2H2O}n (Pht = phthalate, 4,4′-bipy = 4,4′-bipyridine) 1 has been hydrothermally synthesized and characterized by elemental analysis, IR, TG, fluorescence spectrum and single-crystal X-ray diffraction. Yellow crystals crystallize in the monoclinic system, space group P2/n, a = 7.6346(14), b = 11.316(2), c = 10.8133(19) (A), β = 92.444(3)o, V = 933.3(3)(A)3, C18H20N2O8Zn, Mr = 457.73, Dc = 1.629 g/cm3, F(000) = 472, Z = 2, μ(MoKα) = 1.367 mm-1, the final R = 0.0323 and wR = 0.0821 for 1859 observed reflections (I > 2σ(I)). The structure of 1 exhibits a two-dimensional bilayer framework formed by hydrogen bonding interactions. Furthermore, 1 shows yellow photoluminescent pro- perty at room temperature.

  11. Crystal structure of [tris(4,4′-bipyridine]diium bis(1,1,3,3-tetracyano-2-ethoxypropenide trihydrate

    Directory of Open Access Journals (Sweden)

    Fatima Setifi


    Full Text Available The title hydrated salt, C30H26N62+·2C9H5N4O−·3H2O, was obtained as an unexpected product from the hydrothermal reaction between potassium 1,1,3,3-tetracyano-2-ethoxypropenide, 4,4′-bipyridine and iron(II sulfate heptahydrate. The cation lies across a twofold rotation axis in the space group I2/a with the other components all in general positions. In the cation, the H atom linking the pyridine units is disordered over two adjacent sites having occupancies of 0.66 (4 and 0.36 (4, i.e. as N—H...N and N...H—N. The water molecules of crystallization are each disordered over two sets of atomic sites, having occupancies of 0.522 (6 and 0.478 (6 for one, and 0.34 (3 and 0.16 (3 for the other, and it was not possible to reliably locate the H atoms associated with these partial-occupancy sites. In the crystal, four independent C—H...N hydrogen bonds link the ionic components into a three-dimensional network.

  12. Crystal Structure of catena-[(Tetrakis-μ2-acetato-μ2-4,4'-bipyridine) dicopper(Ⅱ)] Acetonitrile Solvate

    Institute of Scientific and Technical Information of China (English)

    WEN Yi-Hang; HE Yin-Hua; FENG Yun-Long; NG Seik Weng


    The title compound,[Cu2(CH3COO)4(C8H10N2)]n·nCH3CN1 (C8H10N2,4,4'-bipy = 4,4'-bipyridine),has been solvothermally synthesized in CH3CN and characterized by X-ray diffraction.The crystal is of monoclinic,space group Cc with a = 22.626(6),b = 14.012(4),c =15.106(4) (A),β = 107.610(3)°,V = 4565(2) (A)3,C20H23Cu2N3O8,Mr = 560.49,Z = 8,Dc = 1.631 g/cm3,μ = 1.914 mm-1,Flack parameter = 0.48(1),F(000) = 2288,R = 0.042 and wR = 0.)98 for 8887 observed reflections (I > 2σ(I)).It consists of nearly linear one-dimensional chains [Cu2(CH3COO)4(C8H10N2)]n derived from paddle-wheel [Cu2(CH3COO)4] unit linked by 4,4'-bipy,and CH3CN as guest molecule regularly decorates between the chains.

  13. Distance dependence of bidirectional concerted proton-electron transfer in phenol-Ru(2,2'-bipyridine)3(2+) dyads. (United States)

    Chen, Jing; Kuss-Petermann, Martin; Wenger, Oliver S


    Proton-coupled electron transfer (PCET) was investigated in three covalent donor-bridge-acceptor molecules with different bridge lengths. Upon photoexcitation of their Ru(bpy)3(2+) (bpy=2,2'-bipyridine) photosensitizer in acetonitrile, intramolecular long-range electron transfer from a phenolic unit to Ru(bpy)3(2+) occurs in concert with release of the phenolic proton to pyrrolidine base. The kinetics of this bidirectional concerted proton-electron transfer (CPET) reaction were studied as a function of phenol-Ru(bpy)3(2+) distance by increasing the number of bridging p-xylene units. A distance decay constant (β) of 0.67±0.23 Å(-1) was determined. The distance dependence of the rates for CPET is thus not significantly steeper than that for ordinary (i.e., not proton coupled) electron transfer across the same bridges, despite the concerted motion of oppositely charged particles into different directions. Long-range bidirectional CPET is an important reaction in many proteins and plays a key role in photosynthesis; our results are relevant in the context of photoinduced separation of protons and electrons as a means of light-to-chemical energy conversion. This is the first determination of β for a bidirectional CPET reaction.

  14. Preparation, physicochemical analysis and molecular modeling investigation of 2,2‧-Bipyridine: β-Cyclodextrin inclusion complex in solution and solid state (United States)

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


    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.

  15. 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


    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.

  16. 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:


    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.

  17. 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: [Department of Chemistry, Missouri State University, Springfield, Missouri 65897 (United States)


    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.

  18. Hydrothermal synthesis and structural studies of a new coordination polymer of lanthanum(Ⅲ) with benzene-1,2,4,5-tetracarboxylic acid and 4,4'-bipyridine

    Institute of Scientific and Technical Information of China (English)

    Masoumeh Tabatabaee; Mahboubeh A. Sharif; Fatemeh Vakili; Saina Saheli


    A new lanthanum complex formulated as { (bpyH2)[La(btc)(H2O)4(NO3)]·2H2O }n (1) (btcH4=benzene-1,2,4,5-tetracarboxylic acid; bpy=4,4'-bipyridine) was hydrothermally synthesized. The complex was characterized by FT-IR spectroscopy, elemental analysis and X-ray diffraction. X-ray crystal structural analysis revealed that the compound belonged to the monoclinic space group C2/c with cell parameters a= 1.42806(7) nm, b=1.10258(5) ran, c=-1.60333(8) nm and β=101.9400(10)°. The complex was polymeric with La<Ⅲ atoms linked by four O atoms from two carboxylate groups of one benzene-1,2,4,5-tetracarboxylate. The LaⅢ atom was ten coordinated in a distorted tetracapped trigonal prism. In the crystal structure, a wide range of noncovalent interactions consisting of hydrogen bonding (of the types of O-H…O, N-H…O and C-H…O) and ion pairing interactions connected the various components into a supramolecular structure.

  19. 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


    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.

  20. False positives and false negatives measure less than 0.001% in labeling ssDNA with osmium tetroxide 2,2’-bipyridine

    Directory of Open Access Journals (Sweden)

    Anastassia Kanavarioti


    Full Text Available Osmium tetroxide 2,2’-bipyridine (OsBp is known to react with pyrimidines in ssDNA and preferentially label deoxythymine (T over deoxycytosine (C. The product, osmylated DNA, was proposed as a surrogate for nanopore-based DNA sequencing due to OsBp’s “perfect” label attributes. Osmylated deoxyoligos translocate unassisted and measurably slow via sub-2 nm SiN solid-state nanopores, as well as via the alpha-hemolysin (α-HL pore. Both nanopores discriminate clearly between osmylated and intact nucleobase; α-HL was also shown to discriminate between osmylated T and osmylated C. Experiments presented here confirm that the kinetics of osmylation are comparable for short oligos and long ssDNA and show that pyrimidine osmylation is practically complete in two hours at room temperature with less than 15 mM OsBp. Under the proposed labeling conditions: deoxyoligo backbone degradation measures less than 1/1,000,000; false positives such as osmylated deoxyadenine (A and osmylated deoxyguanine (G measure less than 1/100,000; false negatives, i.e., unosmylated C measure less than 1/10,000; and unosmylated T must measure substantially lower than 1/10,000 due to the 27-fold higher reactivity of T compared to C. However, osmylated C undergoes degradation that amounts to about 1–2% for the duration of the labeling protocol. This degradation may be further characterized, possibly suppressed, and the properties of the degradation products via nanopore translocation can be evaluated to assure base calling quality in a DNA sequencing effort.

  1. Nano optical sensor binuclear Pt-2-pyrazinecarboxylic acid -bipyridine for enhancement of the efficiency of 3-nitrotyrosine biomarker for early diagnosis of liver cirrhosis with minimal hepatic encephalopathy. (United States)

    Attia, M S; Al-Radadi, Najlaa S


    A new, precise, and very selective method for increasing the impact and assessment of 3-nitrotyrosine (3-Nty) as a biomarker for early diagnosis of liver cirrhosis with minimal hepatic encephalopathy (MHE) disease was developed. The method depends on the formation of the ion pair associate between 3-nitrotyrosine and the optical sensor binuclear Pt-2-pyrazinecarboxylic acid (pca)-Bipyridine (bpy) complex doped in sol-gel matrix in buffer solution of pH 7.3. The binuclear Pt (pca)(bpy) has +II net charge which is very selective and sensitive for [3-Nty](-2) at pH 7.3 in serum sample of liver cirrhosis with MHE diseases. 3-nitrotyrosine (3-Nty) quenches the luminescence intensity of the nano optical sensor binuclear Pt(pca) (bpy) at 528nm after excitation at 370nm, pH 7.3. The remarkable quenching of the luminescence intensity at 528nm of nano binuclear Pt(pca) (bpy) doped in sol-gel matrix by various concentrations of the 3-Nty was successfully used as an optical sensor for the assessment of 3-Nty in different serum samples of (MHE) in patients with liver cirrhosis. The calibration plot was achieved over the concentration range 1.85×10(-5) - 7.95×10(-10)molL(-1) 3-Nty with a correlation coefficient of (0.999) and a detection limit of (4.7×10(-10)molL(-1)). The method increases the sensitivity (93.75%) and specificity (96.45%) of 3-Nty as a biomarker for early diagnosis of liver cirrhosis with MHE in patients.

  2. Photophysical properties of [Ru(2,2‧-bipyridine)3]2+ encapsulated within the Uio-66 zirconium based metal organic framework (United States)

    Larsen, Randy W.; Wojtas, Lukasz


    The ability to encapsulate photo-active guest molecules within the pores of metal organic frameworks (MOFs) affords the opportunity to develop robust photocatalysts as well as solar energy conversion systems. An important criteria for such systems is stability of the new materials towards moisture, high temperatures, etc which preclude the use of many MOF frameworks. Here, the ability to encapsulate [Ru(II)(2,2‧-bipyridine)3]2+([Ru(bpy)3]2+) into the cavities of the zirconium based MOF Uio-66 as well as the photophysical properties of the complex are reported. The X-ray powder diffraction data of the orange Uio-66 powder are consistent with the formation of Uio-66 in the presence of [Ru(bpy)3]2+. The steady state emission exhibits a significant bathochromic shift from 603 nm in ethanol to 610 nm in Uio-66. The corresponding emission decay of the encapsulated [Ru(bpy)3]2+ complex is biexponential with a fast component of 128 ns and a slower component of 1176 ns (20 deg C). The slow component is consistent with encapsulation of [Ru(bpy)3]2+ into cavities with restricted volume that prevents the population of a triplet ligand field transition that is anti-bonding with respect to the Ru-N bonds. The origin of the fast component is unclear but may involve interactions of the [Ru(bpy)3]2+ encapsulated within large cavities formed through missing ligand defect sites within the Uio-66 materials. Co-encapsulated quenchers contained within these larger cavities gives rise to the reduced lifetimes of the [Ru(bpy)3]2+ complexes.

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

    Directory of Open Access Journals (Sweden)

    Juan Granifo


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

  4. 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)


    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.

  5. Recognition of self-assembled water-nitrate cluster in a Co(III)-2,2'-bipyridine host: Synthesis, X-ray structure, DNA cleavage, molecular docking and anticancer activity

    Indian Academy of Sciences (India)



    A mononuclear cobalt(III) complex [Co(bpy)₂Cl₂]NO₃·2H₂O (1) (bpy = 2,2'-bipyridine) has been synthesized and crystallographically characterized. Self-assembly of the lattice water molecules from rectangular tetrameric water cluster interacts with nitrate anion along the c-axis forming a six membered hexagonal water-nitrate cluster. It presents a new mode of association of water molecules with nitrate molecules which is not predicted theoretically or found experimentally. The molecule effectively cleaves bacterial genomic DNA and shows important cytotoxicity against human hepatocarcinoma cell (HepG2).

  6. Synthesis, structural characterization, and benzyl alcohol oxidation activity of mononuclear manganese(II) complex with 2,2'-bipyridine: [Mn(bipy)2(ClO4)2


    KANİ, İbrahim; KURTÇA, Mehmet


    A manganese(II) complex of 2,2'-bipyridine (bipy) was synthesized and characterized by X-ray diffraction, IR, and UV-vis spectroscopy. The activity of the complex was tested for oxidation of benzyl alcohols using t-BuOOH as an oxidant in organic solvents and in an organic/water biphasic system (hexane/H2O, toluene/H2O). The effect of solvent, temperature, oxidant, and some additives (KBr, N(C4H9)Br, and N-bromosuccinimide) on the oxidation of benzyl alcohol is reported. The res...

  7. Coordination Chemistry of 2,2'-Bipyridyl- and 2,2':6',2″-Terpyridyl-Substituted BEDT-TTFs: Formation of a Supramolecular Capsule Motif by the Iron(II) Tris Complex of 2,2'-Bipyridine-4-thiomethyl-BEDT-TTF. (United States)

    Wang, Qiang; Martin, Lee; Blake, Alexander J; Day, Peter; Akutsu, Hiroki; Wallis, John D


    Molecules of tris(2,2'-bipyridine-4-thiomethyl-BEDT-TTF)iron(II) (BEDT-TTF = bis(ethylenedithio)tetrathiafulvalene) assemble in pairs to form a novel supramolecular capsular structure in the solid state. Three BEDT-TTF residues from one complex lie in the three grooves between coordinated bipyridines of the other complex, and vice versa, to form a capsule with 3-fold rotational symmetry and an internal volume of ca. 160 Å(3). Further aspects of the coordination chemistry of this ligand, its 6-substituted isomer, and the 2,2':6'2″-terpyridyl-4'-thiomethyl-BEDT-TTF analogue are described.

  8. Octahedral Complexes with Predetermined Helical Chirality: Xylene-Bridged Bis([4,5]-pineno-2,2'-bipyridine) Ligands (Chiragen[o-, m-, p-xyl]) with Ruthenium(II). (United States)

    Mürner, Hansruedi; von Zelewsky, Alex; Stoeckli-Evans, Helen


    Tetradentate ligands are obtained by joining two optically active [4,5]-pineno-2,2'-bipyridine molecules in a stereoselective reaction, where two new stereogenic centers are created. These ligands are new members of the chiragen family that form OC-6 complexes with predetermined helical chirality. Ru(II) complexes with 4,4'-dimethyl-2,2'-bipyridine occupying the remaining coordination sites have been synthesized with all three new ligands. Characterization of the ruthenium complexes by NMR spectroscopy confirm C(2)-symmetric structures in solution. CD spectra show that the complexes are composed of only one helical diastereomer with the expected absolute configurations. In addition, a strong chiral amplification is observed, if precursors of low enantiomeric purity are used. This is due to the inability of ligands that are heterochiral in the two bpy moieties to coordinate to one center. X-ray structural data were obtained for the complex Delta-[RuCG[o-xyl](4,4'-DMbpy)](PF(6))(2). Crystal data (Mo Kalpha, 298 K): trigonal, space group R3, a = 52.986(4) Å, c = 10.545(1) Å, V = 25639(4) Å(3), Z = 18, R1 = 0.087, and wR2 = 0.0986 for 2609 observed reflections.

  9. 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: [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)


    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.

  10. The bipyridine adducts of N-phenyldithiocarbamato complexes of Zn(II) and Cd(II); synthesis, spectral, thermal decomposition studies and use as precursors for ZnS and CdS nanoparticles. (United States)

    Onwudiwe, Damian C; Strydom, Christien A


    Bipyridine adducts of N-phenyldithiocarbamato complexes, [ML(1)2L(2)] (M=Cd(II), Zn(II); L(1)=N-phenyldithiocarbamate, L(2)=2,2' bipyridine), have been synthesized and characterised. The decomposition of these complexes to metal sulphides has been investigated by thermogravimetric analysis (TGA). The complexes were used as single-source precursors to synthesize MS (M=Zn, Cd) nanoparticles (NPs) passivated by hexadecyl amine (HDA). The growth of the nanoparticles was carried out at two different temperatures: 180 and 220 °C, and the optical and structural properties of the nanoparticles were studied using UV-Vis spectroscopy, photoluminescence spectroscopy (PL), transmission emission microscopy (TEM) and powdered X-ray diffraction (p-XRD). Nanoparticles, whose average diameters are 2.90 and 3.54 nm for ZnS, and 8.96 and 9.76 nm for CdS grown at 180 and 220 °C respectively, were obtained.

  11. Synthesis, Crystal Structure, and Magnetic Properties of Tetraphenylarsonium Tetrachloro(oxalato)rhenate(IV) and Bis(2,2'-bipyridine)tetrachloro(&mgr;-oxalato)copper(II)rhenium(IV). (United States)

    Chiozzone, Raúl; González, Ricardo; Kremer, Carlos; De Munno, Giovanni; Cano, Joan; Lloret, Francesc; Julve, Miguel; Faus, Juan


    Two new rhenium(IV) compounds of formula (AsPh(4))(2)[ReCl(4)(ox)] (1) and [ReCl(4)(&mgr;-ox)Cu(bipy)(2)] (2) (AsPh(4) = tetraphenylarsonium cation, ox = oxalate anion, and bipy = 2,2'-bipyridine) have been synthesized and their crystal structures determined by single-crystal X-ray diffraction. 1 and 2 crystallize in the monoclinic system, space groups P2(1)/c and P2(1)/n, respectively, with a = 22.250(5) Å, b = 11.245(3) Å, c = 19.089(4) Å, beta = 96.59(2) degrees, and Z = 4 for 1 and a = 9.421(2) Å, b = 16.909(4) Å, c = 16.179(4) Å, beta = 93.97(2) degrees, and Z = 4 for 2. The structure of 1 is made up of [ReCl(4)(ox)](2)(-) anions and AsPh(4)(+) cations held united by electrostatic forces. Rhenium(IV) is hexacoordinate, with two oxygens of a chelating ox and four chlorine atoms building a distorted octahedron around the metal atom. There is no contact between the [ReCl(4)(ox)](2)(-) anions, the shortest Re.Re and Cl.Cl distances being 10.345 and 7.209 Å, respectively. This anionic complex is coordinated to a [Cu(bipy)(2)](2+) cation in 2, through one oxalate-oxygen, giving a neutral heterometallic dinuclear unit. The Cu(II) ion shows a very distorted five-coordinated geometry, four bipy-nitrogens occuping the equatorial positions and the oxygen atom the apical one. The basal plane geometry is distorted toward the tetrahedron, the dihedral angle between the mean planes of the two bipy ligands is 37.6(2) degrees. These [ReCl(4)(&mgr;-ox)Cu(bipy)(2)] units are arranged in such a way that a chlorine atom of one of them points toward the copper atom of the neighboring one, forming helicoid chains. The intrachain Re.Cu distances through chloro and oxalato bridges are 4.658 and 4.798 Å, respectively. The magnetic behavior of 1 and 2 has been investigated over the temperature range 1.8-300 K. 1 is a magnetically diluted Re(IV) complex, the great value of zero-field splitting of the ground level (D = 60 cm(-)(1)) accounting for the variation of chi(M)T with T in

  12. Multi-dimensional transition-metal coordination polymers of 4,4'-bipyridine-N,N'-dioxide: 1D chains and 2D sheets. (United States)

    Jia, Junhua; Blake, Alexander J; Champness, Neil R; Hubberstey, Peter; Wilson, Claire; Schröder, Martin


    Reaction of 4,4'-bipyridine -N, N' -dioxide (L) with a variety of transition-metal salts in MeOH affords a range of coordination polymer products. For the complexes [FeCl 3(mu-L)] infinity, 1, and ([Cu(L) 2(OHMe) 2(mu-L)].2PF 6. n(solv)) infinity, 2, 1D chain structures are observed, whereas ([Mn(mu-L) 3].2ClO 4) infinity, 3, and ([Cu(mu-L) 3].2BF 4) infinity, 4, both show 2D sheet architectures incorporating an unusual 3 (6)- hxl topology. The more common 4 (4)- sql topology is observed in [Cd(ONO 2) 2(mu-L) 2] infinity, 5, ([Cu(OHMe) 2(mu-L) 2].2ZrF 5) infinity, 6, ([Cu(L) 2(mu-L) 2].2EF 6) infinity ( 7 E = P; 8 E = Sb), and ([Et 4N][Cu(OHMe) 0.5(mu-L) 2(mu-FSiF 4F) 0.5].2SbF 6. n(solv)) infinity, 9. In 6, the [ZrF 5] (-) anion, formed in situ from [ZrF 6] (2-), forms 1D anionic chains ([ZrF 5] (-)) infinity of vertex-linked octahedra, and these chains thread through a pair of inclined polycatenated ([Cu(OHMe) 2(mu-L) 2] (2+)) infinity 4 (4)- sql grids to give a rare example of a triply intertwined coordination polymer. 9 also shows a 3D matrix structure with 4 (4)- sql sheets of stoichiometry ([Cu(L) 2] (2+)) infinity coordinatively linked by bridging [SiF 6] (2-) anions to give a structure of 5-c 4 (4).6 (6)- sqp topology. The mononuclear [Cu(L) 6].2BF 4 ( 10) and [Cd(L) 6].2NO 3 ( 11) and binuclear complexes [(Cu(L)(OH 2)) 2(mu-L) 2)].2SiF 6. n(solv), 12, are also reported. The majority of the coordination polymers are free of solvent and are nonporous. Thermal treatment of materials that do contain solvent results in structural disintegration of the complex structures giving no permanent porosity.

  13. Simultaneous determination of copper, mercury and zinc in water with a tailored fluorescent bipyridine ligand entrapped in silica sol-gel

    Energy Technology Data Exchange (ETDEWEB)

    Lopes Pinheiro, Silvia C. [University of Campinas, Institute of Chemistry, P.O. Box 6154, Campinas (Brazil); Universidad Complutense de Madrid, Optical Chemosensors and Applied Photochemistry Group (GSOLFA), Faculty of Chemistry, Madrid (Spain); Raimundo, Ivo M. [University of Campinas, Institute of Chemistry, P.O. Box 6154, Campinas (Brazil); Moreno-Bondi, Maria C.; Orellana, Guillermo [Universidad Complutense de Madrid, Optical Chemosensors and Applied Photochemistry Group (GSOLFA), Faculty of Chemistry, Madrid (Spain)


    A novel fluorescent ligand, (4-[(E)-2-(4{sup '}-methyl-2,2{sup '}-bipyridin-4-yl)vinyl]phenol) (abbreviated BSOH), has been designed and prepared for simultaneous determination of heavy metals in water. Its photophysical and photochemical properties in the absence and in the presence of Cd(II), Cu(II), Hg(II), Ni(II) and Zn(II) were determined, and the respective complexation constants (7.4 x 10{sup 3}-2.8 x 10{sup 8} l mol{sup -1}) and stoichiometries were extracted thereof. The Stern-Volmer emission intensity and lifetime plots indicate an efficient static quenching of the indicator dye with the heavy metals. The BSOH fluorescent reagent has been successfully immobilised in a silica sol-gel matrix for automation of the analytical method, and the sensing phase demonstrated a reversible response to Cu(II), Hg(II) and Zn(II) but not to Cd(II) and Ni(II). Characterisation of the sensor showed that its response to those heavy metals is linear in the 2.5 to 50 {mu}mol l{sup -1} range, with a response time (t{sub 90}) on the order of 100 min, providing detection limits of 9.0 x 10{sup -7}, 4.7 x 10{sup -7} and 2.9 x 10{sup -7} mol l{sup -1} for Zn(II), Cu(II) and Hg(II), respectively. Due to the stability of the immobilised ligand, which presented no leaching from the sol-gel matrix, the simultaneous determination of the three cations in water was feasible by employing multivariate calibration techniques coupled to fluorescence quenching measurements. The sensor was validated with recovery tests by addition of Cu(II) and Hg(II) ions to spring waters, providing results with standard errors lower than 4.1 {mu}mol l{sup -1}. (orig.)

  14. Channels with ordered water and bipyridine mol-ecules in the porous coordination polymer {[Cu(SiF6)(C10H8N2)2]·2C10N2H8·5H2O} n. (United States)

    Aubert, Emmanuel; Doudouh, Abdelatif; Peluso, Paola; Mamane, Victor


    The coordination polymer {[Cu(SiF6)(C10H8N2)2]·2C10H8N2·5H2O} n , systematic name: poly[[bis-(μ2-4,4'-bi-pyridine)(μ2-hexa-fluorido-silicato)copper(II)] 4,4'-bi-pyridine disolvate penta-hydrate], contains pores which are filled with water and 4,4'-bi-pyridine mol-ecules. As a result of the presence of these ordered species, the framework changes its symmetry from P4/mmm to P21/c. The 4,4'-bi-pyridine guest mol-ecules form chains inside the 6.5 × 6.9 Å pores parallel to [100] in which the mol-ecules inter-act through π-π stacking. Ordered water mol-ecules form infinite hydrogen-bonded chains inside a second pore system (1.6 × 5.3 Å free aperture) perpendicular to the 4,4'-bi-pyridine channels.

  15. Rhodium-Catalyzed/Copper-Mediated Tandem C(sp(2))-H Alkynylation and Annulation: Synthesis of 11-Acylated Imidazo[1,2-a:3,4-a']dipyridin-5-ium-4-olates from 2H-[1,2'-Bipyridin]-2-ones and Propargyl Alcohols. (United States)

    Li, Ting; Wang, Zhiqiang; Xu, Kun; Liu, Wenmin; Zhang, Xu; Mao, Wutao; Guo, Yongming; Ge, Xiaolin; Pan, Fei


    A rhodium-catalyzed/copper-mediated tandem C(sp(2))-H alkynylation and intramolecular annulation of 2H-[1,2'-bipyridin]-2-ones with propargyl alcohols for the synthesis of 11-acylated imidazo[1,2-a:3,4-a']dipyridin-5-ium-4-olates is described.

  16. 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. (United States)

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


    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

  17. A new series of lanthanide coordination polymers with 2,2‧-bipyridine and glutaric acid: Synthesis, crystal structures and properties of [Ln(bipy)(glut)(NO3) (United States)

    Wang, Chunguang; Xing, Yongheng; Li, Zhangpeng; Li, Jing; Zeng, Xiaoqing; Ge, Maofa; Niu, Shuyun


    A series of new lanthanide coordination polymers, with the formula [Ln(bipy)(glut)(NO 3)] (Ln = Eu ( 1), Tb ( 2), Sm ( 3), Pr ( 4); bipy = 2,2'-bipyridine; H 2glut = glutaric acid), have been synthesized under the hydrothermal condition and characterized by elemental analysis, IR spectroscopy, powder X-ray diffraction, and single-crystal X-ray diffraction. Structural analyses reveal that all four complexes are isostructural and crystallized in monoclinic system, P2 1/ c space group. For these complexes, the Ln 3+ are all linked through glutaric acid ligands to form 1D chain-like polymeric structures, and bipy and NO3- are coordinated on two sides of the chains. The thermogravimetric analysis of 1 and photoluminescent properties of 1 and 2 are discussed in detail.

  18. catena-Poly[[bis(μ2-4-aminobenzenesulfonato-κ2O:Odisilver]-bis(μ2-4,4′-bipyridine-κ2N:N′

    Directory of Open Access Journals (Sweden)

    Yong-Qiang Dai


    Full Text Available In the title compound, [Ag2(C6H6NO3S2(C10H8N22]n, the AgI atom is four-coordinated by two N atoms from two symmetry-related 4,4′-bipyridine (bipy and two O atoms from two independent 4-aminobenzenesulfonate (ABS ligands. The two inter-chain AgI atoms are bridged by two independent ABS ligands through weak Ag—O bonds and Ag...Ag attractions, forming a ladder-like chain coordination polymer [Ag2(ABS2(bipy2]n parallel to [001], which is further linked to generate a two-dimensional structure via N—H...O hydrogen-bonding interactions.

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

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


    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.

  20. catena-Poly[[[pentaaquaeuropium(III]-μ-5-sulfonatoisophthalato-κ4O1,O1′:O3,O3′] 4,4'-bipyridine N,N′-dioxide hemisolvate trihydrate

    Directory of Open Access Journals (Sweden)

    Ai-Zhi Wu


    Full Text Available In the crystal structure of the title compound, {[Eu(C8H3O7S(H2O5]·0.5C10H8N2O2·3H2O}n, the EuIII coordination polymer displays a ribbon motif as the 5-sulfoisopthalate anion uses one of carboxyl –CO2 units to chelate to a Eu atom and the other to bind to other two Eu atoms; the sulfonyl –SO3 unit is not involved in coordination. Adjacent ribbons are linked by O—H...O hydrogen bonds, generating a three-dimensional network. The 4,4′-bipyridine-N,N′-dioxide molecule lies on an inversion centre and is hydrogen-bonded to the complex network. The coordination geometry of the Eu atom is a monocapped square antiprism.

  1. Aqua­(2,2′-bipyridine-κ2 N,N′)[2-(3-thien­yl)malonato-κ2 O,O′]zinc(II) dihydrate (United States)

    Meng, Cai-Xia; Zheng, Xue-Gang; Fu, Feng; Zhang, Xiao-Ning; Zhang, Peng


    In the crystal structure of the title compound, [Zn(C7H4O4S)(C10H8N2)(H2O)]·2H2O, the ZnII ion assumes a trigonal–bipyramidal coordination geometry completed by two N atoms from a 2,2′-bipyridine ligand, two O atoms from a 2-(3-thien­yl)malonate anion and a water mol­ecule. The S atom of the 2-(3-thien­yl)malonate ligand is disordered over two sites with an occupancy ratio of 0.701 (5):0.299 (5). Inter­molecular O—H⋯O hydrogen bonding is present in the crystal structure. PMID:21578631

  2. 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


    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.

  3. Tuning the Excited—state Properties of Cyclometalated Platinum(Ⅱ)Complexes of 6—Pheny1—2,2’bipyridine by Ancillary Acetylide Ligand

    Institute of Scientific and Technical Information of China (English)

    吴梓新; 吴骊珠; 杨清正; 张丽萍; 佟振合


    A series of luminescent cyclometalated platinum(Ⅱ)complexes,(CNN)Pt(C≡CR)[HCNN=4-(4-tolyl)-6-phenyl-2,2’-bipyridine;R=4-chlorophenyl(1),phenyl(2) and 4-tolyl(3)],were synthesized,and their spectroscopic properties have been examined.These complexes are brightly emissive both in fluid solution and in the solid state,attributed to triplet metal-to-ligand charge transfer(3MLCT)state.The excited state energy can be tuned by ancillary acetylide ligands.The emission lifetimes in dichloromethand solution at room temperature were up to 1.64 μs and the emission quantum yields were in the range of 0.03-0.15.

  4. 1.2.4. Synthesis, crystal structure and thermal stability property of Ni(aze(4,4′ –bipy(H2O based on longer-spanning azelaic acid and 4,4′ -bipyridine ligands

    Directory of Open Access Journals (Sweden)

    Ge Song, Feng Ying Bai*, Yan Xie, Yong Heng Xing.


    Full Text Available Abstract: One new three-dimensional (3D supramolecular longer-spanning azelaic acid (H2aze complex: Ni(aze(4,4′– bipy(H2O (4,4′-bipy = 4,4′-bipyridine has been synthesized using hydrothermal conditions and characterized by elemental analysis, IR spectroscopy, UV spectrum, powder X-ray diffraction, TG analysis and single crystal X–ray diffraction. Structural analysis reveals that the title complex is six-coordinate and connected by the azelaic acid and 4,4′-bipy ligands to generate a 2D planar structure, further linked through the interaction of hydrogen bond of C–H···O to form a 3D supramolecular structure . Supporting information: FT-IR, UV-Vis, X-Ray, Cif file

  5. 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


    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.

  6. Synthesisand Crystal Structure of a Cu(II) Complex with Reduced Schiff-base N-(2-Hydroxybenzyl)-D,L-alanine and 4,4'-Bipyridine

    Institute of Scientific and Technical Information of China (English)

    ZHENG Da-Gui; HU Jiu-Rong


    A new complex [Cu2(sala)2(H20)2(4,4'-bipy)]'H20 (sala = N-(2-hydroxybenzyl)- D,L-alaninate, 4,4'-bipy = 4,4'-bipyridine) has been synthesized and characterized by elemental analysis, IR spectroscopy, thermogravimetric analysis and single-crystal X-ray diffraction. The complex crystallizes in monoclinic system, space group C2/c with a = 42.44(3), b = 10.416(8), c = 15.487(13) ./k, fl = 97.455(14)°, C30H36Cu2N4O9, Mr = 723.71, V = 6789(9) A3, Dc = 1.416 g/cm3, Z = 8, F(000) = 2992, μ(MoKa) = 1.308 mm-1, R = 0.0493 and wR = 0.1004 for 4878 observed reflections (I 〉 2σ(I)). Structural analysis shows that each copper(II) atom displays a distorted square-based pyramidal coordination geometry with two oxygen atoms and one nitrogen atom from one N-(2-hydroxybenzyl)-D,L-alaninate, one nitrogen atom from 4,4'-bipyridine ligand and one water molecule. 4,4'-Bipyridine ligand bridges two Cu(II) ions to form a dinuclear compound. The molecular structure is extended into a one-dimensional wavy chain through hydrogen bonds. These 1D chains are further expanded into 2D networks through hydrogen bonds.

  7. 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


    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%.

  8. Poly[diaquabis(μ-4,4′-bipyridine-κ2N:N′bis(ethane-1,2-diol-κObis(μ-sulfato-κ2O:O′dicobalt(II

    Directory of Open Access Journals (Sweden)

    Kai-Long Zhong


    Full Text Available In the title compound, [Co2(SO42(C10H8N22(C2H6O22(H2O2]n, there are two crystallographically independent CoII ions, each of which lies on a twofold rotation axis and has a slightly distorted octahedral environment. One CoII ion is coordinated by two N atoms from two bridging 4,4′-bipyridine (4,4′-bipy ligands, two O atoms from two sulfate ions and two O atoms from aqua ligands. The second CoII ion is similar but with ethane-1,2-diol ligands in place of water molecules. The sulfate anions act as bridging ligands to link two adjacent CoII ions together, leading to the formation of linear ...Co1Co2Co1Co2...chains along the a axis. Adjacent chains are further bridged by 4,4′-bipy ligands, which are also located on the twofold rotation axis, resulting in a two-dimensional layered polymer extending parallel to (001. In the crystal, the layers are linked by extensive O—H...O hydrogen-bonding interactions involving the O atoms of the water molecules and ethane-1,2-diol molecules, resulting in a three-dimensional supramolecular network.

  9. Effect of nonionic fluorosurfactant on the electrogenerated chemiluminescence of the tris(2,2'-bipyridine)ruthenium(II)/tri-n-propylamine system: lower oxidation potential and higher emission intensity. (United States)

    Li, Feng; Zu, Yanbing


    Fluorosurfactants are commercially available, and their applications in electrochemical systems have been the interest of many studies. Here, we describe a novel effect of a nonionic fluorosurfactant (Zonyl FSN) on the electrogenerated chemiluminescence (ECL) of the tris(2,2'-bipyridine)ruthenium(II)/tri-n-propylamine (TPrA) system at gold and platinum electrodes. Compared with its hydrocarbon analogue (Triton X-100), the adsorbed fluorosurfactant species not only rendered the electrode surfaces more hydrophobic but also significantly retarded the growth of the electrode oxide layers. As a result, more facile direct oxidation of TPrA was achieved, which led to the appearance of a low oxidation potential ECL signal (below 1.0 V vs SCE). At the gold electrode, the ECL peak appeared at 0.82 V, approximately 400 mV more negative than usual; while its intensity was approximately 50 times higher. The generation of the intense ECL signal at low oxidation potential may lead to the development of more efficient ECL analysis.

  10. Aqua­(2,2′-bipyridine-κ2 N,N′)(2-methyl­malonato-κ2 O 1,O 3)copper(II) dihydrate (United States)

    Manochitra, P.; Manikandan, N.; Murugavel, S.; Sreeshailam, R.; Sambasiva Rao, P.


    In the title compound, [Cu(C4H4O4)(C10H8N2)(H2O)]·2H2O, the CuII ion displays a slightly distorted square-pyramidal coordination. The water mol­ecule at the apical position shows a long bond [Cu—O = 2.276 (2) Å]. The basal plane is formed by two N atoms of the 2,2′-bipyridine ligand and two carboxyl­ate O atoms from a malonate group. The five-membered chelate ring is almost planar [maximum deviation = −0.006 (2) Å], while the six-membered chelate ring defined by the malonate ligand adopts a distorted boat conformation. In the crystal, CuII complex mol­ecules and lattice water mol­ecules are connected by O—H⋯O and C—H⋯O hydrogen bonds. The crystal packing is further stabilized by π–π inter­actions [centroid–centroid distances = 3.563 (2)–3.828 (2) Å]. PMID:22807729

  11. 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.


    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.

  12. New palladium(II) and platinum(II) 5,5-diethylbarbiturate complexes with 2-phenylpyridine, 2,2'-bipyridine and 2,2'-dipyridylamine: synthesis, structures, DNA binding, molecular docking, cellular uptake, antioxidant activity and cytotoxicity. (United States)

    Icsel, Ceyda; Yilmaz, Veysel T; Kaya, Yunus; Samli, Hale; Harrison, William T A; Buyukgungor, Orhan


    Novel palladium(ii) and platinum(ii) complexes of 5,5-diethylbarbiturate (barb) with 2-phenylpyridine (Hppy), 2,2'-bipyridine (bpy) and 2,2'-dipyridylamine (dpya) have been prepared and characterized by elemental analysis, IR, UV-Vis, NMR and ESI-MS. Single-crystal diffraction measurements show that complex consists of binuclear [Pd2(μ-barb-κN,O)2(ppy-κN,C)2] moieties, while complexes are mononuclear, [M(barb-κN)2(L-κN,N')] (L = bpy or dpya). has a composition of [Pt(dpya-κN,N')2][Ag(barb-κN)2]2·4H2O and was assumed to have a structure of [Pt(barb-κN)(Hppy-κN)(ppy-κN,C)]·3H2O. The complexes were found to exhibit significant DNA binding affinity by a non-covalent binding mode, in accordance with molecular docking studies. In addition, complexes and displayed strong binding with supercoiled pUC19 plasmid DNA. Cellular uptake studies were performed to assess the subcellular localization of the selected complexes. A moderate radical scavenging activity of and was confirmed by DPPH and ABTS tests. Complexes , , and showed selectivity against HT-29 (colon) cell line.

  13. Theoretical and experimental spectroscopic studies of the first highly luminescent binuclear hydrocinnamate of Eu(III), Tb(III) and Gd(III) with bidentate 2,2'-bipyridine ligand

    Energy Technology Data Exchange (ETDEWEB)

    Marques, Lippy F.; Correa, Charlane C.; Garcia, Humberto C. [Departamento de Química-ICE, Universidade Federal de Juiz de Fora, Juiz de Fora-MG 36036-330 (Brazil); Martins Francisco, Thiago [Departamento de Física-ICEx, Universidade Federal de Minas Gerais, Pampulha, Belo Horizonte-MG 30123-970 (Brazil); Ribeiro, Sidney J.L. [Instituto de Química, Universidade Estadual Paulista Júlio de Mesquita Filho-UNESP, CP 355, Araraquara-SP 14801-970 (Brazil); Dutra, José Diogo L.; Freire, Ricardo O. [Pople Computational Chemistry Laboratory, Departamento de Química, Universidade Federal de Sergipe, São Cristóvão-SE 49100-000 (Brazil); Machado, Flávia C., E-mail: [Departamento de Química-ICE, Universidade Federal de Juiz de Fora, Juiz de Fora-MG 36036-330 (Brazil)


    In this paper, the synthesis of three new binuclear lanthanide (III) complexes [Ln{sub 2}(cin){sub 6}(bpy){sub 2}] (Ln=Eu (1), Tb (2), Gd (3), cin=hydrocinnamate anion; bpy=2,2'-bipyridine), and their complete characterization, including single crystal X-ray diffraction, FTIR spectroscopy and thermal analysis (TGA/DTA) are reported. In especial, photophysical properties of Eu(III) complex have been studied in detail via both theoretical and experimental approaches. Crystal structures of 1–3 reveal that all compounds are isostructural and that each lanthanide ion is nine-coordinated by oxygen and nitrogen atoms in an overall distorted tricapped trigonal-prismatic geometry. Eu(III) complex structure was also calculated using the Sparkle model for lanthanide complexes and the intensity parameters (Ω{sub 2}, Ω{sub 4}, and Ω{sub 6}), calculated from the experimental data and from Sparkle/PM3 model. The theoretical emission quantum efficiencies obtained for Sparkle/PM3 structures are in excellent agreement with the experimental values, clearly attesting to the efficacy of the theoretical models. The theoretical procedure applied here shows that the europium binuclear compound displays a quantum yield about 65% suggesting that the system can be excellent for the development of efficient luminescent devices. Highlights: • First binuclear Ln{sup 3+}-hydrocinnamate have been synthesized and characterized. • Eu{sup 3+}, Tb{sup 3+} and Gd{sup 3+} complexes photoluminescence properties were investigated. • Theoretical approaches for Eu{sup 3+} complex luminescence has been performed. • An energy level diagram is used to establish the ligand-to-metal energy transfer. • 65% Quantum yield suggests an excellent system for luminescent devices.

  14. 表面修饰的Ag2S纳米微粒的光学非线性特性%Third-Order Nonlinearities of Ag2S Nanoparticles Capped with 2,2’-Bipyridine and Hexametaphosphate

    Institute of Scientific and Technical Information of China (English)

    王刚; 崔一平; 张宇; 汪昕; 傅德刚; 陆祖宏


    用胶体法制备了表面分别修饰六偏磷酸钠(HMP)和2,2’-联吡啶(BPy)的Ag2S纳米微粒。通过背向简并四波混频实验装置对它们在单光子非共振区域的三阶光学非线性进行了实验研究,分别测量了两种Ag2S纳米微粒在它们超滤液中三阶非线性极化率χ(3)随浓度的变化,并拟合得到了两种纳米微粒的三阶非线性极化率。实验结果表明,双光子共振增强是实验中非线性极化的主要过程,同时实验结果也表明了局域场效应对单光子非共振三阶非线性极化率的增强作用。%Two kinds of Ag2S nanoparticles with different surface-capping molecules (2,2’-bipyridine and hexametaphosphate ) were prepared by colloidal chemical method. Their third-order nonlinear optical properties have been studied in non-resonance region of one photon via degenerate four-wave mixing in phase conjugation geometry. The results show that two-photon resonant process greatly contributes to the third-order nonlinearities of Ag2S nanoparticles. It is also found that the third-order susceptibicities χ(3) are intensively subjected to the surface-capping molecules. This phenomenon is interpreted in terms of local field enhancement effect related to refractive index of the media around nanoparticles.

  15. A New 3D Layered-pillared Cobalt(II)-organic Framework Constructed by Imidazole-4,5-dicarboxylic Acid (H_3IDC) and 4,4'-Bipyridine (bipy)

    Institute of Scientific and Technical Information of China (English)

    YUAN Li; LU Wen-Guan


    A new 3D metal-organic framework of {[Co3(IDC)2(bipy)2(py)2]·7H2O}n (1) was obtained by the hydrothermal reaction of Co(NO3)2·6H2O, imidazole-4,5-dicarboxylic acid (H3IDC), 4,4'-bipyridine (bipy), and pyridine (py), and structurally characterized by elemental analysis, infrared spectroscopy, thermal gravimetric analysis, and single-crystal X-ray diffraction. X-ray diffraction crystal structural analysis reveals that it crystallizes in orthorhombic system, space group Pccn with a = 11.1040(3), b = 19.8834(5), c = 21.3025(5), V = 4703.3(2)3, Mr = 1079.63, Z = 4, Dc = 1.525 Mg·m-3, F(000) = 2212, μ(CuKα) = 8.855 mm-1, the final R = 0.0331 and wR = 0.0713 for 2525 observed reflections with I ≥ 2σ(I). In compound 1, each cobalt(II) ion is six-coordinated with a slightly distorted octahedral coordination geometry, and each μ3-IDC3- acts as a bridge to bond three neighboring Co(II) ions, leading to an infinite 2D network layer structure of [Co3(IDC)2]n with Kagomé lattice. The adjacent layers are further linked by μ2-bipy to form an infinite 3D layered-pillared framework architecture of [Co3(IDC)2(bipy)2(py)2]n.

  16. Synthesis, Structure and Fluorescence of a Copper(II) Complex [Cu2(bipy)2(Hpht)2Cl](Hpht) (bipy = 2,2'-Bipyridine, H2pht = o-Phthalic Acid)

    Institute of Scientific and Technical Information of China (English)

    LI Qiang; ZHENG Fa-Kun; CAI Li-Zhen; CHEN Wen-Tong; GUO Guo-Cong; HUANG Jin-Shun


    The title complex [Cu2(bipy)2(Hpht)2Cl](Hpht) (bipy = 2,2’-bipyridine, H2pht = o-phthalic acid) has been synthesized in the NaOH aqueous solution of CuCl2, Gd(NO3)3, bipy and H2pht, and its crystal structure was determined by single-crystal X-ray diffraction method. It crystallizes in triclinic, space group P, C44H31ClCu2N4O12, Mr = 970.26, a = 8.175(2), b = 16.254(4), c = 16.946(4) (A), α = 62.966(6), β = 84.833(8), γ = 84.348(8)°, V = 1993.4(8) (A)3, Z = 2, Dc = 1.616 g/cm3, F(000) = 988 and μ = 1.207 mm-1. The final R = 0.0429 and wR = 0.0843 for 5682 observed reflections with I > 2σ(I). Each copper(II) atom displays a distorted square-pyramidal geometry with two nitrogen atoms of one chelate 2,2’-bipy molecule, two oxygen atoms from two different bridging carboxylate groups of Hphtˉand one bridging chloride atom occupying the apical position. The two copper(II) atoms are connected by a μ2-Cl atom and two bridging Hpht- ligands in a syn-syn coordination mode to form an isolated dinuclear unit. The molecular structure is extended to a one-dimensional wavy chain through hydrogen bonds. The title complex exhibits blue fluorescent emission at 443 nm (λex = 372 nm) in the solid state at room temperature.

  17. Selectivity of bis-triazinyl bipyridine ligands for americium(III) in Am/Eu separation by solvent extraction. Part 1. Quantum mechanical study on the structures of BTBP complexes and on the energy of the separation. (United States)

    Narbutt, Jerzy; Oziminski, Wojciech P


    Theoretical studies were carried out on two pairs of americium and europium complexes formed by tetra-N-dentate lipophilic BTBP ligands, neutral [ML(NO(3))(3)] and cationic [ML(2)](3+) where M = Am(III) or Eu(III), and L = 6,6'-bis-(5,6-diethyl-1,2,4-triazin-3-yl)-2,2'-bipyridine (C2-BTBP). Molecular structures of the complexes have been optimized at the B3LYP/6-31G(d) level and total energies of the complexes in various media were estimated using single point calculations performed at the B3LYP/6-311G(d,p) and MP2/6-311G(d,p) levels of theory. In the calculations americium and europium ions were treated using pseudo-relativistic Stuttgart-Dresden effective core potentials and the accompanying basis sets. Selectivity in solvent extraction separation of two metal ions is a co-operative function of contributions from all extractable metal complexes, which depend on physico-chemical properties of each individual complex and on its relative amount in the system. Semi-quantitative analysis of BTBP selectivity in the Am/Eu separation process, based on the contributions from the two pairs of Am(III) and Eu(III) complexes, has been carried out. To calculate the energy of Am/Eu separation, a model of the extraction process was used, consisting of complex formation in water and transfer of the formed complex to the organic phase. Under the assumptions discussed in the paper, this simple two-step model results in reliable values of the calculated differences in the energy changes for each pair of the Am/Eu complexes in both steps of the process. The greater thermodynamic stability (in water) of the Am-BTBP complexes, as compared with the analogous Eu species, caused by greater covalency of the Am-N than Eu-N bonds, is most likely the main reason for BTBP selectivity in the separation of the two metal ions. The other potential reason, i.e. differences in lipophilic properties of the analogous complexes of Am and Eu, is less important with regard to this selectivity.

  18. 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


    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.

  19. Mononuclear and Binuclear Ruthenium(II) Complexes Containing 2,2'-Bipyridine or 1,10-Phenanthroline and Pyrazole-3,5-Bis(benzimidazole). Synthesis, Structure, Isomerism, Spectroscopy, and Proton-Coupled Redox Activity. (United States)

    Baitalik, Sujoy; Flörke, Ulrich; Nag, Kamalaksha


    A number of mixed-ligand mononuclear and binuclear ruthenium(II) complexes of composition [(bpy)(2)Ru(H(3)pzbzim)](ClO(4))(2).2H(2)O (1), [(phen)(2)Ru(H(3)pzbzim)](ClO(4))(2).3H(2)O (2), [(bpy)(2)Ru(H(2)pzbzim)Ru(bpy)(2)](ClO(4))(3).5H(2)O (3), [(phen)(2)Ru(H(2)pzbzim)Ru(phen)(2)](ClO(4))(3).4H(2)O (4), [(bpy)(2)Ru(H(2)pzbzim)Ru(phen)(2)](ClO(4))(3).4H(2)O (5), [(bpy)(2)Ru(pzbzim)Ru(bpy)(2)](ClO(4)).3H(2)O (6), and [(phen)(2)Ru(pzbzim)Ru(phen)(2)](ClO(4)).2H(2)O (7), where H(3)pzbzim = pyrazole-3,5-bis(benzimidazole), bpy = 2,2'-bipyridine, and phen = 1,10-phenanthroline, have been prepared and characterized. Complexes 3-5 isolated as mixtures of diastereoisomers have been separated by fractional recrystallization. In the cases of 3 and 4, the meso (LambdaDelta) and racemate (rac) (LambdaLambda, DeltaDelta) forms, and for 5, two enantiomeric pairs [(LambdaDelta, DeltaLambda) and (LambdaLambda, DeltaDelta)] have been obtained. These, as well as the meso and rac diastereoisomers of 6, have been characterized by (1)H and (13)C NMR spectroscopy. The crystal structure of the meso (LambdaDelta) form of 3 (C(57)H(53)N(14)Cl(3)O(17)Ru(2)) has been determined, which crystallizes in the monoclinic space group P2(1)/c with a = 11.672(2) Å, b = 41.696(9) Å, c = 12.871(2) Å, beta = 90.03(2)(o), and Z = 4. The acid-base and redox chemistry of the binuclear complexes has been studied over the pH range 1-12 in acetonitrile-water (3:2) medium. The equilibrium constants of the species involving protonation and deprotonation of the benzimidazole NH protons and the metal oxidation states covering +2 and +3 have been evaluated by spectrophotometric and cyclic voltammetric measurements. During spectrophotometric titrations of the complexes with cerium(IV), the metal-to-ligand charge transfer transitions are replaced by the newly generated ligand-to-metal charge transfer transition. The luminescence spectra of the complexes in solution (at 298 K) and in frozen glass (at 77 K) and

  20. 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


    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.

  1. Bis[μ-2-(4-hydroxyphenylacetato]-κ3O,O′:O;κ3O:O,O′-bis{aqua(4,4′-bipyridine-κN[2-(4-hydroxyphenylacetato-κ2O,O′]erbium(III} monohydrate

    Directory of Open Access Journals (Sweden)

    Jia-Lu Liu


    Full Text Available The title dinuclear complex, [Er2(C8H7O36(C10H8N22(H2O2]·H2O, contains two ErIII atoms in the asymmetric unit, six 2-(4-hydroxyphenylacetate (PAA anions, two 4,4′-bipyridine (bipy molecules, two coordinated water molecules and one solvent water molecule. The central ErIII atoms are nine-coordinated. The coordination environment includes six O atoms from three PAA anions, one bridging O atom from a PAA anion, one O atom from a water molecule and an N atom from a bipy ligand in a distorted tricapped trigonal–prismatic geometry. The occurrence of numerous O—H...O and O—H...N hydrogen bonds involving coordinated and noncoordinated water as well as bipy groups builds up an intricate three-dimensional network.

  2. Synthesis and Screening of Modified 6,6'-Bis(5,5,8,8-tetramethyl-5,6,7,8-tetrahydrobenzo[e][1,2,4]triazin-3-yl)-2,2'-bipyridine Ligands for Actinide and Lanthanide Separation in Nuclear Waste Treatment. (United States)

    Afsar, Ashfaq; Distler, Petr; Harwood, Laurence M; John, Jan; Westwood, James


    Effects of chloro and bromo substitution at the 4-position of the pyridine ring of 6,6'-bis(5,5,8,8-tetramethyl-5,6,7,8-tetrahydrobenzo[e][1,2,4]triazin-3-yl)-2,2'-bipyridine (CyMe4-BTBP) have been studied with regard to the extraction of Am(III) from Eu(III) and Cm(III) from 0.1-3 M HNO3. Similarly to CyMe4-BTBP, a highly efficient (DAm > 10 at 3 M HNO3) and selective (SFAm/Eu > 100 at 3 M HNO3) extraction was observed for Cl-CyMe4-BTBP and Br-CyMe4-BTBP in 1-octanol but in the absence of a phase-transfer agent.

  3. Analysis of Binding Properties Between β-Cyclodextrin Bipyridine-ruthenium Derivative and Vitamins by Their Fluorescence Spectra%β-环糊精联吡啶钌衍生物与维生素包络作用的荧光光谱分析

    Institute of Scientific and Technical Information of China (English)

    郑珊珊; 陈红; 祁彦涛; 王秀华; 樊华军; 赵莹莹; 张帆; 杨帆; 汤杰


    This paper presents a research of the binding interaction of a new synthetized β-cyclodextrin bipyridine-ruthenium derivative[β-CD-Ru(bpy) 3] with a series of vitamins using fluorescent spectrometry.The performance of fluorescence emission ofβ-CD-Ru(bpy) 3 was excellent due to the existence of the center of bipyridine-ruthenium.Based on the effect of molecular recognition betweenβ-cyclodextrin and guest molecule,the fluorescence quenching occured because of the energy transfer between theβ-CD-Ru (bpy) 3 and the vitamin when a kind of vitamin was added.According to the quantitative value of fluorescence quenching,the binding constants of the new derivative with respect to various vitamins were determined by Benesi-Hildebrand Equation.The results show that the binding capacities of the vitamins withβ-CD-Ru (bpy) 3 were in a descending sequence of VB12>VK3 >VC>VA.%合成了一种新型的β-环糊精联吡啶钌衍生物[β-CD-Ru(bpy)3],采用分子荧光光谱法研究了该衍生物对一系列维生素的包络作用.β-CD-Ru(bpy)3的结构中含有发光活性基团联吡啶钌中心,因此具有良好的荧光特性.当加入与β-环糊精有主客体识别作用的维生素时,β-CD-Ru(bpy)3与维生素之间发生能量转移从而导致主体分子发生荧光猝灭.采用Benesi-Hildebrand方程,根据其猝灭值计算了该衍生物与各种维生素的包络常数.实验结果表明,维生素与β-CD-Ru(bpy)3包络作用大小顺序为维生素B12>维生素K3>维生素C>维生素A.

  4. A trinuclear cobalt–cerium complex: bis(2,2′-bipyridine-1κ2N,N′;3κ2N,N′-hexa-μ-methacrylato-1:2κ6O:O′;2:3κ6O:O′-nitrato-2κ2O,O′-2-cerium(III-1,3-dicobalt(II

    Directory of Open Access Journals (Sweden)

    Bin Wu


    Full Text Available In the title trinuclear cobalt-cerium complex, [CeCo2(C4H5O26(NO3(C10H8N22], the CeIII and each of the two CoII ions are bridged by three bidentate methacrylate ligands. The CeIII center is coordinated by six O atoms from six methacrylate ligands and two O atoms from the nitrate anion in a distorted square-antiprismatic geometry. Each CoII ion is coordinated by three O atoms from three methacrylate ligands and two N atoms from a 2,2′-bipyridine ligand in a distorted trigonal-pyramidal geometry. In the crystal structure, π–π interactions between the aromatic rings [centroid–centroid distances of 3.816 (8 and 3.756 (8 Å] link the molecules into chains propagated in [01overline{1}]. Weak intermolecular C—H...O hydrogen bonds further stabilize the crystal packing.

  5. Bis(2,2'-bipyridine)[1,9-bis(diphenylphos-phanyl)-1,2,3,4,6,7,8,9-octahydropyrim-ido[1,2-a]pyrimidin-5-ium]ruthenium(II) hexa-fluorido-phosphate dibromide di-chloro-methane disolvate monohydrate. (United States)

    Shang, Congcong; Vendier, Laure; Sutra, Pierre; Igau, Alain


    In the cation of the title complex, [Ru(C31H32N3P2)(C10H8N2)2](PF6)(Br)2·2CH2Cl2·H2O, the ruthenium ion is coordinated in a distorted octa-hedral geometry by two 2,2'-bi-pyridine (bpy) ligands and a chelating cationic N-di-phenyl-phosphino-1,3,4,6,7,8-hexa-hydro-2-pyrimido[1,2-a]pyrimidine [(PPh2)2-hpp] ligand. The tricationic charge of the complex is balanced by two bromide and one hexa-fluorido-phosphate counter-anions. The compound crystallized with two mol-ecules of di-chloro-methane (one of which is equally disordered about a Cl atom) and a water mol-ecule. In the crystal, one of the Br anions bridges two water mol-ecules via O-H⋯Br hydrogen bonds, forming a centrosymmetric diamond-shaped R (4) 2(8) motif. The cation and anions and the solvent mol-ecules are linked via C-H⋯F, C-H⋯Br, C-H⋯Cl and C-H⋯O hydrogen bonds, forming a three-dimensional network.

  6. Linearly Tetrameric Water Cluster Stabilized by Cyano Groups of Multicomplex [Zn(2,2’-bipyridine)3][Zn(CN)4]·2H2O%[Zn(2,2’-bipyridine)3][Zn(CN)4]·2H2O复配物中线型四聚水簇

    Institute of Scientific and Technical Information of China (English)

    曹鹏; 何军


    A hydrothermal reaction of Zn(CN)2, 2,2’-bipyridine(bipy)afforded a novel multicomplex, [Zn(bipy)3][Zn(CN)4]·2H2O(1), which features a 2D supramolecular network assembled from unprecedented linear water tetramers and anionic [Zn(CN)4]2- moieties through intricate hydrogen bonding interactions. Single-crystal X-ray diffraction, FT-IR, thermogravimetric analysis and photoluminescence spectrum of 1 also have been discussed. 1 exhibits strong photoluminescence maximized at 437 nm upon 310 nm excitation at ambient temperature, of which is close to that of the greenish light.%通过水热合成法,利用Zn(CN)2,2,2’-联吡啶合成出一种新颖的复配物[Zn(bipy)3][Zn(CN)4]·2H2O(1),它的特点是通过复杂的氢键作用,将一种结构新颖的线性四聚体水簇和[Zn (CN)4]2-负电基团连接组装成一种二维超分子网络。并对1进行了包括单晶X-射线衍射、红外、热重以及荧光发射在内的表征与分析。研究发现在室温下310 nm的紫外光激发下,1表现出强烈的荧光发射性质,且发射光波长为437 nm,与绿光非常接近。

  7. 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


    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.

  8. Novel thioarsenates {[Mn(2,2'-bipy)2(SCN)][Mn(2,2'-bipy)](As(V)S4)}2 and {[Mn(2,2'-bipy)2(SCN)]2[As(III)2(S2)2S2]}: introducing an anionic second ligand to modify MnII complex cations of 2,2'-bipyridine. (United States)

    Liu, Guang-Ning; Guo, Guo-Cong; Wang, Ming-Sheng; Huang, Jin-Shun


    Two novel manganese thioarsenates, {[Mn(2,2'-bipy)2(SCN)][Mn(2,2'-bipy)](As(V)S4)}2 (1, 2,2'-bipy = 2,2'-bipyridine) and {[Mn(2,2'-bipy)2(SCN)]2[As(III)2(S2)2S2]} (2), containing thiocyanate-modified Mn-2,2'-bipy complex cations were synthesized. They feature two terminal [Mn(2,2'-bipy)2(SCN)](+) complex cations bridged by a polyanion {[Mn(2,2'-bipy)]2(As(V)S4)2}(2-) for 1 and a cyclic thioarsenate anion (As(III)2S6)(2-) for 2. In 2, the [As(III)2(S2)2S2](2-) anion can be described as two (As(III)S3)(3-) trigonal-pyramids interlinked through S-S bonds. The method to obtain new metal complex cations shown here, introducing an anionic second ligand to modify the number of coordination sites and the charges of the metal complex cations simultaneously, is different from the traditional methods, varying either the TM center or the organic ligand or employing mixed neutral organic ligands, and may open up a new route for preparing novel chalcogenidometalates. Compounds 1 and 2 exhibit wide optical gaps of 2.20 and 2.67 eV, respectively, and photoluminescence with the emission maxima occurring around 440 nm. Magnetic measurements show the presence of antiferromagnetic interactions between Mn(II) centers in the two compounds.

  9. Synthesis, Structures and Spectroanalysis of Two Binuclear Copper(Ⅰ)-4,4'-Bipyridine Complexes%两个双核Cu(Ⅰ)-4,4′-联吡啶配合物的合成、结构和光谱分析

    Institute of Scientific and Technical Information of China (English)

    刘春波; 车广波; 李秀颖; 刘梅; 徐占林; 李文连; 王庆伟


    采用乙醚蒸汽扩散法,由四氟合硼酸四乙腈合铜(Ⅰ)、4,4′-联吡啶、二(2-二苯基膦基)苯基醚或者三苯基膦的反应后的二氯甲烷和乙腈混合溶液中,晶化出[Cu2 (4,4′-bipy)(POP) 2 (CH3CN) 2 (C2H5O) 2](BF4) 2 (1)和[Cu2 (4,4′-bipy)(PPH3) 4 (CH3CN) 2](BF4) 2 (2)两种配合物.对它们进行了元素分析和X射线衍射单晶结构表征,同时测定了UV-Vis光谱及相应的激发态寿命.配合物1和2展示了较好的光物理特性.在275 nm紫外光的激发下,固体粉末样品的最大发射峰位分别位于527和483 nm,这归因于金属干扰的配体内部跃迁.%Crystallization from a mixed solution of dichloromethane (CH2Cl2) and acetonitrile (CH3CN) containing copper(Ⅰ) tetrafluroborate, 4,4'-bipyridine (4,4'-bipy) and either bis-[2-(diphenylphosphino)phenyl]ether (POP) or triphenylphosphine (PPH3), by diethyl ether (Et2O) vapour diffusion methods yielded [Cu2 (4,4'-bipy)(POP) 2 (CH3CN) 2(C2H5O)2](BF4) 2 (1) and [Cu2 (4,4'-bipy)(PPH3) 4 (CH3CN) 2](BF4) 2 (2). Both have been characterized through elemental analysis, X-ray diffraction crystal structure analyses, UV-Vis spectroscopy and measurements of excited state lifetime. Complex 1 and 2 exhibit extraordinary photophysical properties. Under excitation of 275 nm, luminescent wavelengths at 527 nm and at 483 nm of the solid state polycrystalline powders of the two complexes were observed, respectively. They are assigned to originate from metal-perturbed intraligand. CCDC: 727759, 1; 727760, 2.

  10. Energy-transfer rate in crystals of double-complex salts composed of [Ru(N-N)3](2+) (N-N = 2,2'-bipyridine or 1,10-phenanthroline) and [Cr(CN)6](3-): effect of relative orientation between donor and acceptor. (United States)

    Otsuka, T; Sekine, A; Fujigasaki, N; Ohashi, Y; Kaizu, Y


    A block single-crystal was obtained using a diffusion method with a concentrated acetone-water (vol. 1/1) solution of [Ru(phen)(3)]Cl(2).6H(2)O (phen = 1,10-phenanthroline) and a concentrated aqueous solution of K(3)[Cr(CN)(6)], without evaporating solvents. The crystal was identified as a double-complex salt including two acetone and fourteen solvent water molecules, [Ru(phen)(3)](2)[Cr(CN)(6)]Cl.2(CH(3))(2)CO.14H(2)O (1). Measurement of the X-ray diffraction pattern of the double-complex salt was performed using an X-ray diffractometer with an Imaging-Plate (IP) Weissenberg camera. 1 crystallizes in the triclinic space group P1, with a = 13.930(5) A, b = 14.783(5) A, c = 11.137(6) A, alpha = 89.87(4) degrees, beta = 107.47(3) degrees, gamma = 96.68(3) degrees, and Z = 2. The crystal structure is very different from that of [Ru(bpy)(3)](2)[Cr(CN)(6)]Cl.8H(2)O (2) (bpy = 2,2'-bipyridine), which could be obtained using the same procedure and crystallizes in the monoclinic space group C2, with a = 22.414(2) A, b = 13.7686(15) A, c = 22.207(2) A, beta = 90.713(8) degrees, and Z = 4. The distance between the central-metal ions of ruthenium(II) and chromium(III) complexes in [Ru(phen)(3)](2)[Cr(CN)(6)]Cl.2(CH(3))(2)CO.14H(2)O (7.170 A) is shorter than that in [Ru(bpy)(3)](2)[Cr(CN)(6)]Cl.8H(2)O (9.173 A) by about 2 A, while the rate of energy transfer from the (3)MLCT state of [Ru(N-N)(3)](2+) to the (2)E(g) state of [Cr(CN)(6)](3-) in the former salt (9.5 x 10(5) s(-1)) is far slower than that in the latter one (6.0 x 10(6) s(-1)) at 77 K. These results indicate that the energy-transfer rate strongly depends, not upon the distance between central metal ions, rather, upon the mutual relative orientation between the donor and the acceptor complexes in double-complex salts.

  11. An unusual double T5(2) water tape trapped in silver(I) coordination polymer hosts: influence of the solvent on the assembly of Ag(I)-4,4'-bipyridine chains with trans-cyclohexanedicarboxylate and their luminescent properties. (United States)

    Li, Ting; Huang, Xi-He; Zhao, Ya-Feng; Li, Hao-Hong; Wu, Shu-Ting; Huang, Chang-Cang


    In this paper, four silver(I) compounds, namely, {[Ag(4)(bipy)(4)(chda)]·2NO(3)·10H(2)O}(n) (1), {[Ag(2)(bipy)(2)(chda)]·14H(2)O}(n) (2), {[Ag(2)(bipy)(2)(chda)]·3EG·2H(2)O}(n) (3) and {[Ag(2)(bipy)(2)(chda)]·H(2)chda}(n) (4) (where bipy = 4,4'-bipyridine, H(2)chda = trans-cyclohexane-dicarboxylate and EG = ethylene glycol), have been synthesized and characterized by single-crystal X-ray diffraction analyses. In all of these compounds, the Ag(I) centers are linked by bipy ligands to form 1D Ag(I)-bipy chain structures. The chda(2-) anions of compound 1 adopt a μ(4)-coordination mode to connect the Ag(I)-bipy chains, forming a H-beam-like chain. In 2, the chda(2-) anions adopt a μ(2)-coordination mode to connect the Ag(I)-bipy chains resulting in two distinct 2D brick wall-like layers. These layers are further stacked in an ···ABAB··· fashion through interlayer π···π stacking interactions giving rise to a 3D framework consisting of quasi-rectangular channels, in which an unusual double T5(2) water tape is trapped. For 3 and 4, the chda(2-) anions show a similar μ(4)-coordination mode to that of 1 and connect the Ag(I)-bipy chains to form 2D grid layers with identical compositions and connective topologies. The experimental studies show that the final structures are greatly influenced by the molar ratio of the components and the solvents, which can be rationally interpreted by the existence of various supramolecular interactions between the host and guest molecules within these compounds through a systematic structural comparison. Additionally, the thermal stability and luminescent properties of these compounds were also studied.

  12. Syntheses and luminescence properties of ternary europium complexes with succinic acid derivative and 2,2'-bipyridine%铕-丁二酸衍生物-2,2'-联吡啶三元配合物的合成和荧光性质研究

    Institute of Scientific and Technical Information of China (English)

    刘胜利; 欧阳涛; 禹良才; 朱金良


    Six temary Eu ( Ⅲ ) complexes were synthesized by using succinic acid ( L1 ) , methyl - succinic acid ( L2 ) , methylene - succinic acid ( L3 ) , mercapto - succinic acid ( L4 ) , bromo - succinic acid ( L5) , hydroxy - succinic acid ( L6) as the first ligand and 2,2' - bipyridine ( bipy) as the second ligand. The compositions of complexes were Eu2 ( L) 3bipy · 2H2O (L = succinic acid and its derivatives) which were characterized by TG -DTG and rare earth compleximetry. Their properties were characterized by means of IR spectra and fluorescence spectra at room temperature. Fluorescence spectroscopy showed that the changes of substituents had small influence on the positions of complexes ' excitation peaks and emission peaks. but large on the fluorescence intensity, and the fluorescence intensity of complexes decreased in the order of substituents: - SH, - Br, - H, - OH, - CH3 , -CH2.%分别以丁二酸(L1)、2-甲基丁二酸(L2)、2-亚甲基丁二酸(L3)、2-巯基丁二酸(L4)、2-澳基丁二酸(L5)、2-羟基丁二酸(L6)为第一配体,2,2-联吡啶(bipy)为第二配体,合成了6种稀土铕的三元配合物,通过差热分析及稀土络合滴定确定了配合物的组成为Eu2(L)3bipy·2H2O(L=丁二酸及其衍生物).通过红外光谱、荧光光谱表征了配合物的性质.对6种配合物进行荧光光谱研究,结果表明:配体取代基的变化对配合物荧光激发蜂和发射蜂的位置变化影响很小,但对配合物的荧光强度有较大影响,其配合物的荧光强度大小为:-SH>-Br>-H>-OH>-CH3>-CH2.

  13. Selective Zn2+ sensing using a modified bipyridine complex

    Energy Technology Data Exchange (ETDEWEB)

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


    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.

  14. 2,2′-Bipyridin-1-ium 3-nitrobenzenesulfonate

    Directory of Open Access Journals (Sweden)

    Orhan Büyükgüngör


    Full Text Available In the title compound, C10H9N2+·C6H4NO5S−, the dihedral angle between the aromatic rings of the cation is 9.42 (7°. In the crystal, the anions and cations are linked by C—H...O and N—H...O hydrogen bonds, generating R21(5 and R44(14 rings, respectively. These hydrogen bonds also provide packing along [110].

  15. Magnetic coupling through the carbon skeleton of malonate in two polymorphs of ([Cu(bpy)(H2O)][Cu(bpy)(mal)(H2O)])(ClO4)2 (H2mal = malonic acid; bpy = 2,2'-bipyridine). (United States)

    Ruiz-Pérez, C; Hernández-Molina, M; Lorenzo-Luis, P; Lloret, F; Cano, J; Julve, M


    Two polymorphic malonato-bridged copper(II) complexes of formula ([Cu(bpy)(H2O)][Cu(bpy)(mal)(H2O)])-(ClO4)2 (1 and 2) (bpy = 2,2'-bipyridine and mal = malonate dianion) have been prepared and their structures solved by X-ray diffraction methods. Compound 1 crystallizes in the monoclinic space group P2(1)/a, with a = 23.743(3) A, b = 9.7522(5) A, c = 27.731(2) A, beta = 114.580(10) degrees, and Z = 4. Compound 2 crystallizes in the orthorhombic space group Pbcn, with a = 23.700(5) A, b = 25.162(5) A, c = 9.693(5) A, and Z = 4. The structures of 1 and 2 are made up of uncoordinated perchlorate anions and malonate-bridged zigzag copper(II) chains grouped in an isosceles triangle running parallel to the b (1) and c (2) axes. These chains are built by a [Cu(bpy)(mal)(H2O)] unit acting as bis-monodentate ligand toward two [Cu(bpy)(H2O)] adjacent units through its OCCCO skeleton in an anti-anti conformation, whereas the OCO carboxylate bridges exhibit the anti-syn conformation. Compounds 1 and 2 contain four crystallographically independent copper(II) atoms, but the environment of all of them is distorted square pyramidal: the axial position is occupied by a water molecule, whereas the equatorial plane is formed by a chelating bpy and either a bidentate malonate or two carboxylate oxygens from two malonate groups. The equatorial Cu-O(mal) (1.911(4)-1.978(4) (1) and 1.897(5)-1.991(4) A (2)) and Cu-N(bpy) (1.983(4)-2.008(5) (1) and 1.971(6)-2.007(6) A (2)) bonds are somewhat shorter than the axial Cu-O(w) one (2.257(5)-2.524(5) (1) and 2.236(5)-2.505(6) A (2)). The angles subtended at the copper atom by the chelating bpy vary in the ranges 80.9(2)-81.8(2) degrees (1) and 80.4(2)-82.1(2) degrees (2), values which are somewhat smaller than those of the chelating malonate (80.4(2)-82.1(2) degrees (1) and 93.0(2)-93.6(2) degrees (2)). The intrachain copper-copper separations through the OCCCO fragment are 8.227(1) (1) and 8.206(2) A (2), whereas those through the OCO bridging

  16. catena-poly[[[(2,2′-bipyridine-2κ2N,N′-μ-cyanido-1:2κ2N:C-cyanido-2κC-tris(methanol-1κO(nitrato-1κ2O,O′iron(IIyttrium(III]-di-μ-cyanido-1:2′κ2N:C;2:1′κ2C:N] methanol solvate hemihydrate

    Directory of Open Access Journals (Sweden)

    Yan Xu


    Full Text Available The title complex, {[FeIIYIII(CN4(NO3(C10H8N2(CH3OH3]·CH3OH·0.5H2O}n, is built up of ladder-like chains oriented along the c axis. Each ladder consists of two strands based on alternating FeII and YIII ions connected by cyanide bridges. Two such parallel chains are connected by additional cyanide anions (the `rungs' of the ladder, which likewise connect FeII and YIII ions, such that each [Fe(bipy(CN4]2− (bipy is 2,2′-bipyridine unit coordinates with three YIII ions and each YIII ion connects with three different [Fe(bipy(CN4]2− units. The FeII atom is six-coordinated in a distorted octahedral geometry and the YIII atom cation is eight-coordinated in a distorted dodecahedral environment. The uncoordinated methanol solvent molecules are involved in hydrogen-bonding interactions with the one terminal cyanide group and a coordinated methanol molecule from another [YIII(NO3(CH3OH3]2+ unit. Adjacent ladder-like chains are also held together by hydrogen bonds between the terminal cyanide ligands of the [Fe(CN4(bipy]2− units in one chain and the OH donors of CH3OH ligands from [YIII(NO3(CH3OH3] units in neighboring chains. The water molecule exhibits half-occupation.

  17. A bi-TTF with a bipyridine spacer: 4,4′-bis[(3,6,7-trimethylsulfanyltetrathiafulvalen-2-ylsulfanylmethyl]-2,2′-bipyridine

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    Jean-Pierre Legros


    Full Text Available The title compound, C30H28N2S16, is a precursor to hybrid magnetic materials. The complete molecule is generated by a crystallographic inversion centre. In the crystal structure, the TTF core is not planar and adopts a chair conformation; the two C3S2 rings are folded around the S...S hinges, the dihedral angles being 17.14 (8 and 13.46 (7°. There is a short S...S contact [3.4863  (14 Å] in the crystal structure.

  18. Novel Coordination Polymers Constructed from 4,4'-Bipyridine and Phosphate

    Institute of Scientific and Technical Information of China (English)

    Kwang-Hwa; Lii


    The synthesis of open-fiamework metal phosphates has been a subject of intense research owing to their interesting structural chemistry and potential applications as ionexchangers, catalysts and adsorbents. A large number of these materials are synthesized in the presence of organic amines as structure-directing agents. Recently, many research activities have focused on the synthesis of inorganic-organic hybrid frameworks. As compared with inorganic ligands, the advantage of using organic multidentate ligands is the efficacy of rational design of crystalline solids through their coordinating propensities and geometries.  ……

  19. 2-(4-Hydroxyphenylacetic acid–4,4′-bipyridine (1/1

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    Jian-Feng Liu


    Full Text Available In the acid molecule of the title complex, C10H8N2·C8H8O3, the acetyl C—C—C—O torsion angle is −32.1 (3°, and in the molecule of the base, the dihedral angle between the two pyridine rings is 23.41 (10°. In the crystal structure, intermolecular O—H...N hydrogen bonds link the acid and the base molecules into a one-dimensional triple-helix framework extended along the b axis.

  20. 4,4′-Di-tert-butyl-2,2′-bipyridine

    Directory of Open Access Journals (Sweden)

    Tatiana R. Amarante


    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.

  1. Novel Coordination Polymers Constructed from 4,4'-Bipyridine and Phosphate

    Institute of Scientific and Technical Information of China (English)


    @@ The synthesis of open-fiamework metal phosphates has been a subject of intense research owing to their interesting structural chemistry and potential applications as ionexchangers, catalysts and adsorbents. A large number of these materials are synthesized in the presence of organic amines as structure-directing agents. Recently, many research activities have focused on the synthesis of inorganic-organic hybrid frameworks. As compared with inorganic ligands, the advantage of using organic multidentate ligands is the efficacy of rational design of crystalline solids through their coordinating propensities and geometries.

  2. 5,5′-Bis[(trimethylsilylmethyl]-2,2′-bipyridine

    Directory of Open Access Journals (Sweden)

    George V. Meehan


    Full Text Available The molecule of the title compound, C18H28N2Si2, occupies a special position on an inversion centre. The Si—CH2—C(ipso plane is approximately orthogonal to the plane of the pyridine rings, the corresponding dihedral angle being 82.0 (2°.

  3. Sensitive fluorescence detection of lysozyme using a tris(bipyridine)ruthenium(II) complex containing multiple cyclodextrins. (United States)

    Zhang, Fan; Zhao, Ying-Ying; Chen, Hong; Wang, Xiu-Hua; Chen, Qiong; He, Pin-Gang


    A new series of photoactive metallocyclodextrins with increased fluorescence intensity upon binding with ssDNAs/aptamers has been demonstrated to sensitively and selectively detect lysozyme. The detection mechanism relies on the formation of an aptamer-lysozyme complex, which leads to reduction of fluorescence intensity.

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

    Indian Academy of Sciences (India)

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


    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.

  5. Ensemble and single-molecule studies on fluorescence quenching in transition metal bipyridine-complexes.

    Directory of Open Access Journals (Sweden)

    Dominik Brox

    Full Text Available Beyond their use in analytical chemistry fluorescent probes continuously gain importance because of recent applications of single-molecule fluorescence spectroscopy to monitor elementary reaction steps. In this context, we characterized quenching of a fluorescent probe by different metal ions with fluorescence spectroscopy in the bulk and at the single-molecule level. We apply a quantitative model to explain deviations from existing standard models for fluorescence quenching. The model is based on a reversible transition from a bright to a dim state upon binding of the metal ion. We use the model to estimate the stability constants of complexes with different metal ions and the change of the relative quantum yield of different reporter dye labels. We found ensemble data to agree widely with results from single-molecule experiments. Our data indicates a mechanism involving close molecular contact of dye and quenching moiety which we also found in molecular dynamics simulations. We close the manuscript with a discussion of possible mechanisms based on Förster distances and electrochemical potentials which renders photo-induced electron transfer to be more likely than Förster resonance energy transfer.

  6. 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: [Laboratório de Radiações em Biologia (Brazil)


    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.

  7. Bis(μ-carboxyl-atoethyl-phospho-nato)bis-[aqua-(2,2'-bipyridine)manganese(II)]. (United States)

    Ying, Shao-Ming; Chen, Yun; Luo, Qiu-Yan; Xv, Ya-Ping; Liu, Dong-Sheng


    The title compound, [Mn(2)(HO(3)PCH(2)CH(2)COO)(2)(C(8)H(8)N(2))(2)(H(2)O)(2)], was obtained by hydro-thermal synthesis. The manganese(II) ions are six-coordinate and are linked by two 2-carboxy-ethyl-phospho-nate ligands, forming a centrosymmetric dimer. The Mn ions adopts a distorted octahedral coordination geometry. The dimers are further linked by O-H⋯O hydrogen bonds and π-π stacking inter-actions [centroid-centroid distance 4.2754 (4) Å].

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

    Directory of Open Access Journals (Sweden)

    Torben Birk


    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

  9. 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: [State Key Laboratory of Electroanalytical Chemistry, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, Changchun, Jilin 130022 (China)


    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.

  10. Hydrothermal Synthesis and Crystal Structure of Manganese(Ⅱ) Coordination Polymer Assembled by 4-Sulfophthalate and 4,4'-Bipyridine

    Institute of Scientific and Technical Information of China (English)


    @@ Introduction The rational design and synthesis of metal-directed supramolecular framework compounds have received much attention in coordination chemistry because of their potential applications in catalysis, molecular selection, nonlinear optics, ion exchange, and microelectronics[1-4].

  11. Multiple analyte response and molecular logic operations by excited-state charge-transfer modulation in a bipyridine integrated fluorophore. (United States)

    Sreejith, Sivaramapanicker; Divya, Kizhumuri P; Manojkumar, T K; Ajayaghosh, Ayyappanpillai


    The tunable excited-state properties of a new donor-π-acceptor-π-donor-type fluorophore 1 with a bipyridyl moiety and its ability to respond to different analytes in solution and on paper microchannels are described. Furthermore, the multiple analyte response of fluorophore 1 has been exploited to perform multiple logic operations. Molecule 1, by virtue of its excited-state charge transfer, exhibits solvatochromism and reversible modulation of its emission in response to multiple chemical inputs, thus resulting in different fluorescent signals. The intraligand charge-transfer (ILCT) emission of 1 at 574 nm has been modulated to three emission outputs by using different chemical inputs, such as Zn(2+), H(+), and ethylenediaminetetraacetic acid (EDTA). Thus, different logic operations such as AND, 2-input-INH, 3-input-INH, IMP, and a combination of these logic operations could be achieved.

  12. 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: [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)


    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.

  13. Efficient degradation of dye pollutants using dioxygen mediated by iron(Ⅱ) 2,2'-bipyridine loaded layered clay catalyst under visible irradiation

    Institute of Scientific and Technical Information of China (English)

    CHENG Mingming; SUN Zhenying; MA Wanhong; CHEN Chuncheng; ZHAO Jincai; WANG Zhengping


    The organic-inorganic layered solid catalyst Fe(bpy)32+-laponite was able to photodegrade Rhodamine B (RhB) by activation of dioxygen under visible irradiation (λ>420 nm), while the homogeneous aqueous solution Fe(bpy)32+ showed no photoactivity. The catalyst could be repeatedly used and retained its reactivity. The hybrid catalyst could be separated from the suspension by centrifugation or sedimentation. The TOC removal yield of RhB was measured. Reactive oxygen species (ROS) formed during degradation was detected by EPR. A possible mechanism was proposed on the basis of the experimental results.

  14. The selectivity of diglycolamide (TODGA) and bis-triazine-bipyridine (BTBP) ligands in actinide/lanthanide complexation and solvent extraction separation - a theoretical approach. (United States)

    Narbutt, Jerzy; Wodyński, Artur; Pecul, Magdalena


    Theoretical calculations (density functional theory with the scalar relativistic ZORA Hamiltonian) have been performed to obtain the energy and Gibbs free energy of formation of cationic 1 : 3 complexes of americium(iii) and europium(iii) with a tri-O-dentate diglycolamide ligand TEDGA (a model of TODGA extractant), as well as the free energy of their partition between water and an organic diluent. The distribution of electron density over the atoms, bonds, and molecular orbitals was analyzed by means of Mulliken population analysis, the localization procedure of natural bond orbitals, and the Quantum Theory of Atoms-in-Molecules. The stabilities of both [M(TEDGA)(3)](3+) complexes are similar to each other. On the other hand, our recent data for a similar pair of cationic Am/Eu complexes with a softer (HSAB) tetra-N-dentate ligand C2-BTBP show that the [Am(C2-BTBP)(2)](3+) complex is significantly more stable in aqueous solution than its Eu counterpart. The decisive factor stabilizing the Am(3+) complexes over their Eu(3+) analogues is the charge transfer from the ligands, somewhat greater on the 6d(Am(III)) than on 5d(Eu(III)) orbitals. The covalency of M-N bonds in the [M(C2-BTBP)(2)](3+) complexes is greater than that of M-O bonds in [M(TEDGA)(3)](3+), but the latter is not negligible, in particular in the bonds with the oxygen atoms of the amide groups in TEDGA. The analysis of charge distribution over the whole molecules of the complexes shows that the TEDGA molecule is not hard as expected, but a relatively soft Lewis base, only slightly harder than BTBP. This conclusion has been confirmed by the calculation of the chemical hardness of the ligands. Moreover, the comparison of the results of bonding analysis with the calculated energies of complex formation in water and in the gas phase allows us to conclude that the population analysis, QTAIM topological parameters, and SOPT stabilization energy, as well as Wiberg and overlap-weighted NAO indices are the tools for analyzing the covalency rather than the total bond strength.

  15. 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)


    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.

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

    DEFF Research Database (Denmark)

    Birk, Torben; Bendix, Jesper


    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....

  17. Co(II), Ni(II), Cu(II) and Zn(II) complexes of a bipyridine bis-phenol conjugate: generation and properties of coordinated radical species. (United States)

    Arora, Himanshu; Philouze, Christian; Jarjayes, Olivier; Thomas, Fabrice


    Four bis-phenolate complexes [Zn(II)L], [Ni(II)L], [Cu(II)L] and [Co(II)L] (where [H(2)L = 2,2'-[2,2']bipyridinyl-6-yl-bis-4,6-di-tert-butylphenol] have been synthesized. The copper(II) and nickel(II) complexes have been characterized by X-ray diffraction, showing a metal ion within a square planar geometry, slightly distorted towards tetrahedral. The cyclic voltametry (CV) curve of [Zn(II)L] consists of a single bi-electronic reversible wave at 0.06 V vs. Fc/Fc(+). The electrochemically generated dication is a diradical species [Zn(II)L˙˙](2+) that exhibits the typical phenoxyl π-π* band at 395 nm. It is EPR-silent due to magnetic interactions between the phenoxyl moieties. The CV curves of [Ni(II)L] and [Cu(II)L] exhibit two distinct ligand-centred one-electron oxidation waves. The first one is observed at E(1/2)(1) = 0.38 and 0.40 V for the nickel and copper complex, respectively, and corresponds to the formation of M(II)-coordinated phenoxyl radicals. Accordingly, [Ni(II)L˙](+) exhibits a strong absorption band at 960 nm and an (S = ½) EPR signal centred at g(iso) = 2.02. [Cu(II)L˙](+) is EPR-silent, in agreement with a magnetic coupling between the metal and the radical spin. In contrast with the other complexes, [Co(II)L] was found to react with dioxygen (mostly in the presence of pyridine), giving rise to a stable (S = ½) superoxo radical complex [Co(III)L(Py)(O(2)˙)]. One-electron oxidation of [Co(II)L] at -0.01 V affords a diamagnetic cobalt(III) complex [Co(III)L](+) that is inert towards O(2) binding, whereas two-electron oxidation leads to the paramagnetic phenoxyl radical species [Co(III)L˙](+) whose EPR spectrum features an (S = ½) signal at g(iso) = 2.00.

  18. 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


    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.

  19. 2,2′-Dimethyl-4,4′-bipyridine

    Directory of Open Access Journals (Sweden)

    Wilhelm Seichter


    Full Text Available In the crystal structure of the title compound, C12H12N2, the molecule is twisted around the central C—C bond, with a dihedral angle of 8.32 (5° between the mean planes of the pyridyl rings. The crystal structure is stabilized by arene stacking interactions, with a distance of 3.81 (1 Å between the ring centroids.

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

    Directory of Open Access Journals (Sweden)

    Chao Hou


    Full Text Available In the title complex, [Zn(C10H7N2O22(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 and a nearby pyridine ring [O...Cg = 3.977 (2 Å, where Cg is the centroid of the pyridine ring] is observed.

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

    Directory of Open Access Journals (Sweden)

    Hoong-Kun Fun


    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.

  2. Syntheses and Characterization of Mixed Ligands Copper(Ⅱ) Complexes Containing L-α-amino Acids and Bipyridines%L-α-氨基酸铜(Ⅱ)-联吡啶混配配合物的合成及表征

    Institute of Scientific and Technical Information of China (English)

    周晓华; 陈实; 黄鹤; 乐学义


    合成了4种氨基酸-铜(Ⅱ) -2,2′-联二吡啶(Bpy)的混配配合物,用元素分析、摩尔电导率、IR和UV-Vis对配合物进行了表征和结构推测.4种混配配合物的组成分别为:[Cu(Bpy)(L-thre)]·ClO4·H2O, [Cu(Bpy)(L-ile)]·ClO4·0.5H2O, [Cu(Bpy)(L-meth)]·ClO4·0.5H2O, [Cu(Bpy)(L-ly)]·ClO4·H2O(L-thre为苏氨酸,L-ile为异亮氨酸,L-meth为蛋氨酸,L-ly为赖氨酸).Bpy和L-氨基酸皆作为双齿配体与中心铜离子发生配位.

  3. Synthesis, Characterization, and Crystal Structure of a Novel Copper(II) Complex with an Asymmetric Coordinated 2,2'-Bipyridine Derivative: A Model for the Associative Complex in the Ligand-Substitution Reactions of [Cu(tren)L](2+)? (United States)

    Lu Zl, Zhong-lin; Duan Cy, Chun-ying; Tian Yp, Yu-peng; You Xz, Xiao-zeng; Huang Xy, Xiao-ying


    The titled compound, (tris(2-aminoethyl)amine)(4,5-diazafluoren-9-one) copper(II) perchlorate, [Cu(C(6)H(18)N(4))(C(11)H(6)N(2)O)(ClO(4))(2)], 1, has been designed, synthesized, and characterized. The electronic and ESR spectra are very different from those of [Cu(tren)L](2+) complexes where L is monodentate ligand. The X-ray analysis revealed that the complex crystallizes in the monoclinic space group P2(1)/c, with a = 10.726(6) Å, b = 14.921(7) Å, c = 14.649(4) Å, beta = 95.13(3) degrees, and Z = 4. The copper(II) ion is coordinated by four nitrogen atoms from tris(2-aminoethyl)amine (tren) and two nitrogen atoms from 4,5-diazafluoren-9-one (dzf) to form an unusual six-coordinate (4 + 1 + 1') geometry. The structure is very rare, and to our knowledge, it is the first example of an asymmetric bidentate phenanthroline derivative metal complex. The structure could be used as a model of the associative complex in the ligand-exchange and ligand-substitution reactions of [Cu(tren)L](2+) and the catalytic mechanisms of enzymes involving copper sites. From the electronic and variable-temperature ESR spectra in solution, the possible mechanism of these reactions has also been proposed. As a comparison, the complex [Cu(tren)(ImH)(ClO(4))(2)], 2, was also synthesized and characterized, where ImH is imidazole.

  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 (United States)

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


    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. Rhenium(IV) compounds inducing apoptosis in cancer cells. (United States)

    Martínez-Lillo, José; Mastropietro, Teresa F; Lappano, Rosamaria; Madeo, Antonio; Alberto, Marta E; Russo, Nino; Maggiolini, Marcello; De Munno, Giovanni


    The anticancer properties of a series of mononuclear Re(IV) compounds of formula ReCl(4)L (where L is bpy = 2,2'-bipyridine; bpym = 2,2'-bipyrimidine; dmbpy = 4,4'-dimethyl-2,2'-bipyridine; phen = 1,10-phenanthroline) were investigated for the first time. All compounds displayed potent in vitro antiproliferative activity against selected cancer cells.

  6. Coupling of the 4f Electrons in Lanthanide Molecules

    Energy Technology Data Exchange (ETDEWEB)

    Kazhdan, Daniel [Univ. of California, Berkeley, CA (United States)


    (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 SmII/SmIII and YbII/YbIII 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&apos

  7. 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


    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.

  8. 1H-吲唑-3-羧酸4,4'-联吡啶钴配合物的合成与表征%Synthesis and Characterization of 4,4'-bipyridine Directed Assembly of Cobalt (Ⅱ) 1H-Indazole-3-Carboxylic Acid Coordination Complex

    Institute of Scientific and Technical Information of China (English)

    肖汉; 李训碧; 周桂; 覃桂芳; 尹显洪


    采用1H-吲唑-3-羧酸(HL)、4,4'-联吡啶(Bpy)及六水氯化钴(CoCl2·6H2O),以水热合成的方法,合成设计了一种新型的吲唑羧酸舍钴的配合物(1) [Co(L)2(Bpy)]n·4nH2O,通过X-射线单晶衍射仪,热重分析仪,场发射扫描电镜,红外光谱仪及电化学工作站等表征手段对配合物(1)的晶体结构及性质进行了研究.

  9. Synthesis and Crystal Structure of Ternary Copper(Ⅱ) Complex Containing N-(2-hydroxybenzyl)-DL-alanine and 4,4'-bipyridine%Cu(Ⅱ)与N-(2-羟苄基)-DL-丙氨酸、4,4'-联吡啶三元配合物的合成与晶体结构

    Institute of Scientific and Technical Information of China (English)

    胡久荣; 梁福沛; 陈自卢


    @@ 近年来,基于金属和有机配体间的配位键合作用来设计和构筑具有多孔结构的超分子体系已成为现代化学、材料科学领域内非常活跃和充满前景的研究主题之一[1].

  10. 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

    Energy Technology Data Exchange (ETDEWEB)

    Distler, P.; Spendlikova, I. [Czech Technical Univ., Prague (Czech Republic). Dept. of Nuclear Chemistry; John, J. [Czech Technical Univ., Prague (Czech Republic). Dept. of Nuclear Chemistry; Czech Technical Univ., Prague (Czech Republic). Centre for Radiochemistry and Radiation Chemistry; Harwood, L.M.; Hudson, M.J.; Lewis, F.W. [Reading Univ., Berkshire (United Kingdom). Dept. of Chemistry


    Several alkylated cyclohexanones were investigated as potential diluents for the selective extraction of Am(III) from Eu(III) from nitric acid solutions by the CyMe{sub 4}-BTBP ligand. No significant extraction of either of the metal ions was observed for these diluents themselves. In the extractions from 1 M HNO{sub 3}, 3-methylcyclohexanone and 4-methylcyclohexanone gave comparable results to cyclohexanone whereas in the extractions from 4 M HNO{sub 3}, 2-methylcyclohexanone, 3-methylcyclohexanone and 4-methylcyclohexanone all gave superior results. For the monomethylated diluents, D{sub Am} and SF{sub Am/Eu} decreased in the order of alkyl substitution 2 > 4 {proportional_to} 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.)

  11. Protein surface recognition using geometrically pure Ru(ii) tris(bipyridine) derivatives† †This article is part of the ‘Emerging Investigators’ themed issue for ChemComm ‡ ‡Electronic supplementary information (ESI) available: Synthetic procedures, characterization and fluorescence binding studies. See DOI: 10.1039/c0cc04754f Click here for additional data file.


    Filby, M.H.; Muldoon, J.; Dabb, Serin; Fletcher, Nick; Ashcroft, A.E.; Wilson, A J


    This manuscript illustrates that the geometric arrangement of protein-binding groups around a ruthenium(II) core leads to dramatic differences in cytochrome c (cyt c) binding highlighting that it is possible to define synthetic receptors with shape complementarity to protein surfaces.

  12. 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;


    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....

  13. Binding of copper(II) polypyridyl complexes to DNA and consequences for DNA-based asymmetric catalysis

    NARCIS (Netherlands)

    Draksharapu, Apparao; Boersma, Arnold J; Leising, Miriam; Meetsma, Auke; Browne, Wesley R; Roelfes, Gerard


    The interaction between salmon testes DNA (st-DNA) and a series of Cu-II polypyridyl complexes, i.e. [Cu(dmbpy)(NO3)(2)] (1) (dmbpy = 4,4'-dimethyl-2,2'-bipyridine), [Cu(bpy)(NO3)(2)] (2) (bpy = 2,2'-bipyridine), [Cu(phen)(NO3)(2)] (3) (phen = phenanthroline), [Cu(terpy)(NO3)(2)]center dot H2O (4) (

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


    Sini, Alessandro


    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...

  15. 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.


    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...

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

    Directory of Open Access Journals (Sweden)

    Pei-Hsuan Chiang


    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.

  17. Hexa-μ-acetato-1:2κ4O,O′;1:2κ2O:O;2:3κ4O,O′;2:3κ2O:O-bis(4,4′-dimethyl-2,2′-bipyridine-1κ2N,N′;3κ2N,N′-2-calcium-1,3-dizinc

    Directory of Open Access Journals (Sweden)

    Md. Alamgir Hossain


    Full Text Available In the centrosymmetric trinuclear ZnII...CaII...ZnII title complex, [CaZn2(CH3COO6(C12H12N22], the CaII ion lies on an inversion centre and is octahedrally coordinated by six acetate O atoms. The ZnII ion is coordinated by two N atoms from a bidentate dimethylbipyridine ligand and three O atoms from acetate ligands bridging to the CaII ion, leading to a distorted square-pyramidal coordination sphere. The Zn...Ca distance is 3.4668 (5 Å.

  18. 4,4′-Bipyridine–trans,trans-hexa-2,4-dienedioic acid (1/1

    Directory of Open Access Journals (Sweden)

    Suk-Hee Moon


    Full Text Available The title cocrystal, C10H8N2·C6H6O4, crystallizes with half-molecules of 4,4′-bipyridine and trans,trans-hexa-2,4-dienedioic acid in the asymmetric unit, as each is located about a crystallographic inversion center. The bipyridine molecule is planar from symmetry. In the dicarboxylic acid molecule, the O—C—C—C torsion angle is −13.0 (2°. In the crystal, O—H...N and C—H...O hydrogen bonds generate a three-dimensional network.

  19. 4,4′-Bipyridine–cyclohexane-1,2,4,5-tetracarboxylic acid (1/1

    Directory of Open Access Journals (Sweden)

    Jian-Qiang Liu


    Full Text Available In the title 1:1 adduct, C10H8N2·C10H12O8, the dihedral angle between the pyridine rings in the 4,4-bipyridine molecule is 8.33 (13°. In the crystal, the cyclohexane-1,2,4,5-tetracarboxylic acid molecules interact with each other through intermolecular O—H...O hydrogen bonds, forming an infinite chain along the a axis, which is further linked perpendicularly by O—H...N hydrogen bonds involving bipyridine, resulting in a supramolecular corrugated sheet parallel to the (110 plane.

  20. 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


    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.

  1. Synthesis of diorganoplatinum(IV) complexes by the Ssbnd S bond cleavage with platinum(II) complexes (United States)

    Niroomand Hosseini, Fatemeh; Rashidi, Mehdi; Nabavizadeh, S. Masoud


    Reaction of [PtR2(NN)] (R = Me, p-MeC6H4 or p-MeOC6H4; NN = 2,2‧-bipyridine, 4,4‧-dimethyl-2,2‧-bipyridine, 1,10-phenanthroline or 2,9-dimethyl-1,10-phenanthroline) with MeSSMe gives the platinum(IV) complexes cis,trans-[PtR2(SMe)2(NN)]. They are characterized by NMR spectroscopy and elemental analysis. The geometries and the nature of the frontier molecular orbitals of Pt(IV) complexes containing Ptsbnd S bonds are studied by means of the density functional theory.

  2. Living atom transfer radical polymerization of 4-acetoxystyrene

    DEFF Research Database (Denmark)

    Gao, Bo; Chen, Xianyi; Ivan, Bela


    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 initi......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...

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

    DEFF Research Database (Denmark)

    Stadler, Robert; Jacobsen, Karsten Wedel


    . For bipyridine the charge distribution is defined by a balance between electrostatic repulsion effects and the filling of the LUMO, where the molecule loses electrons to the leads. BPDT, on the other hand, gains electrons. As a direct consequence the Fermi level of the metal is found at the energetically higher...

  4. Construction of Insulin 18-mer Nanoassemblies Driven by Coordination to Iron(II) and Zinc(II) Ions at Distinct Sites

    DEFF Research Database (Denmark)

    Munch, Henrik K.; Nygaard, Jesper; Christensen, Niels Johan;


    coordination with two different metal ions. Selective attachment of an abiotic 2,2′-bipyridine (bipy) ligand to HI, yielding HI–bipy, enabled ZnII-binding hexamers to SA into trimers of hexamers, [[HI–bipy]6]3, driven by octahedral coordination to a FeII ion. The structures were studied in solution by small...

  5. Chromogenic detection of Sarin by discolouring decomplexation of a metal coordination complex. (United States)

    Ordronneau, Lucie; Carella, Alexandre; Pohanka, Miroslav; Simonato, Jean-Pierre


    An innovative chromogenic sensing concept based on decomplexation of a tris-(bipyridine)iron(II) coordination complex has been developed for the detection of organophosphorus nerve agents. It was evaluated both on a simulant and real Sarin in vapour and liquid phases.

  6. Long-term stability for cobalt-based dye-sensitized solar cells obtained by electrolyte optimization. (United States)

    Gao, Jiajia; Bhagavathi Achari, Muthuraaman; Kloo, Lars


    A significant improvement in the long-term stability for cobalt-based dye-sensitized solar cells (DSCs) under light-soaking conditions has been achieved by optimization of the composition of tris(2,2'-bipyridine) Co(ii)/Co(iii) electrolytes. The effects of component exchanges and changes were also studied during the optimization process.

  7. In Vitro Polarized Resonance Raman Study of N719 and N719-TBP in Dye Sensitized Solar Cells

    DEFF Research Database (Denmark)

    Hassing, Søren; Jernshøj, Kit Drescher; Lund, Torben;


    Abstract: The working efficiency of dye-sensitized solar cells (DSCs) depends on the long-term stability of the dye itself and on the microscopic structure of the dye-semiconductor interface. Previous experimental studies of DSCs based on ruthenium dye with bipyridine ligands (N719) adsorbed...

  8. Multistep electrochemical reduction path of clusters [Os3(CO)10(α-diimine)]: Comparison of electrochemical and photochemical Os-Os(α-diimine) bond cleavage

    NARCIS (Netherlands)

    F. Hartl; J.W.M. van Outersterp


    Electrochemical reduction of the triangular clusters [Os-3(CO)(10)(alpha-dimine)] (alpha-dimine = 2,2'-bipyridine (bpy), 2,2'-bipyrimidine (bpym)) and [Os-3(CO)(10)(mu-bpym) ReBr(CO)(3)] produces primarily the corresponding radical anions. Their stability is strongly determined by the pi acceptor ab

  9. Electron transfer between galactose oxidase and an electrode via a redox polymer network

    NARCIS (Netherlands)

    Stigter, E.C.A.; Carnicero, A.M.; Lugt, J.P. vann der; Somers, W.A.C.


    Galactose oxidase from Dactyllium dendroides was purified and immobilised on a carbon electrode in a redox polymer network of a polyvinylpyridine, partially N-complexed with osmiumbis(bipyridine)chloride (POsEA). The current density of the electrodes depended on the concentration of phosphate elutio

  10. Highly selective CO2 adsorption accompanied with low-energy regeneration in a two-dimensional Cu(II) porous coordination polymer with inorganic fluorinated PF6(-) anions. (United States)

    Noro, Shin-ichiro; Hijikata, Yuh; Inukai, Munehiro; Fukushima, Tomohiro; Horike, Satoshi; Higuchi, Masakazu; Kitagawa, Susumu; Akutagawa, Tomoyuki; Nakamura, Takayoshi


    High selectivity and low-energy regeneration for adsorption of CO(2) gas were achieved concurrently in a two-dimensional Cu(II) porous coordination polymer, [Cu(PF(6))(2)(4,4'-bpy)(2)](n) (4,4'-bpy = 4,4'-bipyridine), containing inorganic fluorinated PF(6)(-) anions that can act as moderate interaction sites for CO(2) molecules.

  11. Molecular Mechanism of Action for Allosteric Modulators and Agonists in CC-chemokine Receptor 5 (CCR5)

    DEFF Research Database (Denmark)

    Karlshøj, Stefanie; Amarandi, Roxana Maria; Larsen, Olav;


    The small molecule metal ion chelators bipyridine and terpyridine complexed with Zn(2+) (ZnBip and ZnTerp) act as CCR5 agonists and strong positive allosteric modulators of CCL3 binding to CCR5, weak modulators of CCL4 binding, and competitors for CCL5 binding. Here we describe their binding site...

  12. Chemical topology: Tying up some loose ends (United States)

    Fenlon, Edward E.


    A linear molecule containing three bipyridine ligands can be wrapped around a single metal-ion template to form an open-knot complex. The loose ends of the knot can be 'tied' together through esterification or olefin-metathesis reactions to form closed knots that do not unravel when the metal template is removed.

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

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


    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.

  14. 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


    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.

  15. A chemical system that mimics decoding operations. (United States)

    Giansante, Carlo; Ceroni, Paola; Venturi, Margherita; Sakamoto, Junji; Schlüter, A Dieter


    The chemical information stored in equilibrium mixtures of molecular species is larger than the sum of information carried by the individual molecules. Protonation equilibria in dilute dichloromethane solution of a shape-persistent macrocycle bearing two 2,2'-bipyridine units and two Coumarin 2 moieties (see figure) can be exploited to mimic decoding operations.

  16. Zero-field slow magnetic relaxation in a uranium(III) complex with a radical ligand. (United States)

    Coutinho, Joana T; Antunes, Maria A; Pereira, Laura C J; Marçalo, Joaquim; Almeida, Manuel


    [U(Tp(Me2))2(bipy˙)], a uranium(III) complex with a radical bipyridine ligand which has magnetic properties with contributions from both the ligand and the metal, presents slow relaxation of the magnetisation at low temperatures, already under zero static magnetic field, and energy barriers slightly above the non-radical analogues.

  17. 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;


    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 ...

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

    Institute of Scientific and Technical Information of China (English)


    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.

  19. Controlled/"Living" Radical Polymerization of (-)-Menthyl Methacrylate

    Institute of Scientific and Technical Information of China (English)


    The atom transfer radical polymerization(ATRP) of (-)-menthyl methacrylate((-)-MnMA) mediated by CuCl/bipyridine and ethyl 2-bromopropionate or 1-phenylethyl bromide in THF system has been studied. The dependence of the specific rotation on molecular weight and the CD of Poly((-)-MnMA) thus obtained was investigated.

  20. Reverse Atom Transfer Radical Polymerization of (-)-Menthyl Methacrylate

    Institute of Scientific and Technical Information of China (English)


    The reverse atom transfer radical polymerization(RATRP) of (-)-menthyl methacrylate ((-)-MnMA) with AIBN(AIBN/CuCl2/bipyridine(bipy) or (-)sparteine((-)Sp) =1/2/4) initiating system in THF has been studied. The dependence of the specific rotation on molecular weight was investigated.

  1. Re-mediated C-C coupling of pyridines and imidazoles. (United States)

    Espinal Viguri, Maialen; Huertos, Miguel A; Pérez, Julio; Riera, Lucía; Ara, Irene


    Rhenium tricarbonyl complexes with three N-heterocyclic ligands (N-alkylimidazoles or pyridines) undergo deprotonation with KN(SiMe(3))(2) and then oxidation with AgOTf to afford complexes with pyridylimidazole or bipyridine bidentate ligands resulting from deprotonation, C-C coupling and rearomatization.

  2. Electron transfer between a quinohemoprotein alcohol dehydrogenase and an electrode via a redox polymer network

    NARCIS (Netherlands)

    Stigter, E.C.A.; Jong, G.A.H. de; Jongejan, J.A.; Duine, J.A.; Lugt, J.P. van der; Somers, W.A.C.


    A quinohemoprotein alcohol dehydrogenase (QH-EDH) from Comamonas testosteroni was immobilized on an electrode in a redox polymer network consisting of a polyvinylpyridine partially N-complexed with osmiumbis-(bipyridine)chloride. The enzyme effectively transfers electrons to the electrode via the po

  3. A Rapid Synthetic Method for the Preparation of Two Tris-Cobalt(III) Compounds. (United States)

    Jackman, Donald C.; Rillema, D. Paul


    Reports a method of preparation for tris(ethylenediamine)cobalt(III) and tris(2,2'-bipyridine)cobalt(III) that will shorten the preparation time by approximately 3 hours. Notes the time for synthesis and isolation of compound one was 1 hour (yield 38 percent) while compound two took 50 minutes (yield 71%). (MVL)

  4. Synthesis and characterization of novel heteroleptic ruthenium sensitizer for nanocrystalline dye-sensitized solar cells

    NARCIS (Netherlands)

    Sivakumar, R.; Marcelis, A.T.M.; Anandan, S.


    A novel heteroleptic ruthenium complex of the type [Ru(bpin)(dcbpyH2)Cl]Cl (where bpin is 2,6-bis(pyrazol-1-yl)isonicotinic acid and dcbpyH2 is 4,4'-dicarboxy-2,2'-bipyridine) was synthesized and characterized for tuning the LUMO level of the ruthenium sensitizer to achieve greater stabilization in

  5. Electrochemiluminescent Properties of Organic Films with Incorporated Carbon Nanotubes

    Directory of Open Access Journals (Sweden)

    Yu.T. Zholudov


    Full Text Available This work describes the study of the electrochemical and electrochemiluminescent properties of electrodes modified by films of polyvinyl alcohol containing luminophor tris-bipyridine ruthenium and carbon nanotubes. Studied electrode structures showed good applicability for the development of nanotechnological ECL-sensors intended for the assay in aqueous mediums.

  6. 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


    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.

  7. High efficiency solid-state sensitized heterojunction photovoltaic device

    KAUST Repository

    Wang, Mingkui


    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.

  8. Mechanism of Polysulfone-Based Anion Exchange Membranes Degradation in Vanadium Flow Battery. (United States)

    Yuan, Zhizhang; Li, Xianfeng; Zhao, Yuyue; Zhang, Huamin


    The stability of hydrocarbon ion exchange membranes is one of the critical issues for a flow battery. However, the degradation mechanism of ion exchange membranes has been rarely investigated especially for anion exchange membranes. Here, the degradation mechanism of polysulfone based anion exchange membranes, carrying pyridine ion exchange groups, under vanadium flow battery (VFB) medium was investigated in detail. We find that sp(2) hybrid orbital interactions between pyridinic-nitrogen in 4,4'-bipyridine and benzylic carbon disrupt the charge state balance of pristine chloromethylated polysulfone. This difference in electronegativity inversely induces an electrophilic carbon center in the benzene ring, which can be attacked by the lone pair electron on the vanadium(V) oxygen species, further leading to the degradation of polymer backbone, while leaving the 4,4'-bipyridine ion exchange groups stable. This work represents a step toward design and construction of alternative type of chemically stable hydrocarbon ion exchange membranes for VFB.

  9. A one-dimensional double-chain coordination polymer: [Mn(C12H13NO6S)(C10H8N2)]n. (United States)

    Liang, Fu-Pei; Chen, Man-Sheng; Hu, Rui-Xiang; Chen, Zi-Lu


    In the title compound, poly[[(2,2'-bipyridine-kappa(2)N,N')manganese(II)]-micro(3)-N-tosyl-L-glutamato-kappa(4)O,O':O":O"'], [Mn(tsgluo)(bipy)](n), where tsgluo is N-tosyl-L-glutamate (C(12)H(13)NO(6)S) and bipy is 2,2'-bipyridine (C(10)H(8)N(2)), the Mn atoms are octahedrally coordinated by two N atoms of one bipy ligand and by four O atoms of three tsgluo(2-) anions. The gamma-carboxyl group coordinates to the Mn(II) atom in a chelating mode, while the alpha-carboxyl group coordinates in a bidentate-bridging mode. The complex displays a one-dimensional double-chain structure.

  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)



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

    Directory of Open Access Journals (Sweden)

    Lingamallu Giribabu


    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.

  12. In Situ Solid-State Reactions Monitored by X-ray Absorption Spectroscopy: Temperature-Induced Proton Transfer Leads to Chemical Shifts. (United States)

    Stevens, Joanna S; Walczak, Monika; Jaye, Cherno; Fischer, Daniel A


    The dramatic colour and phase alteration with the solid-state, temperature-dependent reaction between squaric acid and 4,4'-bipyridine has been probed in situ with X-ray absorption spectroscopy. The electronic and chemical sensitivity to the local atomic environment through chemical shifts in the near-edge X-ray absorption fine structure (NEXAFS) revealed proton transfer from the acid to the bipyridine base through the change in nitrogen protonation state in the high-temperature form. Direct detection of proton transfer coupled with structural analysis elucidates the nature of the solid-state process, with intermolecular proton transfer occurring along an acid-base chain followed by a domino effect to the subsequent acid-base chains, leading to the rapid migration along the length of the crystal. NEXAFS thereby conveys the ability to monitor the nature of solid-state chemical reactions in situ, without the need for a priori information or long-range order.

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

    Directory of Open Access Journals (Sweden)

    Mohammed A. Al-Anber


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

  14. Applications of capillary electrophoresis with chemiluminescence detection in clinical, environmental and food analysis. A review

    Energy Technology Data Exchange (ETDEWEB)

    Lara, Francisco J.; Airado-Rodríguez, Diego; Moreno-González, David; Huertas-Pérez, José F.; García-Campaña, Ana M., E-mail:


    This paper reviews the latest developments and analytical applications of chemiluminescence detection coupled to capillary electrophoresis (CE-CL). Different sections considering the most common CL systems have been included, such as the tris(2,2′-bipyridine)ruthenium(II) system, the luminol and acridinium derivative reactions, the peroxyoxalate CL or direct oxidations. Improvements in instrumental designs, new strategies for improving both resolution and sensitivity, and applications in different fields such as clinical, pharmaceutical, environmental and food analysis have been included. This review covers the literature from 2010 to 2015. - Highlights: • An up-to-date critical review about the evolution of CE-CL is presented. • Tris(2,2′-bipyridine)ruthenium(II) and luminol as the most used CL systems. • Instrumental designs and strategies for improving resolution and sensitivity. • Applications in clinical, pharmaceutical, environmental and food analysis.

  15. Osmium-labeled polynucleotides: reaction of osmium tetraoxide, with poly-1,N6-ethenoadenylic acid. (United States)

    Marzilli, L G; Hanson, B E; Kapili, L; Rose, S D; Beer, M


    Osmium tetraoxide, in the presence of ligands such as pyridine and bipyridine, adds across the etheno bridge of 1,N6-etheno-9-methyladenine and poly-1,N6-ethenoadenylic acid. The Os:P ratio in the labeled polynucleotide was approximately equal to 1 when bipyridine was used as the stabilizing ligand. A similar study with polycytidylic acid, which had been partially modified with chloroacetaldehyde so that some bases were converted to 3,N4-ethenocytosine, gave an OS:P ratio of approximately equal to 1.3. Calf-thymus DNA, in which the adenine and cytosine bases were modified by chloroacetaldehyde, gave an Os:P ratio of approximately equal to 1 after 24 h. These results suggest that 3,N4-ethenocytosine will add two Os labels.

  16. Two-photon absorption of Zn(II) octupolar molecules. (United States)

    Mazzucato, Simone; Fortunati, Ilaria; Scolaro, Sara; Zerbetto, Michele; Ferrante, Camilla; Signorini, Raffaella; Pedron, Danilo; Bozio, Renato; Locatelli, Danika; Righetto, Stefania; Roberto, Dominique; Ugo, Renato; Abbotto, Alessandro; Archetti, Graziano; Beverina, Luca; Ghezzi, Sergio


    In this work we present an investigation of the non-linear optical (NLO) properties of two octupolar chromophores: [Zn(4,4'-bis(dibutylaminostyryl)-[2,2']-bipyridine)(3)](2+) and [Zn(4,4'-bis((E)-2-(N-(TEG)pyrrol-2-yl)vinyl)-[2,2']-bipyridine)(3)](2+) with Zn(ii) as the coordination center, using two-photon emission technique (TPE) in fs-pulse temporal regime. Compared to the free ligands, our results do not show a net increase in the two-photon absorption (TPA) cross-section for the octupolar complexes, once normalized to the ligand unit. This is in partial disagreement with a previous theoretical study investigating the first molecule where a significant increase of the TPA cross-section was predicted (X. J. Liu, et al., J. Chem. Phys., 2004, 120, 11 493).

  17. Photonics of a conjugated organometallic Pt-Ir polymer and its model compounds exhibiting hybrid CT excited states. (United States)

    Soliman, Ahmed M; Fortin, Daniel; Zysman-Colman, Eli; Harvey, Pierre D


    Trans- dichlorobis(tri-n-butylphosphine)platinum(II) reacts with bis(2- phenylpyridinato)-(5,5'-diethynyl-2,2'-bipyridine)iridium(III) hexafluorophosphate to form the luminescent conjugated polymer poly[trans-[(5,5'-ethynyl-2,2'-bipyridine)bis(2- phenylpyridinato)-iridium(III)]bis(tri-n-butylphosphine)platinum(II)] hexafluorophosphate ([Pt]-[Ir])n. Gel permeation chromatography indicates a degree of polymerization of 9 inferring the presence of an oligomer. Comparison of the absorption and emission band positions and their temperature dependence, emission quantum yields, and lifetimes with those for models containing only the [Pt] or the [Ir] units indicates hybrid excited states including features from both chromophores.

  18. Reversible supramolecular assembly at specific DNA sites: nickel-promoted bivalent DNA binding with designed peptide and bipyridyl-bis(benzamidine) components. (United States)

    Sánchez, Mateo I; Mosquera, Jesús; Vázquez, M Eugenio; Mascareñas, José L


    At specific DNA sites, nickel(II) salts promote the assembly of designed components, namely a bis(histidine)-modified peptide that is derived from a bZIP transcription factor and a bis(benzamidine) unit that is equipped with a bipyridine. This programmed supramolecular system with emergent properties reproduces some key characteristics of naturally occurring DNA-binding proteins, such as bivalence, selectivity, responsiveness to external agents, and reversibility.


    Institute of Scientific and Technical Information of China (English)

    Tokuji Miyashita; Tatsuo Taniguchi; Yoshihito Fukasawa


    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.

  20. Fast two-photon neuronal imaging and control using a spatial light modulator and ruthenium compounds (United States)

    Peterka, Darcy S.; Nikolenko, Volodymyr; Fino, Elodie; Araya, Roberto; Etchenique, Roberto; Yuste, Rafael


    We have developed a spatial light modulator (SLM) based microscope that uses diffraction to shape the incoming two-photon laser source to any arbitrary light pattern. This allows the simultaneous imaging or photostimulation of different regions of a sample with three-dimensional precision at high frame rates. Additionally, we have combined this microscope with a new class of two photon active neuromodulators with Ruthenium BiPyridine (RuBi) based cages that offer great flexibility for neuronal control.

  1. Self-assembly of novel supramolecular silver(I) compound based on mixed ligands bipy/TST3- H3TST=2,4,6-tris (4-sulfophenylamino)-1,3,5-triazine

    NARCIS (Netherlands)

    Yu, Yunfang; Wei, Yongqin; Broer, Ria; Wu, Kechen


    The novel supramolecular silver(I) compound with formula [Ag-6(TST)(2)(bipy)(6)(H2O)(2)](n) center dot 3nH(2)O (1) based on assembly of Ag(I) and mixed ligand bipy/TST3-, bipy = 2,2'-bipyridine, H3TST = 2,4,6-tris(4-sulfophenylamino)-1,3,5-triazine, has been prepared by hydrothermal method. In the s

  2. {sup 57}Fe Moessbauer Spectroscopic Study on the Assembled Iron Complexes

    Energy Technology Data Exchange (ETDEWEB)

    Nakashima, S. [Hiroshima University, Natural Science Center for Basic Research and Development (N-BARD) (Japan); Asada, Y.; Okuda, T. [Hiroshima University, Department of Chemistry, Graduate School of Science (Japan)


    {sup 57}Fe Moessbauer spectroscopy was carried out to know the electronic states of the assembled iron complexes. The IS value revealed a high-spin Fe{sup II} state in the bipyridine and pyrazine iron complexes with NCS or NCSe. The dissociation behavior of ligand was investigated by TG, and the resultant change in the coordination sphere around iron atom was reflected in the change in QS value.

  3. Modulation in Selectivity and Allosteric Properties of Small-Molecule Ligands for CC-Chemokine Receptors

    DEFF Research Database (Denmark)

    Thiele, Stefanie; Malmgaard-Clausen, Mikkel; Engel-Andreasen, Jens;


    Among 18 human chemokine receptors, CCR1, CCR4, CCR5, and CCR8 were activated by metal ion Zn(II) or Cu(II) in complex with 2,2'-bipyridine or 1,10-phenanthroline with similar potencies (EC(50) from 3.9 to 172 μM). Besides being agonists, they acted as selective allosteric enhancers of CCL3. Thes...

  4. Multi-responsive metal-organic lantern cages in solution. (United States)

    Brega, Valentina; Zeller, Matthias; He, Yufan; Lu, H Peter; Klosterman, Jeremy K


    Soluble copper-based M4L4 lantern-type metal-organic cages bearing internal amines were synthesized. The solution state integrity of the paramagnetic metal-organic cages was demonstrated using NMR, DLS, MS, and AFM spectroscopy. 1D supramolecular pillars of pre-formed cages or covalent host-guest complexes selectively formed upon treatment with 4,4'-bipyridine and acetic anhydride, respectively.

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

    Institute of Scientific and Technical Information of China (English)


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

  6. Protein dynamics in an intermediate state of myoglobin: optical absorption, resonance Raman spectroscopy, and x-ray structure analysis.


    N. Engler; Ostermann, A; Gassmann, A.; Lamb, D C; Prusakov, V E; J. Schott; Schweitzer-Stenner, R; Parak, F. G.


    A metastable state of myoglobin is produced by reduction of metmyoglobin at low temperatures. This is done either by irradiation with x-rays at 80 K or by electron transfer from photoexcited tris(2, 2'-bipyridine)-ruthenium(II) at 20 K. At temperatures above 150 K, the conformational transition toward the equilibrium deoxymyoglobin is observed. X-ray crystallography, Raman spectroscopy, and temperature-dependent optical absorption spectroscopy show that the metastable state has a six-ligated ...

  7. 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.


    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.

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

    Directory of Open Access Journals (Sweden)

    Lei Zhu


    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.

  9. Control of dark current in photoelectrochemical (TiO2/I--I3-)) and dye-sensitized solar cells. (United States)

    Ito, Seigo; Liska, Paul; Comte, Pascal; Charvet, Raphaël; Péchy, Peter; Bach, Udo; Schmidt-Mende, Lukas; Zakeeruddin, Shaik Mohammed; Kay, Andreas; Nazeeruddin, Mohammad K; Grätzel, Michael


    The ruthenium complex bis-tetrabutylammonium cis-dithiocyanato-N,N'-bis-2,2'-bipyridine-4-carboxylic acid, 4'-carboxylate ruthenium(II), N-719, was found to block the dark current of dye sensitized solar cells (DSC), based on mesoporous TiO2 films deposited on a F-doped tin oxide electrode and the effect was compared to surface treatment by TiCl4 and the introduction of a compact TiO2 blocking layer.

  10. A set of homologous hetarylenediyne macrocycles by oxidative acetylene-acetylene coupling. (United States)

    Opris, Dorina M; Ossenbach, Alexander; Lentz, Dieter; Schlüter, A Dieter


    The synthesis of a set of bipyridine-containing macrocycles by oxidative acetylene-acetylene dimerization is described. The cycles are separated by preparative GPC, and the smallest homologue is analyzed by single-crystal X-ray diffraction, which shows a layered structure with channels that are partially filled with parts of the flexible chains of adjacent macrocycles. The cyclic trimer has a D3h symmetry and is a possible candidate for the formation of metal organic supramolecular assemblies on surfaces.

  11. The kinetics and mechanism of the substitution of benzylideneacetone by azadienes in the irontricarbonylbenzylideneacetone complex


    Squizani, F; E. Stein(INFN Turin); VICHI, EJS


    The kinetics of the substitution reactions of benzylideneacetone (bda) by the azadienes 2,2'-bipyridine (bipy), 2-acetylpyridineanil (apa), and diacetyldianil (dad), in the Fe(bda)(CO)(3) complex was performed in toluene in the temperature range between 40 and 55 degrees C. The results of this study showed that the mechanism of the reactions with bipy and dad - which are symmetric ligands, aromatic and aliphatic, respectively - involves two parallel reaction paths, one being dissociative and ...

  12. Electrochemical Characterisation of an Os (II) Conjugated Polymer in Aqueous Electrolytes


    McCormac, Timothy; Cassidy, John F; Crowley, Karl; Trouillet, Lise; Lafolet, Frédéric; Guillerez, Stephane


    The electrochemical behaviour of an Os (II) complex of the structurally well-defined conjugated polymer alternating regioregularly alkylated thiophene and 2,2’-bipyridine units (P4Os) has been elucidated in aqueous solution. In typical aqueous electrolyte systems the cyclic voltammogram of the resulting P4Os film exhibits a one electron reversible process corresponding to the Os3+/2+ redox system. However the observance of this reversible couple did depend upon the concentration of the sup...

  13. μ-4,4′-Bipyridyl-1:2κ2N:N′-methanol-2κO-tetrakis(tri-tert-butoxysilanethiolato-1κ4O,S;2κ2S-dizinc(II

    Directory of Open Access Journals (Sweden)

    Katarzyna Baranowska


    Full Text Available The title compound, [Zn2(C12H27O3SSi4(C10H8N2(CH4O], is a binuclear complex with the two ZnII atoms linked via a bridging 4,4′-bipyridyl ligand. One of the ZnII atoms is penta-coordinated by two O,S-chelating tri-tert-butoxysilanethiolate units and one N atom of a 4,4′-bipyridine ligand, and the other ZnII atom is tetrahedrally coordinated by two tri-tert-butoxysilanethiolate anions acting as monodentate S ligands, the methanol O atom and the other N atom of the 4,4′-bipyridine ligand. This non-symmetrical coordination induces twisting and bending in the 4,4′-bipyridine ligand and introduces chirality into the system. The crystal studied exhibits inversion twinning. One tert-butyl group is disordered approximately equally over two positions.

  14. Synthesis, structure and some properties of a manganese(II) benzoate containing diimine (United States)

    Paul, Pranajit; Roy, Subhadip; Sarkar, Sanjoy; Chowdhury, Shubhamoy; Purkayastha, R. N. Dutta; Raghavaiah, Pallepogu; McArdle, Patrick; Deb, Lokesh; Devi, Sarangthem Indira


    A new monomeric manganese(II) benzoate complex containing nitrogen donor 2,2‧-bipyridine, [Mn(OBz)2(bipy)(H2O)] (OBz = benzoate, bipy = 2,2‧-bipyridine) has been synthesized from aqueous methanol medium and characterized by analytical, spectroscopic and single crystal X-ray diffraction studies. The compound exhibits moderate to appreciable antimicrobial activity. The complex crystallizes in space group P21/n. Mn(II) atom is ligated by two N atoms of bipyridine, three O atoms from a monodentate and a bidentate benzoate ligand and a water molecule forming distorted octahedral structure. The coordinated water molecule forms intramolecular hydrogen bonds and links the monomer molecules into hydrogen bonded dimer. The hydrogen bonded dimers are involved in intermolecular C-H···O and π-π stacking interactions. Density functional theory (DFT) computation was carried out to compute the frequencies of relevant vibrational modes and electronic properties, the results are in compliance with the experimentally obtained structural and spectral data.

  15. Direct Electrochemical Synthesis and Crystal Structure of a New Mononuclear Copper(Ⅱ) Complex: [(bipy)2Cu(PhCOO)]ClO4·(benzil) (benzil = 1,2-Diphenyl-ethane-1,2-dione)

    Institute of Scientific and Technical Information of China (English)

    YUAN Ya-Xian; GU Ren-Ao; YAO Jian-Lin


    A new mononuclear copper(Ⅱ) complex [(bipy)2Cu(PhCOO)]ClO4·(benzil) (bipy=2,2'-bipyridine, benzil=1,2-diphenyl-ethane-1,2-dione) was synthesized by direct electrochemical oxidation of Cu electrode in an acetonitrile solution with benzoic acid, 2,2'-bipyridine and benzoin. As soon as the current flowed in the cell, benzoin was oxidized to benzil quickly. The crystal structure was determined by X-ray diffraction. It belongs to monoclinic system, space group P21/c with a=14.860(2), b=20.784(3), c=11.9150(17) (A), β=101.401(3)°, V=3607.3(9) (A)3, Z=4, Mr=806.69, Dc=1.485 g/cm3, F(000)=1660, μ=0.742 mm-1, R=0.0788 and wR=0.1519 for 6254 observed reflections (Ⅰ > 2σ(Ⅰ)). The complex contains a mononuclear [(bipy)2Cu(PhCOO)]+ cation, a solvate benzil molecule and a ClO4- anion which locates around the cation outside acting as the counter ion. The Cu(Ⅱ) ion is coordinated by two 2,2'-bipyridines and one benzoato ligand to form a distorted square-pyramid.

  16. Synthesis, characterization, thermal and DNA-binding properties of new zinc complexes with 2-hydroxyphenones. (United States)

    Mrkalić, Emina; Zianna, Ariadni; Psomas, George; Gdaniec, Maria; Czapik, Agnieszka; Coutouli-Argyropoulou, Evdoxia; Lalia-Kantouri, Maria


    The neutral mononuclear zinc complexes with 2-hydroxyphenones (ketoH) having the formula [Zn(keto)2(H2O)2] and [Zn(keto)2(enR)], where enR stands for a N,N'-donor heterocyclic ligand such as 2,2'-bipyridine (bipy), 1,10-phenanthroline (phen) or 2,2'-dipyridylamine (dpamH), have been synthesized and characterized by IR, UV and (1)H NMR spectroscopies. The 2-hydroxyphenones are chelated to the metal ion through the phenolate and carbonyl oxygen atoms. The crystal structures of [bis(2-hydroxy-4-methoxy-benzophenone)(2,2'-bipyridine)zinc(II)] dimethanol solvate and [bis(2-hydroxy-benzophenone)(2,2'-bipyridine)zinc(II)] dimethanol solvate have been determined by X-ray crystallography. The thermal stability of the zinc complexes has been investigated by simultaneous TG/DTG-DTA technique. The ability of the complexes to bind to calf-thymus DNA (CT DNA) has been studied by UV-absorption and fluorescence emission spectroscopy as well as viscosity measurements. UV studies of the interaction of the complexes with DNA have shown that they can bind to CT DNA and the corresponding binding constants to DNA have been calculated and evaluated. The complexes most probably bind to CT DNA via intercalation as concluded by studying the viscosity of a DNA solution in the presence of the complexes. Competitive studies with ethidium bromide (EB) have shown that the reported complexes can displace the DNA-bound EB, suggesting strong competition with EB for the intercalation site.

  17. 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


    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.

  18. Post-Synthetic Shaping of Porosity and Crystal Structure of Ln-Bipy-MOFs by Thermal Treatment

    Directory of Open Access Journals (Sweden)

    Philipp R. Matthes


    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.

  19. 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


    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.

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

    Indian Academy of Sciences (India)

    Paladugu Suresh; Ganesan Prabusankar


    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.

  1. Single-Molecule Electrochemical Transistor Utilizing a Nickel-Pyridyl Spinterface

    DEFF Research Database (Denmark)

    Brooke, Richard J.; Jin, Chengjun; Szumski, Doug S.


    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 calculations reveal that this behavior arises because charge transport is mediated by spin-polarized Ni d...

  2. Two Zn(II) coordination complexes assembled by trithiocyanuric acid and two different N-donor auxiliary ligands. (United States)

    He, Xiao Xiao; Guo, Ya Mei


    The dipyridyl-type building blocks 4-amino-3,5-bis(pyridin-3-yl)-1,2,4-triazole (3-bpt) and 4,4'-bipyridine (bpy) have been used to assemble with Zn(II) in the presence of trithiocyanuric acid (ttcH3) to afford two coordination compounds, namely bis[4-amino-3,5-bis(pyridin-3-yl)-1,2,4-triazole-κN(3)]bis(trithiocyanurato-κ(2)N,S)zinc(II), [Zn(C3H2N3S3)2(C12H10N6)2]·2H2O, (1), and catena-poly[[[bis(trithiocyanurato-κ(2)N,S)zinc(II)]-μ-4,4'-bipyridine-κ(2)N:N'] 4,4'-bipyridine monosolvate], {[Zn2(C3H2N3S3)4(C10H8N2)3]·C10H8N2}n, (2). Single-crystal X-ray analysis indicates that complex (1) is a mononuclear structure, while complex (2) presents a one-dimensional chain coordination motif. In both complexes, the central Zn(II) cation adopts an octahedral geometry, coordinated by four N- and two S-donor atoms. Notably, trithiocyanurate (ttcH2(-)) adopts the same bidentate chelating coordination mode in each complex and exists in the thione tautomeric form. The 3-bpt co-ligand in (1) adopts a monodentate coordination mode and serves as a terminal pendant ligand, whereas the 4,4'-bipyridine (bpy) ligand in (2) adopts a bidentate-bridging coordination mode. The different coordination characters of the different N-donor auxiliary ligands lead to structural diversity for complexes (1) and (2). Further analysis indicates that the resultant three-dimensional supramolecular networks for (1) and (2) arise through intermolecular N-H...S and N-H...N hydrogen bonds. Both complexes have been further characterized by FT-IR spectroscopy and elemental analyses.

  3. 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


    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.

  4. 4,4',4"-trimethyl-2,2':6',2"-terpyridine by oxidative coupling of 4-picoline. (United States)

    Robo, Michael T; Prinsell, Michael R; Weix, Daniel J


    Alkylated terpyridine ligands are an increasingly important component of catalysis and dyes but are costly because their synthesis is challenging and often low-yielding. We report an improved method for the Pd/C-catalyzed dehydrogenative coupling of 4-picoline to form the bi- and terpyridine. The addition of MnO2 improves the yield of the reaction, making the reaction useful on a large scale (up to 200 mmol). The use of Pd(OAc)2 or Pd/C/pivalic acid leads to the selective formation of bipyridine.

  5. New Coordinative Compounds with 4-(4’-pyridylpyridinium Disubstituted Monoylides

    Directory of Open Access Journals (Sweden)

    Rodica Postolachi


    Full Text Available The complexes with manganese(II, iron(II, cobalt(II, nickel(II and copper(II of 2-(4, 4’-bipyridin-1-ium-1-yl-1-(4-bromophenylamino-3-(4-methoxyphenyl-3-oxo-1-thioxopropan-2-ide (ylide, Y were synthesized and characterized. The obtained compounds with 1 : 2 metal/ligand ratios have been characterized by FTIR, UV Vis spectroscopy, ESI MS spectrometry, molecular conductance, magnetic measurements and thermal analysis. The ylide ligand forms chelates with metallic (II ions through their amide nitrogen and oxygen atoms.

  6. 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


    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.

  7. Comparative Studies with Zwitterionic Platinum(II) Bis(pyrazolyl)borate and 2,2‘-Bipyridylborate Complexes


    Thomas, Christine M.; Peters, Jonas C.


    A comparison between the mononuclear platinum complexes of three structurally different monoanionic borato ligands is presented:  [Ph_2B(pyrazolyl)_2]- ([Ph_2B(pz)_2], 1), [4-Ph_3B(2,2‘-bipyridine)]- ([(4-BPh_3)bpy], 2), and [Ph_2B(CH_2PPh_2)_2]- ([Ph_2BP_2], 3). The new bipyridylborate ligand 2 is introduced in this study. The relative trans influence of these ligands has been assessed by comparison of the structural and spectroscopic (NMR) data of the platinum dimethyl complexes [[Ph_2B(pz)...

  8. An unusual chain constructed from heteropolyanions and isopolyanions: [{Cu(2,2'-bipy)} 6(Mo 6O 22)][SiMo 12O 40 (United States)

    Zhang, Chun-Jing; Zhang, Chun-Hua; Pang, Hai-Jun; Wang, Da-Peng; Kong, Qing-Jiao; Yang, Xiao-Dan; Yao, Feng; Tang, Qun; Wang, Hui-Yuan; Chen, Ya-Guang


    A new compound based on transition metal complexes modified heteropolyanions and isopolyanions: [{Cu(2,2'-bipy)} 6(Mo 6O 22)][SiMo 12O 40] ( 1) (2,2'-bipy = 2,2'-bipyridine), has been hydrothermally synthesized and characterized by elemental analysis, IR, TG and single-crystal X-ray diffraction. In compound 1, each of the [Mo 6O 22] 8- clusters is surrounded by six {Cu(2,2'-bipy)} 2+ fragments forming [{Cu(2,2'-bipy)} 6(Mo 6O 22)] 4+ cations which further alternately link the [SiMo 12O 40] 4- anions to result in an unusual 1D chain.

  9. Synthesis and Crystal Structure of a New Manganese Complex

    Institute of Scientific and Technical Information of China (English)

    WANG Jian; LIU Ping; CHEN Yun


    @@ In order to study the relationship between the manganese ion and the biological coordination agent, the role ofmanganese ion in the active sites and the structure of the active sites in the manganese enzymes, small molecule complexes are often applied to modeling the structure and the properties of reaction in the active centers. In this pa per, we will report the synthesis and crystal structure of a new manganese(Ⅱ) complex, catena[ aqua-(p-methoxybenzoato- O, O′ ) - (p-methoxybenzoato- O )- (2,2′-bipyridine)-manganese (Ⅱ) ] (p-methoxybenzoic acid). The crystal structure was confirmeded by X-ray crystallography analysis.

  10. Synthesis, characterization and DNA-binding studies of ruthenium(II) mixed-ligand complexes containing dipyrido[1,2,5]oxadiazolo[3,4-b]quinoxaline (United States)

    Peng, Bin; Chen, Xiang; Du, Ke-Jie; Yu, Bo-Le; Chao, Hui; Ji, Liang-Nian


    A novel ligand dipyrido[1,2,5]oxadiazolo[3,4-b]quinoxaline (dpoq) and its complexes [Ru(bpy) 2(dpoq)] 2+ and [Ru(phen) 2(dpoq)] 2+ (bpy = 2,2'-bipyridine; phen = 1,10-phenanthroline) have been synthesized and characterized by elemental analysis, electrospray mass spectra and 1H NMR. The interaction of Ru(II) complexes with calf thymus DNA (CT-DNA) was investigated by absorption spectroscopy, fluorescence spectroscopy, thermal denaturation and viscosity measurements. Results suggest that two Ru(II) complexes bind to DNA via an intercalative mode.

  11. Two novel CPs with double helical chains based rigid tripodal ligands: Syntheses, crystal structures, magnetic susceptibility and fluorescence properties (United States)

    Wang, Xiao; Hou, Xiang-Yang; Zhai, Quan-Guo; Hu, Man-Cheng


    Two three-dimensional coordination polymers (CPs), namely [Cd(bpydb)- (H2bpydb)]n·0.5nH2O (1), and [Cu2(bpydb)2]n (2) (2,6-di-p-carboxyphenyl-4,4'- bipyridine1 = H2bpydb), containing a novel double-helical chains, which have been solvothermal synthesized, characterized, and structure determination. CPs 1-2 reveal the new (3,5)-net and (3,6)-net alb topology, respectively. The fluorescence properties of CPs 1-2 were investigated, and magnetic susceptibility measurements indicate that compound 1 has dominating antiferromagnetic couplings between metal ions.

  12. The oxidation of water by cerium(IV) catalysed by nanoparticulate RuO2 on mesoporous silica. (United States)

    King, Nicola C; Dickinson, Calum; Zhou, Wuzong; Bruce, Duncan W


    Mesoporous silicates are prepared by templating on the hexagonal (H1) mesophase of surfactant bipyridine complexes of ruthenium(II) using a true liquid-crystal templating approach. On calcination, the surfactant template is removed except for the central metal ion that is oxidised, forming nanoparticles of RuO2 that deposit within the pores. RuO2 is a known oxidation catalyst and, despite its anhydrous nature in these silicates, is found to be very active in catalyzing the oxidation of water by acidic CeIV.

  13. Self-assembly of heteroleptic dinuclear metallosupramolecular kites from multivalent ligands via social self-sorting

    Directory of Open Access Journals (Sweden)

    Christian Benkhäuser


    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.

  14. Comparison of physical and photophysical properties of monometallic and bimetallic ruthenium(II) complexes containing structurally altered diimine ligands

    Energy Technology Data Exchange (ETDEWEB)

    Macatangay, A.; Jackman, D.C.; Merkert, J.W. [Univ. of North Carolina, Charlotte, NC (United States)] [and others


    The physical and photophysical properties of a series of monometallic, [Ru(bpy){sub 2}(dmb)]{sup 2+}, [Ru(bpy){sub 2}(BPY)]{sup 2+}, [Ru(bpy)(Obpy)]{sup 2+} and [Ru(bpy){sub 2}(Obpy)] {sup 2+}, and bimetallic, [(Ru(bpy){sub 2}){sub 2}(BPY)]{sup 4+} and [(Ru(bpy){sub 2}){sub 2}(Obpy)]{sup 4+}, complexes are examined, where bpy is 2,2{prime}-bipyridine, dmb is 4,4{prime}-dimethyl-2,2{prime}-bipyridine, BPY is 1,2-bis(4-methyl-2,2{prime}-bipyridin-4{prime}-yl)ethane, and Obpy is 1,2-bis(2,2{prime}-bipyridin-6-yl)ethane. The complexes display metal-to-ligand charge transfer transitions in the 450 nmn region, intraligand {pi}{yields}{pi}* transitions at energies greater than 300 nm, a reversible oxidation of the ruthenium(II) center in the 1.25-1.40 V vs SSCE region, a series of three reductions associated with each coordinated ligand commencing at {minus}1.3 V and ending at {approximately}{minus}1.9 V, and emission from a {sup 3}MLCT state having energy maxima between 598 and 610 nm. The Ru{sup III}/Ru{sup II} oxidation of the two bimetallic complexes is a single, two one-electron process. Relative to [Ru(bpy){sub 2}(BPY)]{sup 2+}, the Ru{sup III}/Ru{sup II} potential for [Ru-(bpy){sub 2}(Obpy)]{sup 2+} increases from 1.24 to 1.35 V, the room temperature emission lifetime decreases from 740 to 3ns, and the emission quantum yield decreases from 0.078 to 0.000 23. Similarly, relative to [(Ru(bpy){sub 2}){sub 2}(BPY)]{sup 4+}, the Ru{sup III}/Ru{sup II} potential for [(Ru(bpy){sub 2}){sub 2}(Obpy)]{sup 4+} increases from 1.28 to 1.32 V, the room temperature emission lifetime decreases from 770 to 3 ns, and the room temperature emission quantum yield decreases from 0.079 to 0.000 26.

  15. A new 3-D Gd-Cu heterometallic polymer [Gd_2Cu_3(bpy)_2-(ip)_6]·6H_2O with a non-interpenetrated α-Po net

    Institute of Scientific and Technical Information of China (English)

    JIA XiangLi; ZHOU Jian; ZHAO JunWei; LI ZhaoHui; ZHENG ShouTian; YANG GuoYui


    A new 3-D porous Gd-Cu heterometallic polymer Gd_2Cu_3(bpy)_2(ip)_6]·6H_2O (1) (bpy = 2,2'-bipyridine, H_2ip = isophthalic acid) has been hydrothermally synthesized and structurally characterized. Com-pound 1 crystallizes in the triclinic space group P1 and displays a 3-D non-interpenetrated α-Po net-work with 1-D channels filled transversely by the hexa-nuclear chain-like (H_2O)_6. The EPR and thermal stability of 1 were investigated.

  16. Linear homobimetallic 4-thioacetyl-substituted NCN pincer palladium(II) and platinum(II) complexes with N-bidentate connecting units (NCN = [C6H2(CH2NMe2)2-2,6-R-4]−)

    NARCIS (Netherlands)

    Döring, K.; Taher, D.; Walfort, B.; Lutz, M.; Spek, A.L.; van Klink, G.P.M.; van Koten, G.; Lang, H.


    The synthesis and characterization of homobimetallic palladium and platinum complexes of type [(Me(O)CS-4-NCN–M ← N∩N → M–NCN-4-SC(O)Me](OTf)2 (Me(O)CS-4-NCN = [C6H2(CH2NMe2)2-2,6-SC(O)Me-4]−; N∩N = 4,4′-bipyridine (bipy); M = Pd, 12; M = Pt, 13) is reported. The required bifunctional thio-acetyl NC

  17. Magnetic field induced absorption of zero-phonon lines in (Ru(bpy)3)(PF6)2 and (Ru(bpy)3)(ClO4)2 single crystals

    Energy Technology Data Exchange (ETDEWEB)

    Hensler, G.; Gallhuber, E.; Yersin, H.


    In recent studies they have investigated the spectroscopic properties of (Ru(bpy)3)X2 single crystals (with X = PF6 and ClO4 and bpy = 2,2'-bipyridine). In particular, it was possible to discover sharp, purely electronic (zero-phonon) transitions corresponding to the two lowest excited states in the emission spectra of (Ru(bpy)3)(ClO4)2 and (Ru(bpy)3)(PF6)2. They communicate here the observation of the corresponding zero-phonon lines also in the absorption spectra and report on changes of the absorption under application of high magnetic fields.

  18. Synthesis of new pyrrole–pyridine-based ligands using an in situ Suzuki coupling method

    Directory of Open Access Journals (Sweden)

    Matthias Böttger


    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.

  19. Conjugates of the fungal cytotoxin illudin M with improved tumour specificity. (United States)

    Schobert, Rainer; Biersack, Bernhard; Knauer, Sebastian; Ocker, Matthias


    A simplified procedure for the isolation of gram quantities of illudin M from culture broths of basidiomycete Omphalotus olearius is described. Esters of illudin M with docosahexaenoic acid, chlorambucil, demethylcantharidinic acid (endothall) and 2,2'-bipyridyl-5,5'-dicarboxylic acid were synthesised and tested for cytotoxicity and induction of apoptosis in two clinically relevant tumour cell lines (Panc-1 pancreas carcinoma and HT-29 colon carcinoma) and in non-malignant human foreskin fibroblasts. The demethylcantharidin and the bipyridine conjugates retained the cytotoxicity of the parent illudin M while displaying an improved specificity for the tumour cells over the fibroblasts.

  20. 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.;


    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 studied....... This protein drug system was designed to form non-native homo-oligomers through selective coordination of two divalent metal ions, Fe(II) and Zn(II), respectively. The insulin type chosen for this study is a variant designed for a reduced tendency toward native dimer formation at physiological concentrations...

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

    Directory of Open Access Journals (Sweden)

    Malapaka Chandrasekharam


    Full Text Available 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(NCS2, BPFC” has been synthesized and characterized by FT-IR, 1H-NMR, and ESI-MASS spectroscopes. The sensitizer showed molar extinction coefficient of 18.5×103 M−1cm−1, larger as compared to the reference N719, which showed 14.4×103 M−1cm−1. The test cells fabricated using BPFC sensitizer employing high performance volatile electrolyte, (E01 containing 0.05 M I2, 0.1 M LiI, 0.6 M 1,2-dimethyl-3-n-propylimidazolium iodide, 0.5 M 4-tert-butylpyridine in acetonitrile solvent, exhibited solar-to-electric energy conversion efficiency (η of 4.65% (short-circuit current density (SC = 11.52 mA/cm2, open-circuit voltage (OC = 566 mV, fill factor = 0.72 under Air Mass 1.5 sunlight, lower as compared to the reference N719 sensitized solar cell, fabricated under similar conditions, which exhibited η-value of 6.5% (SC = 14.3 mA/cm2, OC = 640 mV, fill factor = 0.71. UV-Vis measurements conducted on TiO2 films showed decreased film absorption ratios for BPFC as compared to those of reference N719. Staining TiO2 electrodes immediately after sonication of dye solutions enhanced film absorption ratios of BPFC relative to those of N719. Time-dependent density functional theory (TD-DFT calculations show higher oscillation strengths for 4,4-bis(9,9-dibutyl-7-(3,6-di-tert-butyl-9H-carbazol-9-yl-9H-fluoren-2-yl-2,2-bipyridine relative to 2,2-bipyridine-4,4-dicarboxylic acid and increased spectral response for the corresponding BPFC complex.

  2. Electron and proton transfer assemblies and new porous materials from nanometer-scale building blocks (United States)

    Johnson, Stacy Ann

    Elegant examples of molecular engineering are found in nature that make our current small devices seem primitive. By using naturally occurring examples we can better imagine how to construct useful three dimensional nanoscaled devices. Electron and proton transfer composites were prepared using a multilayer film growth technique, in which single anionic sheets derived from inorganic solids are interleaved with cationic polyelectrolytes. This method allows for the growth of concentric monolayers of redox-active polymers on high-surface-area silica supports, and for vectorial electron transfer reactions through the layers of the "onion." Photoinduced charge separation has been observed in composites consisting of an inner polycationic layer of poly(styrene- co-N-vinylbenzyl-N'-methyl-4,4 '-bipyridine), and an outer polycationic layer of poly[Ru(bpy) 2(vbpy)]2+, vbpy = 4-vinyl-4'-methyl- 2,2'-bipyridine, bpy = 2,2' -bipyridine, which are separated by a thin inorganic sheet of Zr(HOPO 3)2·H2O. Following the logic of the proton transport mechanism found in biological membranes, a photosensitive proton pump was constructed using the same electrostatic adsorption technique. This composite was prepared with a polymeric form of a luminescent ruthenium complex, poly[Ru(bpy) 2(bpm)]2+, bpy = 2,2'-bipyridine bpm = 2,2'-bipyrimidine. The pH of a solution in which the composites were suspended changed reversibly when irradiated with visible light. A series of microporous polymer replicas were synthesized using inorganic templates. Zeolites were used as templates to prepare microporous polymer replicas with nanometer sized pore networks. Phenol-formaldehyde polymers were synthesized and cured within the channel networks of zeolites Y, beta, and L. Dissolution of the aluminosilicate framework in aqueous IHF yields an organic replica. The zeolite template exerts important topological effects on the structure and physical properties of the replica. A similar process is described

  3. 4,4′-Bipyridine–3-(thiophen-3-ylacrylic acid (1/2

    Directory of Open Access Journals (Sweden)

    Malaichamy Sathiyendiran


    Full Text Available In the title 1/2 adduct, C10H8N2·2C7H6O2S, the dihedral angle between the pyridine rings is 18.41 (11°. In the thiopheneacrylic acid molecules, the dihedral angles between the respective thiophene and acrylic acid units are 5.52 (17° and 23.92 (9°. In the crystal, the components are linked via O—H...N hydrogen-bonding interactions, forming units of two 3-thiopheneacrylic acid molecules and one 4,4′-bipyridine molecule.


    Institute of Scientific and Technical Information of China (English)

    CHENDean; HUANGShizhuan; 等


    Two kinds of rhodium catalysts supported on cross-linked styrene-divinylbenzene copolymers containing bipyridine or o-phenylene diamine have been prepared and found to display high activity for methyl acetate carbonylation to form acetic anhydride,the activities are even higher than their homogeneous counterparts. XPS analysis was used to characterize the synthetic catalysts.The apparent activation parameters were determined to be Eα=73.3KJ/mol,ΔH≠=66.3KJ/mol,ΔS≠=-28.6eu.These parameters are very close to those in methanol carbonylation and imply to have analogous mechanism in both cases.

  5. Ferrocene and cobaltocene derivatives for non-aqueous redox flow batteries. (United States)

    Hwang, Byunghyun; Park, Min-Sik; Kim, Ketack


    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.

  6. Electron Transfer Mediators for Photoelectrochemical Cells Based on Cu(I Metal Complexes

    Directory of Open Access Journals (Sweden)

    Michele Brugnati


    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.

  7. Characterization of a trinuclear ruthenium species in catalytic water oxidation by Ru(bda)(pic)2 in neutral media. (United States)

    Zhang, Biaobiao; Li, Fei; Zhang, Rong; Ma, Chengbing; Chen, Lin; Sun, Licheng


    A Ru(III)-O-Ru(IV)-O-Ru(III) type trinuclear species was crystallographically characterized in water oxidation by Ru(bda)(pic)2 (H2bda = 2,2'-bipyridine-6,6'-dicarboxylic acid; pic = 4-picoline) under neutral conditions. The formation of a ruthenium trimer due to the reaction of Ru(IV)[double bond, length as m-dash]O with Ru(II)-OH2 was fully confirmed by chemical, electrochemical and photochemical methods. Since the oxidation of the trimer was proposed to lead to catalyst decomposition, the photocatalytic water oxidation activity was rationally improved by the suppression of the formation of the trimer.

  8. High catalytic activity of heteropolynuclear cyanide complexes containing cobalt and platinum ions: visible-light driven water oxidation. (United States)

    Yamada, Yusuke; Oyama, Kohei; Gates, Rachel; Fukuzumi, Shunichi


    A near-stoichiometric amount of O2 was evolved as observed in the visible-light irradiation of an aqueous buffer (pH 8) containing [Ru(II) (2,2'-bipyridine)3 ] as a photosensitizer, Na2 S2 O8 as a sacrificial electron acceptor, and a heteropolynuclear cyanide complex as a water-oxidation catalyst. The heteropolynuclear cyanide complexes exhibited higher catalytic activity than a polynuclear cyanide complex containing only Co(III) or Pt(IV) ions as C-bound metal ions. The origin of the synergistic effect between Co and Pt ions is discussed in relation to electronic and local atomic structures of the complexes.

  9. Fluorinated Boronic Acid-Appended Bipyridinium Salts for Diol Recognition and Discrimination via (19)F NMR Barcodes. (United States)

    Axthelm, Jörg; Görls, Helmar; Schubert, Ulrich S; Schiller, Alexander


    Fluorinated boronic acid-appended benzyl bipyridinium salts, derived from 4,4'-, 3,4'-, and 3,3'-bipyridines, were synthesized and used to detect and differentiate diol-containing analytes at physiological conditions via (19)F NMR spectroscopy. An array of three water-soluble boronic acid receptors in combination with (19)F NMR spectroscopy discriminates nine diol-containing bioanalytes--catechol, dopamine, fructose, glucose, glucose-1-phosphate, glucose-6-phosphate, galactose, lactose, and sucrose--at low mM concentrations. Characteristic (19)F NMR fingerprints are interpreted as two-dimensional barcodes without the need of multivariate analysis techniques.

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

    Energy Technology Data Exchange (ETDEWEB)

    Luis, R. Fernandez de; Urtiaga, M.K. [Dpto. Mineralogia y Petrologia, Facultad de Ciencia y Tecnologia, Universidad del Pais Vasco/UPV/EHU, Apdo. 644, 48080 Bilbao (Spain); Mesa, J.L.; Rojo, T. [Dpto. Quimica Inorganica, Facultad de Ciencia y Tecnologia, Universidad del Pais Vasco UPV/EHU, Apdo. 644, 48080 Bilbao (Spain); Arriortua, M.I. [Dpto. Mineralogia y Petrologia, Facultad de Ciencia y Tecnologia, Universidad del Pais Vasco/UPV/EHU, Apdo. 644, 48080 Bilbao (Spain)], E-mail:


    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 {l_brace}Ni/Bpy/VO{r_brace} and {l_brace}Ni/Bpe/VO{r_brace} 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.

  11. Two supramolecular architectures constructed from dinuclear zinc(II) unit (United States)

    Lou, Ben-Yong; Yuan, Da-Qiang; Wang, Rui-Hu; Xu, Ying; Wu, Ben-Lai; Han, Lei; Hong, Mao-Chun


    Two supramolecular architectures, [Zn 2( D, L-sala) 2(4-H 2Npy) 2·2H 2O] n ( 1) (4-H 2Npy=4-aminopyridine) and [Zn 2( D, L-sala) 2(4,4'-bpy)·0.5H 2O] n ( 2) (4,4'-bpy=4,4'-bipyridine), have been constructed from dinuclear zinc(II) unit [Zn 2( D, L-sala) 2] (sala= N-(2-hydroxybenzyl)-alanine anion). For 1, four dimmers link together through N-H⋯O hydrogen bonds to give rise to a square ring that is extended into two-dimensional supramolecular network. For 2, dinuclear units are connected by 4,4'-bipyridine to generate a one-dimensional chain with ladder structure, which is connected through hydrogen bonds into three-dimensional supramolecular framework. Complex 1 exhibits intense photoluminescence at 402 nm upon photo-excitation at 348 nm, while complex 2 gives two intense photoluminescent peaks at 464 and 613 nm upon photo-excitation at 350 nm.

  12. Transport of Carbonate Ions by Novel Cellulose Fiber Supported Solid Membrane

    Directory of Open Access Journals (Sweden)

    A. G. Gaikwad


    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: ] | View in 

  13. Syntheses and Crystal Structure of [Cu(pyr)3].Hg2I6

    Institute of Scientific and Technical Information of China (English)

    SONGJun-Ling; ZENGHui-Yi; 等


    A new compound containing discrete cationic and anionic complexes,[Cu(pyr)3].Hg2I6 (C30H24CuHg2I6N6),where pyr=2,2′-bipyridine,was prepared by the reaction of CuBr with pyr and HgI2 in mixed solvent of acetone,methanol and acetonitrile,Single-crystal X-ray diffraction analysis indicates that it crystallizes in an orthorhombic system,Pna21(No.33),a=33.1595(7),b=9.4605(1),c=13.0899(2)°↑A,V=4106.4(1)°↑A3,Mr=1694.67,Dc=2.741 g/cm3,Z=4,F(000)=3012,μ(Mokα)=12.511mm-1,R=0.0736,wR=0.1360(I>2σ(I)) and S=1.218,The structure consists of discrete [Hg2I6]2- anions and [Cu(bipyridine3]2+ cations .The double tetrahedral [Hg2I6]2- unit is formed by sharing one tetrahedral edge and possesses approximate D2h symmetry,The mononuclear Cu2+ ion is coordinated by six N atoms from three pyr molecules to form a slightly disordered octahedral geometry.

  14. Hierarchical assembly of collagen peptide triple helices into curved disks and metal ion-promoted hollow spheres. (United States)

    Przybyla, David E; Rubert Pérez, Charles M; Gleaton, Jeremy; Nandwana, Vikas; Chmielewski, Jean


    A 27 amino acid collagen-based peptide (Hbyp3) was designed to radially display nine hydrophobic bipyridine moieties from a triple helical scaffold. Self-assembly of such functionalized triple helices led to the formation of micrometer-scaled disks with a curved morphology, presumably mediated by aromatic interactions, with a height that is in the range of the length of the triple helical peptide. Higher order assembly of these curved disks into micrometer-sized hollow spheres was accomplished through metal-ligand interactions between bipyridine groups of the disks and metal ions such as Fe(II), Co(II), Zn(II) and Cu(II). The thickness of the shell of these hollow spheres corresponds well with the thickness of the collagen peptide-based triple helix and the corresponding self-assembled disks. Addition of a metal ion chelator was found to reverse the assembly of the hollow spheres back to the curved disk structures. These data support the formation of the hollow spheres from the self-assembled disks of Hbyp3 upon addition of metal ions.

  15. Synthesis and Crystal Structure of Cu2 (pba) (bpy) 2 Cl2·4H2O

    Institute of Scientific and Technical Information of China (English)

    朱志成; 毛新平; 徐正; 黄小荥


    A new copper complex, Cu2 (pba)(bpy)2Cl2·4H2O (here pba was pro-pylenebis (oxamic acid), bpy was bipyridine), was synthesized. Crystal structure of thetitle complex was determined. It belongs to the tetragonal system, molecular formulaCu2Cl2Oi0N6C27H32, Mr = 798. 58, space group P4t212, a = b = 9. 484(4), c =35.918(9) A, V = 3235(2) A3, Dx = 1. 64gcm-3 and F(000) = 1568, μ =1. 546mm 1 for Z = 4. The crystal structure was solved by direct methods for final R =0.048 and Rω, = 0.060 for 1992 observed reflections with I >3a (I). The complex hasa C2 symmetry. A chloride anion, two nitrogen atoms from bipyridine and two oxygenatoms from the oxamide carbonyl and carboxyl coordinated to the CuⅡ ion forming asquare pyramidal geometry. In each molecule, two bpy are almost parallel.

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

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


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

  17. Synthesis, characterization, and DNA binding, photocleavage, cytotoxicity, cellular uptake, apoptosis, and on-off light switching studies of Ru(II) mixed-ligand complexes containing 7-fluorodipyrido[3,2-a:2',3'-c]phenazine. (United States)

    Deepika, Nancherla; Kumar, Yata Praveen; Shobha Devi, Chittimalli; Reddy, Putta Venkat; Srishailam, Avudoddi; Satyanarayana, Sirasani


    Four new ruthenium(II) polypyridyl complexes-[Ru(phen)2(7-F-dppz)](2+) (7-F-dppz is 7-fluorodipyrido[3,2-a:2',3'-c]phenazine, phen is 1,10-phenanthroline), [Ru(bpy)2(7-F-dppz)](2+)(2) (bpy is 2,2'-bipyridine), [Ru(dmb)2(7-F-dppz)](2+) (dmb is 4,4'-dimethyl-2,2'-bipyridine), and [Ru(hdpa)2(7-F-dppz)](2+) (hdpa is 2,2'-dipyridylamine)-have been synthesized and characterized. Their DNA binding behavior has been explored by various spectroscopic titrations and viscosity measurements, which indicated that all the complexes bind to calf thymus DNA by means of intercalation with different binding strengths. The light switching properties of these complexes have been evaluated, and their antimicrobial activities have been investigated. Photoinduced DNA cleavage studies have been performed. All the complexes exhibited efficient photocleavage of pBR322 DNA on irradiation. The cytotoxicity of these complexes has been evaluated by 3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyltetrazolium bromide assay with various tumor cell lines. Cellular uptake was studied by flow cytometry and confocal microscopy. Flow cytometry experiments showed that these complexes induced apoptosis of HeLa cell lines.

  18. Catalytic water oxidation by mononuclear Ru complexes with an anionic ancillary ligand. (United States)

    Tong, Lianpeng; Inge, A Ken; Duan, Lele; Wang, Lei; Zou, Xiaodong; Sun, Licheng


    Mononuclear Ru-based water oxidation catalysts containing anionic ancillary ligands have shown promising catalytic efficiency and intriguing properties. However, their insolubility in water restricts a detailed mechanism investigation. In order to overcome this disadvantage, complexes [Ru(II)(bpc)(bpy)OH2](+) (1(+), bpc = 2,2'-bipyridine-6-carboxylate, bpy = 2,2'-bipyridine) and [Ru(II)(bpc)(pic)3](+) (2(+), pic = 4-picoline) were prepared and fully characterized, which features an anionic tridentate ligand and has enough solubility for spectroscopic study in water. Using Ce(IV) as an electron acceptor, both complexes are able to catalyze O2-evolving reaction with an impressive rate constant. On the basis of the electrochemical and kinetic studies, a water nucleophilic attack pathway was proposed as the dominant catalytic cycle of the catalytic water oxidation by 1(+), within which several intermediates were detected by MS. Meanwhile, an auxiliary pathway that is related to the concentration of Ce(IV) was also revealed. The effect of anionic ligand regarding catalytic water oxidation was discussed explicitly in comparison with previously reported mononuclear Ru catalysts carrying neutral tridentate ligands, for example, 2,2':6',2″-terpyridine (tpy). When 2(+) was oxidized to the trivalent state, one of its picoline ligands dissociated from the Ru center. The rate constant of picoline dissociation was evaluated from time-resolved UV-vis spectra.

  19. Terpyridine and Quaterpyridine Complexes as Sensitizers for Photovoltaic Applications

    Directory of Open Access Journals (Sweden)

    Davide Saccone


    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.

  20. 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


    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.

  1. On the viability of cyclometalated Ru(II) complexes as dyes in DSSC regulated by COOH group, a DFT study. (United States)

    Wang, Jian; Bai, Fu-Quan; Xia, Bao-Hui; Feng, Lu; Zhang, Hong-Xing; Pan, Qing-Jiang


    The Ru(II) complexes [Ru(bpp)(dcbpy)Cl](+) (1), [Ru(tcbpp)(bpy)Cl](+) (2), and [Ru(tc'bpp)(bpy)Cl](+) (3) (bpp = 2,6-bis(N-pyrazolyl)pyridine, dcbpy = 4,4'-dicarboxyl-bipyridine, bpy = bipyridine, tcbpp = 4-carboxyl-2,6-bis(2-carboxyl-N-pyrazolyl)pyridine, tc'bpp = 4-carboxyl-2,6-bis(4-carboxyl-N-pyrazolyl)pyridine) are studied theoretically using density functional theory (DFT) techniques to explore their properties as dye in a solar cell. The calculated geometry structure and absorption spectrum of 1 are consistent with its experimental results. The calculation results indicate which sites the COOH groups attach to can significantly influence the electronic structure of the complex. By migrating the COOH groups from the bpy ligand in 1 to bpp ligand in 2 and 3, the nature of LUMO changes from bpy-localized to bpp dominated. The calculated low-lying absorptions at λ > 370 nm of the three complexes are categorized as metal-to-ligand charge-transfer (MLCT) transitions and the transition terminates at the orbital populated by the COOH appended ligand. The atomic spin density analysis also indicates that the ligand which is modified by the COOH groups is the ideal spot for the captured electron to situate. It can be predicted that the performance of 2 and 3 in the dye-sensitized solar cell can be enhanced as compared with 1.

  2. Luminescent hybrid materials based on covalent attachment of Eu(III)-tris(bipyridinedicarboxylate) in the mesoporous silica host MCM-41. (United States)

    Ilibi, Maturi; de Queiroz, Thiago Branquinho; Ren, Jinjun; De Cola, Luisa; de Camargo, Andrea Simone Stucchi; Eckert, Hellmut


    A luminescent inorganic-organic hybrid material was synthesized by covalent immobilization of a europium bipyridine carboxylate complex on the inner pore walls of the mesoporous silica host MCM-41 using the grafting method. Guest-host binding was achieved through double functionalization of the host surface with organosilane reagents (trimethylsilyl, TMS, and aminopropyltriethoxysilane, APTES) followed by reaction of the active amino sites of the APTES residue with the ligand 2,2'-bipyridyl-6,6'-dicarboxylic acid. Addition of EuCl3 solution dissolved in ethanol results in the formation of an immobilized complex having the probable formula Eu(L)x(3 ≥ x ≥ 1)(H2O)y, whose detailed photophysical properties were investigated. In the final step, an additional 2,2'-bipyridine-6 monocarboxylic acid ligand was added in an attempt to complete the coordination sphere of the rare earth ion. Each of the synthesis steps was monitored by (1)H, (13)C, and (29)Si solid state NMR spectroscopies, allowing for a quantitative assessment of the progress of the reaction and the influence of the paramagnetic species on the spectra. Based on these data and additional characterizations by chemical analysis, thermogravimetric analysis (TGA), N2 sorption, X-ray diffraction and FT-IR spectroscopy, a comprehensive quantitative picture of the covalent binding and complexation process was developed.

  3. Turn-On Fluorescent Chemosensor for Fluoride Based on Pyreneamide Derivative

    Energy Technology Data Exchange (ETDEWEB)

    Jeon, Nam Joong; Hong, Sung Won; Hong, Ju Hyun; Jeong, Ju Mi; Nam, Kye Chun [Seoul National University, Seoul (Korea, Republic of)


    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{sup -} 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{sup -} 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.

  4. Zeolite-mediated photochemical charge separation using a surface-entrapped ruthenium-polypyridyl complex. (United States)

    Kim, Yanghee; Lee, Hyunjung; Dutta, Prabir K; Das, Amitava


    Employing the strategy of quaternization of the 2,2' N atoms of the conjugated bipyridine ligand 1,4-bis[2-(4'-methyl-2,2'-bipyrid-4-yl)ethenyl]benzene (L), a polypyridyl complex of ruthenium(II) was tethered on the surface of zeolite Y. Electrochemical and spectroscopic properties of the complex suggest that, upon visible photoexcitation of the MLCT band, the electron is localized on the conjugated ligand rather than the bipyridines. Electron transfer from the surface complex to bipyridinium ions (methyl viologen) within the zeolite was observed. Visible light photolysis of the ruthenium-zeolite solid ion-exchanged with diquat and suspended in a propyl viologen sulfonate solution led to permanent formation of the blue propyl viologen sulfonate radical ion in solution. The model that is proposed involves intrazeolitic charge transfer to ion-exchanged diquat followed by interfacial (zeolite to solution) electron transfer to propyl viologen sulfonate in solution. Because of the slow intramolecular back-electron-transfer reaction and the forward electron propagation via the ion-exchanged diquat, Ru(III) is formed. This Ru(III) complex formed on the zeolite is proposed to react rapidly with water in the presence of light, followed by reaction with the propyl viologen sulfonate, to form pyridones and regeneration of Ru(II), which then continues the photochemical process.

  5. Mechanistic investigation of CO2 hydrogenation by Ru(II) and Ir(III) aqua complexes under acidic conditions: two catalytic systems differing in the nature of the rate determining step. (United States)

    Ogo, Seiji; Kabe, Ryota; Hayashi, Hideki; Harada, Ryosuke; Fukuzumi, Shunichi


    Ruthenium aqua complexes [(eta(6)-C(6)Me(6))Ru(II)(L)(OH(2))](2+) {L = bpy (1) and 4,4'-OMe-bpy (2), bpy = 2,2'-bipyridine, 4,4'-OMe-bpy = 4,4'-dimethoxy-2,2'-bipyridine} and iridium aqua complexes [Cp*Ir(III)(L)(OH(2))](2+) {Cp* = eta(5)-C(5)Me(5), L = bpy (5) and 4,4'-OMe-bpy (6)} act as catalysts for hydrogenation of CO(2) into HCOOH at pH 3.0 in H(2)O. The active hydride catalysts cannot be observed in the hydrogenation of CO(2) with the ruthenium complexes, whereas the active hydride catalysts, [Cp*Ir(III)(L)(H)](+) {L = bpy (7) and 4,4'-OMe-bpy (8)}, have successfully been isolated after the hydrogenation of CO(2) with the iridium complexes. The key to the success of the isolation of the active hydride catalysts is the change in the rate-determining step in the catalytic hydrogenation of CO(2) from the formation of the active hydride catalysts, [(eta(6)-C(6)Me(6))Ru(II)(L)(H)](+), to the reactions of [Cp*Ir(III)(L)(H)](+) with CO(2), as indicated by the kinetic studies.

  6. 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


    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.)

  7. Zinc complexes of the antibacterial drug oxolinic acid: structure and DNA-binding properties. (United States)

    Tarushi, Alketa; Psomas, George; Raptopoulou, Catherine P; Kessissoglou, Dimitris P


    The neutral mononuclear zinc complexes with the quinolone antibacterial drug oxolinic acid in the absence or presence of a nitrogen donor heterocyclic ligand 2,2'-bipyridine or 1,10-phenanthroline have been synthesized and characterized. The experimental data suggest that oxolinic acid is on deprotonated mode acting as a bidentate ligand coordinated to the metal ion through the ketone and one carboxylato oxygen atoms. The crystal structures of (chloro)(oxolinato)(2,2'-bipyridine)zinc(II), 2, and bis(oxolinato)(1,10-phenanthroline)zinc(II), 3, have been determined with X-ray crystallography. The biological activity of the complexes has been evaluated by examining their ability to bind to calf-thymus DNA (CT DNA) with UV and fluorescence spectroscopies. UV studies of the interaction of the complexes with DNA have shown that they can bind to CT DNA and the DNA-binding constants have been calculated. Competitive studies with ethidium bromide (EB) have shown that complex 3 exhibits the ability to displace the DNA-bound EB indicating that it binds to DNA in strong competition with EB.

  8. Knigth's Move in the Periodic Table, From Copper to Platinum, Novel Antitumor Mixed Chelate Copper Compounds, Casiopeinas, Evaluated by an in Vitro Human and Murine Cancer Cell Line Panel. (United States)

    Gracia-Mora, I; Ruiz-Ramírez, L; Gómez-Ruiz, C; Tinoco-Méndez, M; Márquez-Quiñones, A; Lira, L R; Marín-Hernández, A; Macías-Rosales, L; Bravo-Gómez, M E


    We synthesized a novel anticancer agents based on mixed chelate copper (II) complexes, named Casiopeínas((R)) has of general formula [Cu(N-N)(N-O)H(2)O]NO(3) (where, N-N = diimines as 1,10- phenanthroline, 2,2-bipyridine, or substituted and N-O=aminoeidate or [Cu(N-N)(O-O)H(2)O]NO(3) (where NN= diimines as 10-phenanthroline, 2,2-bipyridine or substituted Casiopeínas I, II, IV, V, VI, VII VIII and O-O=acetylacetonate, salicylaldehidate Casiopínas III). We evaluated the in vitro antitumor activity using a human cancer cell panel and some nurine cancer cells. Eleven Casiopeinas are evaluated in order to acquire some structure-activity correlations and some monodentated Casiopeinäs analogues; cisplatinum was used as control drug. The 50% growth inhibition observed is, in all cases reach with concentrations of Casiopeina's 10 or 100 times lower than cisplatinum. In a previous work we reported the induction of apoptosis by Casiopeina II. The results indicate that Casiopeinass are a promising new anticancer drug candidates to be developed further toward clinical trials.

  9. Synthesis of Fe–Li–Cr Multinuclear Complexes as Molecular Magnet Materials

    Directory of Open Access Journals (Sweden)

    Iis Siti Jahro


    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.

  10. Copper-mediated C-H activation/C-S cross-coupling of heterocycles with thiols

    KAUST Repository

    Ranjit, Sadananda


    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.

  11. Synthesis, crystal structure and properties of a new organic-inorganic hybrid Dawson-like polyoxotungstate [Co(2,2'-bpy)3]2[Co(2,2'-bpy)2Cl][Co(2,2'-bpy)2]H2-[SbW18O60]·4H2O

    Institute of Scientific and Technical Information of China (English)


    A new organic-inorganic hybrid polyoxometalate based on Dawson-like polyoxotungstate anion [SbW18O60]9-, formulated [Co(2,2'-bpy)3]2[Co(2,2'-bpy)2Cl][Co(2,2'-bpy)2]H2[SbW18O60]·4H2O (2,2'-bpy= 2,2(-bipyridine) has been synthesized from Sb2O3, Na2WO4, CoCl2, and 2,2'-bipyridine materials by hydrothermal method, and which was characterized by elemental analyses, IR, XPS, EPR, TG, and X-ray single crystal diffraction. Structure analysis shows that the polyoxoanion self-assembled under hydrothermal conditions consists of a Dawson-like polyoxotungstate cluster anion [SbW18O60]9- encapsulating a pyramidal {SbO3} group within the {W18} cluster cage. EPR spectra show that the high-spin octahedral CoⅡ and low-spin CoⅡ ions coexist in the title compound. Magnetic properties indicate that the compound is antiferromagnetic.

  12. Molecular and electronic structures of the members of the electron transfer series [Mn(bpy)3]n (n = 2+, 1+, 0, 1-) and [Mn(tpy)2]m (m = 4+, 3+, 2+, 1+, 0). An experimental and density functional theory study. (United States)

    Wang, Mei; England, Jason; Weyhermüller, Thomas; Wieghardt, Karl


    The members of the electron transfer series [Mn(bpy)3](n) (n = 2+, 1+, 0, 1-) and [Mn(tpy)2](m) (m = 2+, 1+, 0) have been investigated using a combination of magnetochemistry, electrochemistry, and UV-vis-NIR spectroscopy; and X-ray crystal structures of [Mn(II)((Me)bpy(•))2((Me)bpy(0))](0), [Li(THF)4][Mn(II)(bpy(•))3], and [Mn(II)(tpy(•))2](0) have been obtained (bpy = 2,2'-bipyridine; (Me)bpy = 4,4'-dimethyl-2,2'-bipyridine; tpy = 2,2':6,2″-terpyridine; THF = tetrahydrofuran). It is the first time that the latter complex has been isolated and characterized. Through these studies, the electronic structures of each member of both series of complexes have been elucidated, and their molecular and electronic structures further corroborated by broken symmetry (BS) density functional theoretical (DFT) calculations. It is shown that all one-electron reductions that comprise the aforementioned redox series are ligand-based. Hence, all species contain a central high-spin Mn(II) ion (SMn = 5/2). In contrast, the analogous series of Tc(II) and Re(II) complexes possess low-spin electron configurations.

  13. Molecular metal sulfide cluster model for substrate binding to oil-refinery hydrodesulfurization catalysts. (United States)

    Herbst, Konrad; Monari, Magda; Brorson, Michael


    Reaction between [(eta5-Cp')3Mo3S4]+ and [Ni(1,5-cod)2] (Cp' = methylcyclopentadienyl; 1,5-cod = 1,5-cyclooctadiene) in THF at ambient temperature yielded a coordinatively unsaturated cubane-like cluster cation, [(eta5-Cp')3Mo3S4Ni]+. The ligand sphere at the Ni atom could be saturated by coordinating dimethyl sulfide, diethyl sulfide, di(tert-butyl) sulfide, tetrahydrothiophene, thiochroman-4-ol, 1,4-dithiane, pyridine, quinoline, or 4,4'-bipyridine. The products structurally model a mode of substrate coordination on proposed binding sites of heterogeneous MoNi sulfide hydrotreating catalysts. No stable coordination compounds could be isolated for thiophene derivatives. X-ray crystal structures are reported for the ligand-bridged dicluster compounds [[(eta5-Cp')3Mo3S4Ni]2(mu-C4H4S2)][pts]2 (C4H8S2 = 1,4-dithiane) and [[(eta5-Cp')3Mo3S4Ni]2(mu-bipy)][pts]2 (bipy = 4,4'-bipyridine).

  14. TD-DFT Studies on Electronic and Spectral Properties of Platinum(Ⅱ) Complexes with Phenol and Pyridine Groups

    Institute of Scientific and Technical Information of China (English)

    ZHAO Shan-shan; SHI Li-li; SU Zhong-min; GENG Yun; ZHAO Liang


    The molecular structures of the ground and the lowest triplet states for a series of Pt(ll) complexes PtLCl(1)[L=6-(2-hydroxyphenyl)-2,2'-bipyridine],Pt(pp)2[pp=2-(2-hydroxyphenyl)pyridine](2),PtbpyC12(bpy=2,2'-bipyridine)(3),and the free tridentate L ligand(4) were optimized by the density functional theory B3LYP and UB3LYP methods,respectively.On the basis of optimized geometries,the spectral properties were investigated with time-dependent density functional theory(TD-DFT).In comparison with those of complexes 2 and 3,the more rigid structure of complex 1 together with its low rate of the radiationless decay via nonemissive d-d state leads to higher photoluminescence quantum efficiency.And the phosphorescence quantum efficiency of complex 1 can be easily controlled by modifying auxiliary ligands.The introduction of fluorine ligand into complexes can effectively increase the radiation transition rate and decrease the radiationless d-d transition rate,and as a result,a novel complex PtLF(5) might be a good phosphorescent material suitable for organic electronic devices.

  15. Effects of tethering alkyl chains for amphiphilic ruthenium complex dyes on their adsorption to titanium oxide and photovoltaic properties. (United States)

    Ni, Jen-Shyang; Hung, Chun-Yi; Liu, Ken-Yen; Chang, Yu-Hsun; Ho, Kuo-Chuan; Lin, King-Fu


    Ruthenium (II) complex dye, Ru(4,4'-dicarboxyl-2,2'-bipyridine)(4-nonyl-2,2'-bipyridine) (NCS)(2), (denoted as RuC9) tethering single alkyl chain was synthesized and well characterized. Its adsorption behavior onto the mesoporous TiO(2) and photovoltaic properties were compared with Z907 which has similar chemical structure but tethers two alkyl chains. RuC9 dyes tend to aggregate into vesicles in the acetonitrile/t-butanol co-solvent as a result of the amphiphilic structure, whereas Z907 dyes aggregate into lamellae. The dye-sensitized solar cell (DSSC) with RuC9 dye showed higher short-circuit photocurrent than that with Z907, attributing to its higher molar optical extinction coefficient and more adsorption amount onto the mesoporous TiO(2). However, the DSSC with Z907 dye has higher open-circuit photovoltage and power conversion efficiency, presumably due to the fact that Z907 with more alkyl chains formed a molecular layer with higher hydrophobicity. It reduced the charge recombination in the interface between the dye-sensitized mesoporous TiO(2) and electrolyte as verified by the electrochemical impedance spectroscopy and intensity modulated photocurrent and photovoltage spectroscopies.

  16. Synthesis and Crystal Structure of a Novel Three-dimensional Cu(II) Compound {[Cu(2,2'-bipy)(C7H4O5S)(H2O)2]·(H2O}n

    Institute of Scientific and Technical Information of China (English)

    SU Wei; CAO Rong; BI Wen-Hua; LI Xing


    The title compound, {[Cu(2,2'-bipy)(C7H4O5S)(H2O)2](H2O}n (2,2'-bipy = 2,2'- bipyridine), was synthesized by the hydrothermal reaction of Cu(NO3)2(3H2O, 2,2'-bipyridine and 2-sulphobenzoic acid, and structurally characterized by single-crystal X-ray diffraction analysis. The crystal is of triclinic, space group P with a = 9.21(3), b = 10.17(3), c = 10.77(3) (A), α = 77.017(16), β = 89.80(8), γ = 68.46(7)°, V = 911(5) (A)3, Z = 2, (D/s)max = 0.001, Mr = 473.94, Dc = 1.728 g/cm3, μ(MoKα) = 1.365 mm-1, F(000) = 486, the final R = 0.0246 and wR = 0.0628 for 3809 observed reflections with I > 2σ(I). The mononuclear crystal structure extends into a two-dimensional net- work via hydrogen-bonding interactions and a three-dimensional framework is further formed by means of π-π stacking interactions.

  17. Syntheses and Crystal Structure of [Cu(pyr)3]·Hg2I6

    Institute of Scientific and Technical Information of China (English)

    宋俊玲; 曾卉一; 杨冰苹; 董振超; 郭国聪; 黄锦顺


    A new compound containing discrete cationic and anionic complexes, [Cu(pyr)3](Hg2I6 (C30H24CuHg2I6N6), where pyr = 2,2'-bipyridine, was prepared by the reaction of CuBr with pyr and HgI2 in a mixed solvent of acetone, methanol and acetonitrile. Single-crystal X-ray diffraction analysis indicates that it crystallizes in an orthorhombic system, Pna21 (No. 33), a = 33.1595(7), b = 9.4605(1), c = 13.0899(2) A。, V = 4106.4(1) A。3, Mr = 1694.67, Dc = 2.741 g/cm3, Z = 4, F(000) = 3012, μ(MoKα) = 12.511 mm-1, R = 0.0736, wR = 0.1360 (I > 2σ(I)) and S = 1.218. The structure consists of discrete [Hg2I6]2- anions and [Cu(bipyridine)3]2+ cations. The double tetrahedral [Hg2I6]2- unit is formed by sharing one tetrahedral edge and possesses approximate D2h symmetry. The mononuclear Cu2+ ion is coordinated by six N atoms from three pyr molecules to form a slightly disordered octahedral geometry.

  18. Effect of methylene spacers on the spectral, electrochemical, and structural properties of bis(4,4'-disubstituted-2,2'-bipyridyl) ruthenium(II) dye analogues. (United States)

    Lense, Sheri; Hardcastle, Kenneth I; MacBeth, Cora E


    Two new ruthenium complexes, [Ru(L1OMe)2(NCS)2] and [Ru(L2OMe)2(NCS)2] (where L1OMe = 2,2'-bipyridine-4,4'-di(methyl ethanoate) and L2OMe = 2,2'-bipyridine-4,4'-di(methyl propionate)), have been synthesized and characterized using spectroscopic and electrochemical techniques. The [Ru(L2OMe)2(NCS)2] complex has also been characterized by X-ray diffraction studies and reveals a distorted octahedral coordination geometry about the ruthenium center. Cyclic voltammetry studies of both complexes exhibit quasi-reversible Ru(II/III) couples and a number of ligand reduction events. The complex with one methylene spacer between the bipyridyl ligand and the methyl ester functional group, [Ru(L1OMe)2(NCS)2], was particularly unstable under reducing conditions. The properties of these complexes are compared with the ethyl ester analogue of the N3 photosensitizer [Ru(L0OEt)2(NCS)2].

  19. Cytotoxicity of Ru(II) piano-stool complexes with chloroquine and chelating ligands against breast and lung tumor cells: Interactions with DNA and BSA. (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


    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.

  20. Electronic and optical response of functionalized Ru(II) complexes: joint theoretical and experimental study

    Energy Technology Data Exchange (ETDEWEB)

    Kilina, Svetlana [Los Alamos National Laboratory; Tretiak, Sergei [Los Alamos National Laboratory; Sykora, Milan [Los Alamos National Laboratory; Albert, Victor [UNIV OF FLORIDA; Badaeva, Ekaterina [UNIV OF WASHINGTON; Koposov, Alexey [UNIV OF WASHINGTON


    New photovoltaic and photocatalysis applications have been recently proposed based on the hybrid Ru(II)-bipyridine-complex/semiconductor quantum dot systems. In order to attach the Ru(II) complex to the surface of a semiconductor, a linking bridge -- a carboxyl group -- needs to be added to one or two of the 2,2'-bipyridine (bpy) ligands. Such changes in the ligand structure affect electronic and optical properties and, consequently, the charge transfer reactivity of Ru(II)-systems. In this study, we analyze the effects brought by functionalization of bipyridine ligands with the methyl, carboxyl, and carboxilate groups on the electronic structure and optical response of the [Ru(bpy){sub 3}]{sup 2+} complex. First principle calculations based on density functional theory (DFT) and time dependent DFT (TDDFT) are used to simulate the ground and excited-state properties, respectively, of functionalized Ru-complexes in the gas phase and acetonitrile solution. In addition, an effective Frenkel exciton model is used to explain the optical activity and splitting patterns of the low-energy excited states in all molecules. All theoretical results nicely complement and allow for detailed interpretation of experimental absorption spectra of Ru-complexes that have been done in parallel with our theoretical investigations. We found that the carboxyl group breaks the degeneracy of two low-energy optically bright excited states and red-shifts the absorption spectrum, while leaves ionization and affinity energies of complexes almost unchanged. Experimental studies show that deprotonation of the carboxyl group in the Ru-complexes results in a slight blue shift and decrease of oscillator strengths of the low energy absorption peaks. Comparison of experimental and theoretical linear response spectra of deprotonated complexes demonstrate strong agreement if the theoretical calculations are performed with the addition of a dielectric continuum model. A polar solvent is found to

  1. 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: [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)


    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.

  2. Bis(μ-bis{[4-(2-pyridylpyrimidin-2-yl]sulfanyl}methanedisilver(I bis(perchlorate

    Directory of Open Access Journals (Sweden)

    Hai-Bin Zhu


    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].

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

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


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

  4. Eu(Ⅲ) complex-doped PMMA having fast radiation rate and high emission quantum efficiency

    Institute of Scientific and Technical Information of China (English)

    Jin Li Zhang; Bo Wei Chen; Xuan Luo; Kai Du


    Three Eu(Ⅲ) ternary complexes,Eu(hfa-H)3(Phen),Eu(hfa-H)3(Bipy) and Eu(hfa-H)3(Bath) (hfa =hexafluoroacetylacetonate,Phen =1,10-phenanthroline,Bipy =2,2′-bipyridine,Bath =bathophenanthroline),were synthesized.Their luminescent properties were studied by incorporating deuterated Eu(Ⅲ) complexes in a poly(methylmethacrylate) (PMMA) matrix,and the results indicated that luminescent PMMA including Eu(hfa-D)3(Bath) showed promising results for applications to novel organic Eu(Ⅲ) devices,such as the high-power laser materials.Additionally,all the three Eu(Ⅲ) complexes exhibited good thermostabilization.

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

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


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

  6. A small electron donor in cobalt complex electrolyte significantly improves efficiency in dye-sensitized solar cells (United States)

    Hao, Yan; Yang, Wenxing; Zhang, Lei; Jiang, Roger; Mijangos, Edgar; Saygili, Yasemin; Hammarström, Leif; Hagfeldt, Anders; Boschloo, Gerrit


    Photoelectrochemical approach to solar energy conversion demands a kinetic optimization of various light-induced electron transfer processes. Of great importance are the redox mediator systems accomplishing the electron transfer processes at the semiconductor/electrolyte interface, therefore affecting profoundly the performance of various photoelectrochemical cells. Here, we develop a strategy--by addition of a small organic electron donor, tris(4-methoxyphenyl)amine, into state-of-art cobalt tris(bipyridine) redox electrolyte--to significantly improve the efficiency of dye-sensitized solar cells. The developed solar cells exhibit efficiency of 11.7 and 10.5%, at 0.46 and one-sun illumination, respectively, corresponding to a 26% efficiency improvement compared with the standard electrolyte. Preliminary stability tests showed the solar cell retained 90% of its initial efficiency after 250 h continuous one-sun light soaking. Detailed mechanistic studies reveal the crucial role of the electron transfer cascade processes within the new redox system.

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

    DEFF Research Database (Denmark)

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


    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...... sensitized lanthanide-centered PL upon higher energy excitation of the nanocrystal host but not upon excitation at the lowest energy QD absorption band. Growth of the ZnS shell led to the depletion of about 60% of the lanthanide ions present together with depletion of nearly all of the lanthanide-centered PL....... On these bases, we conclude that the lanthanide-centered PL from the CdSe(Ln) cores originates with Ln(3+)-related trap states associated with the QD surface....

  8. The effect of thermal motion on the electron localization in metal-to-ligand charge transfer excitations in [Fe(bpy)3](2+). (United States)

    Domingo, Alex; Sousa, Carmen; de Graaf, Coen


    Accurate electronic structure calculations of the lowest excited states have been performed on twenty snapshots of a molecular dynamics simulation of [Fe(bpy)3](2+) dissolved in water. The thermal motion distorts the structure of the complex from its average D3 symmetry, causing the localization on one bipyridine ligand of the excited electron in the metal-to-ligand charge transfer (MLCT) state. The excitation energy is about 0.25 eV lower than that for the delocalized description of the MLCT state and is in good agreement with experiments. The composition of the MLCT band is carefully analyzed and the effect of thermal motion on the mechanism of light-induced spin crossover is discussed.

  9. The first one-pot synthesis of metal-organic frameworks functionalised with two transition-metal complexes. (United States)

    Platero-Prats, Ana E; Bermejo Gómez, Antonio; Samain, Louise; Zou, Xiaodong; Martín-Matute, Belén


    The synthesis of a metal-organic framework (UiO-67) functionalised simultaneously with two different transition metal complexes (Ir and Pd or Rh) through a one-pot procedure is reported for the first time. This has been achieved by an iterative modification of the synthesis parameters combined with characterisation of the resulting materials using different techniques, including X-ray absorption spectroscopy (XAS). The method also allows the first synthesis of UiO-67 with a very wide range of loadings (from 4 to 43 mol %) of an iridium complex ([IrCp*(bpydc)(Cl)Cl](2-) ; bpydc=2,2'-bipyridine-5,5'-dicarboxylate, Cp*=pentamethylcyclopentadienyl) through a pre-functionalisation methodology.

  10. Poly[[bis(μ-4,4′-bipyridyl-κ2N:N′bis(thiocyanato-κNmanganese(II] diethyl ether disolvate

    Directory of Open Access Journals (Sweden)

    Mario Wriedt


    Full Text Available In the title compound, {[Mn(NCS2(C10H8N22]·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 thicyanate anions are bridged by the bipy ligands into layers parallel to (001. The diethyl ether solvent molecules occupy the voids of the structure.

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

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


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

  12. Cyclic Water Clusters in Tape-Like and Cage-Like Structures

    Directory of Open Access Journals (Sweden)

    Fuhou Lei


    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.

  13. 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


    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.

  14. Septipyridines as conformationally controlled substitutes for inaccessible bis(terpyridine-derived oligopyridines in two-dimensional self-assembly

    Directory of Open Access Journals (Sweden)

    Daniel Caterbow


    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.

  15. Spectroscopic, solvent influence and thermal studies of ternary copper(II) complexes of diester and dinitrogen base ligands. (United States)

    Emara, Adel A A; Abu-Hussein, Azza A A; Taha, Ahmed A; Mahmoud, Nelly H


    New mixed-ligand copper(II) complexes containing the bidentate dinitrogen ligands [N,N,N',N'-tetramethylethylenediamine (tmen), 2,2'-bipyridine (bipy) and 1,10-phenanthroline (phen)] and the bidentate dioxygen ligands [diethylmalonate (DEM), ethylacetoacetate (EAA) and ethylbenzoylacetate (EBA)] were prepared. The complexes were characterized by elemental analysis, infrared, mass and ESR spectral data, magnetic and molar conductance measurements and thermal gravimetric analysis. From the investigation, the geometries of the complexes are square planar for perchlorate complexes and a square pyramid or octahedral for the nitrate complexes. Solvatochromic behavior of the Cu(II) complexes indicates strong solvatochromism of their solutions in polar and non-polar solvents. The observed solvatochromism is due to the solute-solvent interaction between the chelate cation and the solvent molecules.

  16. Gradients of Rectification: Tuning Molecular Electronic Devices by the Controlled Use of Different-Sized Diluents in Heterogeneous Self-Assembled Monolayers. (United States)

    Kong, Gyu Don; Kim, Miso; Cho, Soo Jin; Yoon, Hyo Jae


    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.

  17. An Efficient Way for the Recognition of Zinc Ion via the Fluorescence Enhancement

    Institute of Scientific and Technical Information of China (English)

    桑秋光; 杨镜奎


    This study concentrates on the spectral and complexing properties of a tetraoxycalix[2]arene[2]triazine derivative bearing two bipyridines (Calix-BIPY2) in a mixture of acetonitrile : chloroform (4 : 1, V: V). The results show that Calix-BIPY2 has a highly selectivity and sensitivity towards Zn2+ over various competing eations (K+, Cu2+, Cd2+, Co2+, Fe2+, Hg2+, Ag+, Al3+ and pb2+). The complexation of Zn2+ induces a remarkable fluorescence enhancement due to combination effects of the binding strength, electron spins state of metal ions, photoinduced charge transfer (PCT) and the rigidity of the complexing unit offered by calixarene-based hosts.

  18. A Star of David catenane (United States)

    Leigh, David A.; Pritchard, Robin G.; Stephens, Alexander J.


    We describe the synthesis of a [2]catenane that consists of two triply entwined 114-membered rings, a molecular link. The woven scaffold is a hexameric circular helicate generated by the assembly of six tris(bipyridine) ligands with six iron(II) cations, with the size of the helicate promoted by the use of sulfate counterions. The structure of the ligand extension directs subsequent covalent capture of the catenane by ring-closing olefin metathesis. Confirmation of the Star of David topology (two rings, six crossings) is provided by NMR spectroscopy, mass spectrometry and X-ray crystallography. Extraction of the iron(II) ions with tetrasodium ethylenediaminetetraacetate affords the wholly organic molecular link. The self-assembly of interwoven circular frameworks of controlled size, and their subsequent closure by multiple directed covalent bond-forming reactions, provides a powerful strategy for the synthesis of molecular topologies of ever-increasing complexity.

  19. Coordination behavior of N-benzoylamino acids: Synthesis and structure of mixed-ligand complexes of palladium(Ⅱ) with N-benzoylamino acid dianion and diamine

    Institute of Scientific and Technical Information of China (English)

    龚钰秋; 陈耀峰; 顾建明; 胡秀荣


    Four new mixed-ligand complexes of pailadiumt(Ⅱ) with L1(N-benzoyl-α-amino acid dianion) and L2[ethyldiamine (en),2,2’-bipyridine (Bpy) and 1,10-phenanthroline (Phen)] were synthesized.Ail the complexes have been characterized by elemental analyses,molar conductance,infrared and 1H NMR spectra and therme-gravimetric analyses.Crystal structures of [Pd(Bpy)(Bzval-N,O)] and [Pd(en) (Bzphe-N,O)] H2O have been do termmed by X-ray diffraction analysis.The results indicate that in all the complexes hgand L1 coordinates to palladium (Ⅱ) through deprotonated amide nitrogen and carboxylic oxygen,and there are some intramolecular nonrovalent in teractions in the complexes.

  20. Zinc acetylacetonate hydrate adducted with nitrogen donor ligands: Synthesis, spectroscopic characterization, and thermal analysis (United States)

    Brahma, Sanjaya; Shivashankar, S. A.


    We report synthesis, spectroscopic characterization, and thermal analysis of zinc acetylacetonate complex adducted by nitrogen donor ligands, such as pyridine, bipyridine, and phenanthroline. The pyridine adducted complex crystallizes to monoclinic crystal structure, whereas other two adducted complexes have orthorhombic structure. Addition of nitrogen donor ligands enhances the thermal property of these complexes as that with parent metal-organic complex. Zinc acetylacetonate adducted with pyridine shows much higher volatility (106 °C), decomposition temperature (202 °C) as that with zinc acetylacetonate (136 °C, 220 °C), and other adducted complexes. All the adducted complexes are thermally stable, highly volatile and are considered to be suitable precursors for metal organic chemical vapor deposition. The formation of these complexes is confirmed by powder X-ray diffraction, Fourier transform infrared spectroscopy, mass spectroscopy, and elemental analysis. The complexes are widely used as starting precursor materials for the synthesis of ZnO nanostructures by microwave irradiation assisted coating process.

  1. Synthesis,crystal structures and fluorescence properties of four mixed-ligands Zn(Ⅱ) and Cd(Ⅱ) coordination compounds

    Institute of Scientific and Technical Information of China (English)

    ZHAO LiMin; REN Peng; ZHANG ZhenJie; FANG Ming; SHI Wei; CHENG Peng


    Four new coordination compounds,[Zn(dba)(bpy)]n (1),{[Zn(dba)(phen)].2H2O}n (2),[Cd(dba)(bpy)(H2O)2](3) and [Cd2(dba)2(phen)2]n (4) (H2dba = 2,5-dihydroxy-p-benzenediacetic acid,bpy = 2,2'-bipyridine,phen =1,10-phenanthroline) have been prepared via solvothermal method and characterized by single-crystal X-ray diffraction,infrared spectroscopy,elemental analysis and powder X-ray diffraction.1 and 2 possess 1D infinite chain structures.Complex 3 exhibits a mononuclear structure.Complex 4 owns binuclear symmetry units,which were bridged via the dba ligands forming a 2D framework.The fluorescence properties of 1-4 have been studied.

  2. Synthesis, crystal structures and fluorescence properties of four mixed-ligands Zn(Ⅱ) and Cd(Ⅱ) coordination compounds

    Institute of Scientific and Technical Information of China (English)


    Four new coordination compounds, [Zn(dba)(bpy)]n (1), {[Zn(dba)(phen)]·2H2O}n (2), [Cd(dba)(bpy)(H2O)2] (3) and [Cd2(dba)2(phen)2]n (4) (H2dba = 2,5-dihydroxy-p-benzenediacetic acid, bpy = 2,2′-bipyridine, phen = 1,10-phenanthroline) have been prepared via solvothermal method and characterized by sin-gle-crystal X-ray diffraction, infrared spectroscopy, elemental analysis and powder X-ray diffraction. 1 and 2 possess 1D infinite chain structures. Complex 3 exhibits a mononuclear structure. Complex 4 owns binuclear symmetry units, which were bridged via the dba ligands forming a 2D framework. The fluorescence properties of 1―4 have been studied.

  3. Microwave Irradiated Reactions of N-Phenacylpyridinium Chloride with Aromatic Aldehydes and Ketones

    Institute of Scientific and Technical Information of China (English)

    Ping WU; Xi Mei CAI; Rong YAO; Chao Guo YAN


    In the system of ammonium acetate and acetic acid and under microwave irradiation,N-phenacylpyridinium chloride 1 reacted with chalcone 2 to give 2,4,6-triarylpyrididnes 3a-g in high yields. 3a-g can also be prepared from one-pot reaction of 1 with aromatic aldehydes 4 and substituted acetophenones 5. Under the same conditions 1 can also react with pyridinecar boxaldehyde 6a-c and acetophenone to yield bipyridine derivatives 7a-c. 1 reacted with aromatic aldehyde and cyclohexanone 6 to yield 2,4-diaryltetrahydroquinolines 8a-d. At last 1 reacted with aromatic aldehydes to give 2,4,6-triarylpyrimidine 9a-i. The structure of the products was characterized with 1H NMR and IR and mass spectroscopy.

  4. A Chiral Helical Compound Based on Achiral Components

    Institute of Scientific and Technical Information of China (English)

    ZHANG Qi-Wei; WANG Gui-Xian


    The title compound, [Cu(dpa)(2,2'-bipy)(H2O)2]n 1 (H2dpa = diphenic acid and 2,2'- bipy = 2,2'-bipyridine), has been synthesized and its structure was determined by single-crystal X-ray diffraction. The crystal is of orthorhombic, space group P212121 with a = 10.597(4), b = 11.317(4), c = 17.630(7) (A), V = 2114.3(14)(A)3, C24H20CuN2O6, Mr = 495.97, Z = 4, Dc = 1.558 g/cm3, μ = 1.079 mm-1, F(000) = 1020, Flack value = 0.052(18), R = 0.0430 and wR = 0.1016 for 3381 observed reflections (Ⅰ > 2σ(Ⅰ)). In compound 1, the dpa ligands link metal ions into helical structures in the same direction.

  5. Tris(2,2′-bipyridinecopper(II pentacyanidonitrosoferrate(II methanol disolvate monohydrate

    Directory of Open Access Journals (Sweden)

    Julia A. Rusanova


    Full Text Available The title complex [Cu(C10H8N23][Fe(CN5(NO]·2CH3OH·H2O, consists of discrete [Cu(bpy3]2+ cations (bpy is 2,2′-bipyridine, [Fe(CN5NO]2− anions and solvent molecules of crystallization (two methanol molecules and one water molecules per asymmetric unit. The CuII ion adopts a distorted octahedral environment, coordinated by six N atoms from three bpy ligands. The cation charge is balanced by a nitroprusside counter-anion, which has a slightly distorted octahedral coordination geometry. In the crystal, anions and solvent molecules are involved in O—H...N and O—H...O hydrogen bonds, which form chains along [100]. The cations are located between these chains.

  6. Synthesis, characterization, DNA binding properties, fluorescence studies and toxic activity of cobalt(III) and ruthenium(II) polypyridyl complexes. (United States)

    Nagababu, Penumaka; Shilpa, Mynam; Latha, J Naveena Lavanya; Bhatnagar, Ira; Srinivas, P N B S; Kumar, Yata Praveen; Reddy, Kotha Laxma; Satyanarayana, Sirasani


    The new ligand 4-(isopropylbenzaldehyde)imidazo[4,5-f ][1,10]phenanthroline (ippip) and its complexes [Ru(phen)(2)(ippip)](2+)(1),[Co(phen)(2)(ippip)](3+)(2),[Ru(bpy)(2)(ippip)](2+)(3),[Co(bpy)(2)(ippip)](3+)(4)(bpy=2,2-bipyridine) and (phen=1,10-phenanthroline) were synthesized and characterized by ES(+)-MS, (1)H and (13)C NMR. The DNA binding properties of the four complexes were investigated by different spectrophotometric methods and viscosity measurements. The results suggest that complexes bind to calf thymus DNA (CT-DNA) through intercalation. When irradiated at 365 nm, the complexes promote the photocleavage of pBR322 DNA, and complex 1 cleaves DNA more effectively than 2, 3, 4 complexes under comparable experimental conditions. Furthermore, photocleavage studies reveal that singlet oxygen ((1)O(2)) plays a significant role in the photocleavage.

  7. Synthesis and tunability of highly electron-accepting, N-benzylated "phosphaviologens". (United States)

    Stolar, Monika; Borau-Garcia, Javier; Toonen, Mark; Baumgartner, Thomas


    We report a structure-property study on phosphoryl-bridged viologen analogues with a remarkably low reduction threshold. Utilizing different benzyl groups for N-quaternization, we were able to confirm the p-benzyl substituent effect on the electronic tunability of the system while maintaining the characteristic chromic response of viologens with two fully reversible one-electron reductions. Due to the considerably increased electron-acceptor properties of the phosphoryl-bridged bipyridine precursor, N-benzylation was found to be very challenging and required the development of new synthetic strategies toward the target viologen species. This study also introduces a new and convenient way for the anion exchange of viologen systems by utilizing methyl triflate. Finally, the practical utility of the new species was verified in simplified proof-of-concept electrochromic devices.

  8. Syntheses and Characterization of Some Tetradentate Schiff-Base Complexes and Their Heteroleptic Analogues

    Directory of Open Access Journals (Sweden)

    A. A. Osowole


    Full Text Available VO(IV, Ni(II and Cu(II complexes of the asymmetric Schiff base [(HOC6H3(OCH3C(C6H5:N(CH2CH2N:C(CH3CH:C(C6H5OH], and their heteroleptic analogues with triphenyl phosphine and 2,2’-bipyridine have been synthesized and characterized by elemental analyses, conductance, magnetic, infrared and electronic spectral measurements. The ligand is tetradentate coordinating via the imine N and enolic O atoms. The Ni(II and Cu(II complexes adopt a four coordinate square planar geometry, the VO(IV complex is five coordinate square-pyramidal and the heteroleptic complexes are 6-coordinate, octahedral. The assignment of geometry is collaborated by magnetic moments and electronic spectra measurements. The compounds are non-electrolyte in nitromethane and are magnetically dilute.

  9. Synthesis and Crystal Structure of the First Hybrid Manganese Phosphate with 1-D Framework of Dinuclear Structure

    Institute of Scientific and Technical Information of China (English)


    A novel hybrid manganese phosphate, [(bipy)Mn(H2PO4)2] (bipy = 2,2'-bipyridine) 1, was synthesized, and its structure is characteristic of 1-D framework involving a dinuclear structure made up of edge-sharing Mn(II) octahedra. 1 crystallizes in the monoclinic system, space group C2/c with a = 12.230(2), b = 17.800(4), c = 13.530(3)(A), β = 105.00(3)o, V = 2845.0(10)(A)3, Z = 8. Dc = 1.892 g/cm3, F(000) = 1640, Mr = 405.10, μ(MoKα) = 1.198 mm-1, R = 0.0306 and wR = 0.0657 for 2093 observed reflections (I > 2σ(I)).

  10. Rare earth Ibuprofen complexes: Highlighting a pharmaceutical (United States)

    Kaup, Gina; Meiners, Denise; Kynast, Ulrich H.


    Complexes of Gd3+, Eu3+ and Tb3+ with the widely applied, nonsteroidal, anti-inflammatory drug Ibuprofen ("ibu") have been prepared and characterized with respect to their photo-physical properties. The native complexes proved to be non-luminescent, but acquired very high quantum efficiencies of up to 75% with Eu3+ on co-coordination with bidentate ligands (1,10-phenanthroline, 2,2‧-bipyridine), accompanied by luminescent life times approaching 2 ms. However, due to energy back transfer to the ligand's triplet and the lack of suitable Tb3+ receptor states, the long life times could not grant the expected high efficiencies for Tb(ibu)3phen, the highest value amounting to 27% only despite an accompanying decay of 1.927 ms.

  11. A biomimetic copper water oxidation catalyst with low overpotential. (United States)

    Zhang, Teng; Wang, Cheng; Liu, Shubin; Wang, Jin-Liang; Lin, Wenbin


    Simply mixing a Cu(II) salt and 6,6'-dihydroxy-2,2'-bipyridine (H2L) in a basic aqueous solution afforded a highly active water oxidation catalyst (WOC). Cyclic voltammetry of the solution at pH = 12-14 shows irreversible catalytic current with an onset potential of ~0.8 V versus NHE. Catalytic oxygen evolution takes place in controlled potential electrolysis at a relatively low overpotential of 640 mV. Experimental and computational studies suggest that the L ligand participates in electron transfer processes to facilitate the oxidation of the Cu center to lead to an active WOC with low overpotential, akin to the use of the tyrosine radical by Photosystem II to oxidize the CaMn4 center for water oxidation.


    Institute of Scientific and Technical Information of China (English)

    Jie Bai; Jie-bin Pang; Kun-yuan Qiu; Yen Wei


    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.

  13. 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)


    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.

  14. Electronic Spectra of Bare and Solvated Ruthenium Polypyridine Complexes (United States)

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


    We present work on a prototypical water oxidation catalyst, namely the aqua-complex [(bpy)(tpy)Ru-OH_2]2+ (2,2'-bpy = bipyridine, tpy = 2,2':6',2"-terpyridine), and its hydrated clusters [(bpy)(tpy)Ru-OH_2]2+ ·(H2O)_n, with n = 1 - 4. This complex is the starting species in a catalytic cycle for water oxidation. We couple electrospray ionization mass spectrometry with laser spectroscopy to circumvent challenges that arise in reactive solutions from speciation. Here, we report the electronic spectrum of [(bpy)(tpy)Ru-OH_2]2+ by photodissociation spectroscopy of mass selected, cryogenically prepared ions, and we examine effects of its microhydration environment on its electronic structure. In particular, we investigate the solvatochromic shift of the spectral envelope upon sequential addition of water molecules up to the tetrahydrate.

  15. Interaction of water-soluble bridged porphyrin with DNA

    Institute of Scientific and Technical Information of China (English)

    Kai WANG; Zhi ZHANG; Qianni GUO; Xiaoping BAO; Zaoying LI


    A water-soluble porphyrin dimer (Por Dimer) containing eight positive charges, bridged by 4,4'-dicarboxy-2,2'-bipyridine, has been synthesized. With Meso-tetrakis(N-methyl-pyridium-4-yl)porphyrin (H2TMPyP) as the reference compound, the water-sol-uble porphyrin dimer was investigated for its inter-action with DNA by absorption, fluorescence, and circular dichroism (CD) spectroscopy. The apparent affinity binding constant (Kapp= 1.2×106) of Por Dimer binding to CT DNA was measured by a com-petition method with ethidium bromide (EB) (that of H2TMPyP was 6.9×106). The cleavage ability of Por Dimer to pBR322 plasmid DNA was studied by gel electrophoresis. The results suggest that the binding modes of Por Dimer were complex and involve both intercalation and outside binding.

  16. One-Pot Hydrothermal Synthesis of Two New Copper(Ⅱ) Complexes with 4-Carboxyphenoxy Acetic Acid

    Institute of Scientific and Technical Information of China (English)

    ZHUANG Wen-Juan; SUN Chang-Yan; JIN Lin-Pei


    The one-pot hydrothermal reaction of CuCl2 with H2CPOA and 4,4′-bpy results in two new coordination polymers, [Cu(CPOA)(4,4′-bpy)(H2O)2]·1.5H2O (1) and [Cu2(HCPOA)4(4,4′-bpy)4] (2) (H2CPOA=4-carboxyphenoxy acetic acid, 4,4′-bpy=4,4′-bipyridine) since CPOA2- anions reach equilibrium with HCPOA- anions in the reaction system.Thecrystalstructure of 1 shows a triple interpenetration CdSO4-like net with 1D channel, in which lattice water molecules are located. Complex 2 is a ladder-like 1D double chainstructure assembled through coordination bonds and O-H…N hydrogen bonds.

  17. Enhanced photocurrent production by photosystem I with modified viologen derivatives

    Energy Technology Data Exchange (ETDEWEB)

    Yamanoi, Yoshinori, E-mail: [Department of Chemistry, School of Science, University of Tokyo, 7-3-1 Hongo, Bunkyo-ku, Tokyo 113-0033 (Japan); Terasaki, Nao [National Institute of Advanced Industrial Science and Technology (AIST), 807-1 Shuku-machi, Tosu, Saga 841-0052 (Japan); Miyachi, Mariko [Department of Chemistry, School of Science, University of Tokyo, 7-3-1 Hongo, Bunkyo-ku, Tokyo 113-0033 (Japan); Inoue, Yasunori [Department of Applied Biological Science, Faculty of Science and Technology, Tokyo University of Science, Yamazaki 2641, Noda, Chiba 278-8510 (Japan); Nishihara, Hiroshi, E-mail: [Department of Chemistry, School of Science, University of Tokyo, 7-3-1 Hongo, Bunkyo-ku, Tokyo 113-0033 (Japan)


    This paper describes the construction of a photogenerated electron transfer system based on photosystem I (PSI) and modified molecular wires. Gold electrode surfaces were functionalized with sodium 3-mercapto-1-propanesulfonate and the 2,2 Prime -dimethyl-4,4 Prime -bipyridine cation to form a self-assembled monolayer, which enabled the subsequent immobilization of PSI. A higher photocurrent was observed in the presence of sodium ascorbate as an electron donor under irradiation at 680 nm. - Highlights: Black-Right-Pointing-Pointer Molecular wire was prepared by stepwise alkylation of 2,2 Prime -dimethyl-4,4 Prime -bipridine. Black-Right-Pointing-Pointer Oxidation potentials of the modified molecular wire shifted negatively. Black-Right-Pointing-Pointer Modified gold electrode showed a higher current density than that of previous system.


    Directory of Open Access Journals (Sweden)



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

  19. Structural Diversity of Metallosupramolecular Assemblies Based on the Bent Bridging Ligand 4,4′-Dithiodipyridine

    Directory of Open Access Journals (Sweden)

    Rüdiger W. Seidel


    Full Text Available 4,4′-Dithiodipyridine (dtdp, also termed 4,4′-dipyridyldisulfide, is a bridging ligand of the 4,4′-bipyridine type. The introduction of the disulfide moiety inevitably leads to a relatively rigid angular structure, which exhibits axial chirality. More than 90 metal complexes containing the dtdp ligand have been crystallographically characterised until now. This review focuses on the preparation and structural diversity of discrete and polymeric metallosupramolecular assemblies constructed from dtdp as bridging ligands. These encompass metallamacrocycles with M2L2 topology and coordination polymers with periodicity in one or two dimensions. One-dimensional coordination polymers represent the vast majority of the metallosupramolecular structures obtained from dtdp. These include repeated rhomboids, zigzag, helical and arched chains among other types. In this contribution, we make an attempt to provide a comprehensive account of the structural data that are currently available for metallosupramolecular assemblies based on the bent bridging ligand dtdp.

  20. 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


    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...

  1. In Vitro Polarized Resonance Raman Study of N719 and N719-TBP in Dye Sensitized Solar Cells

    DEFF Research Database (Denmark)

    Hassig, Søren; Jernshøj, Kit; Phuong, Nguyen Tuyet;


    The working efficiency of dye-sensitized solar cells (DSCs) depends on the long-term stability of the dye itself and on the microscopic structure of the dye-semiconductor interface. Previous experimental studies of DSCs based on ruthenium dye with bipyridine ligands (N719) adsorbed to the TiO2......substrate applied FTIR,un-polarized Raman (RS) and un-polarized resonance Raman (RRS) spectroscopy. In the un-polarized RRS studies of N719/TiO2 – DSCs the discussion of the adsorption of N719 was based on the rather weak carbonyl or carboxyl group stretching vibrations and on minor spectral changes...... of overlapping Raman modes, whereas conclusions about the dye-stability was based on the observation that fresh and aged DSCs had almost identical RRS spectra. In the present paper we address the problems mentioned above, by utilizing the unique property of Raman scattering that the polarization of the scattered...

  2. Synthesis, Bonding, and Reactivity of Vanadium(IV) Oxido-Fluorido Compounds with Neutral Chelate Ligands of the General Formula cis-[V(IV)(═O)(F)(L(N-N))2](+). (United States)

    Passadis, Stamatis S; Tsiafoulis, Constantinos; Drouza, Chryssoula; Tsipis, Athanassios C; Miras, Haralampos N; Keramidas, Anastasios D; Kabanos, Themistoklis A


    Reaction of the oxidovanadium(IV)-L(N-N) species (L(N-N) is bipy = 2,2'-bipyridine or bipy-like molecules) with either BF4(-) or HF and/or KF results in the formation of compounds of the general formula cis-[V(IV)(═O)(F)(L(N-N))2](+). Structural and spectroscopic (electron paramagnetic resonance) characterization shows that these compounds are in the tetravalent oxidation state containing a terminal fluorido ligand. Density functional theory calculations reveal that the V(IV)-F bond is mainly electrostatic, which is reinforced by reactivity studies that demonstrate the nucleophilicity of the fluoride ligand in a halogen exchange reaction and in fluorination of various organic substrates.

  3. Luminescence of a conjugated polymer containing europium (III) chelate

    Energy Technology Data Exchange (ETDEWEB)

    Liang, Hao; Xie, Fang, E-mail:


    A europium (III) chelate has been incorporated in a conjugated polymer, poly-[2,2′-bipyridine-5,5′-diyl-(2,5-dihexyl-1,4-phenylene)]. From the absorbance and emission spectra measurement and using the Judd–Ofelt theory, an efficient energy transfer between the conjugated polymer and the europium (III) chelate has been confirmed. The luminescence lifetime of Eu{sup 3+} ion in the conjugated polymer is 0.352 ms and the emission cross section of this material is 3.11×10{sup −21} cm{sup 2}. -- Highlights: • A europium chelate has been incorporated in a conjugated polymer. • Energy transfer in the conjugated polymer containing europium chelate is efficient. • The conjugated polymer containing europium chelate is a promising optical material.

  4. Activation of the CXCR3 chemokine receptor through anchoring of a small molecule chelator ligand between TM-III, -IV, and -VI

    DEFF Research Database (Denmark)

    Rosenkilde, Mette M; Andersen, Michael B; Nygaard, Rie;


    between the extracellular ends of transmembrane (TM) III and TM-IV to anchor aromatic chelators at a location corresponding to the presumed binding pocket for adrenergic receptor agonists. In this construct, free metal ions had no agonistic effect in accordance with the optimal geometry of the metal ion...... site in molecular models built over the inactive form of rhodopsin. In contrast, the aromatic chelators bipyridine or phenanthrolene in complex with Zn(II) or Cu(II) acted as potent agonists displaying signaling efficacies similar to or even better than the endogenous chemokine agonists. Molecular...... modeling and molecular simulations combined with mutational analysis indicated that the metal ion site-anchored chelators act as agonists by establishing an aromatic-aromatic, second-site interaction with TyrVI:16 on the inner face of TM-VI. It is noteworthy that this interaction required...

  5. Efficient hydrogenation of organic carbonates, carbamates and formates indicates alternative routes to methanol based on CO2 and CO. (United States)

    Balaraman, Ekambaram; Gunanathan, Chidambaram; Zhang, Jing; Shimon, Linda J W; Milstein, David


    Catalytic hydrogenation of organic carbonates, carbamates and formates is of significant interest both conceptually and practically, because these compounds can be produced from CO2 and CO, and their mild hydrogenation can provide alternative, mild approaches to the indirect hydrogenation of CO2 and CO to methanol, an important fuel and synthetic building block. Here, we report for the first time catalytic hydrogenation of organic carbonates to alcohols, and carbamates to alcohols and amines. Unprecedented homogeneously catalysed hydrogenation of organic formates to methanol has also been accomplished. The reactions are efficiently catalysed by dearomatized PNN Ru(II) pincer complexes derived from pyridine- and bipyridine-based tridentate ligands. These atom-economical reactions proceed under neutral, homogeneous conditions, at mild temperatures and under mild hydrogen pressures, and can operate in the absence of solvent with no generation of waste, representing the ultimate 'green' reactions. A possible mechanism involves metal-ligand cooperation by aromatization-dearomatization of the heteroaromatic pincer core.

  6. A New Initiator Cholesteryl Chloroformate for Cupper-Based Atom Transfer Radical Polymerization of Methyl Methacrylate

    Institute of Scientific and Technical Information of China (English)

    曹健; 楚娟; 张可达


    The polymerization of metyl methacrylate (MMA) was studied in detail by use of CuCl/L as a catalyst and cholesteryl chloroformate (CC) as an initiator. It was found that the atom transfer radical polymerization of MMA could proceed when L equals to a multidentate aliphatic amine ligand, N,N,N',N",N"-penta(methyl acrylate)diethylenetriamine (MA5-DETA), and no polymerization was occurred while L=2,2'-bipyridine and 1,10-phenanthroline. The linear proportionality of the molecular weights to the conversions and straight lines observed in ln[M]0/[M] versus time plots indicated that the present polymerization system had the typical controlled polymerization characteristics.

  7. Synthesis of nanostructured NiO/Co3O4 through thermal decomposition of a bimetallic (Ni/Co) metal-organic framework as catalyst for cyclooctene epoxidation (United States)

    Abbasi, Alireza; Soleimani, Mohammad; Najafi, Mahnaz; Geranmayeh, Shokoofeh


    Hydrothermal approach has led to the formation of a three-dimensional metal-organic framework (MOF), [NiCo(μ2-tp)(μ4-tp)(4,4‧-bpy)2]n (1) (tp = terephthalic acid and 4,4‧-bpy = 4,4‧-bipyridine) which was characterized by means of single-crystal X-ray diffraction analysis, powder X-ray diffraction (PXRD), FT-IR spectroscopy, scanning electron microscopy (SEM) and inductive coupled plasma optical emission spectroscopy (ICP-OES). Thermal decomposition of the MOF afforded nanostructured mixed metal oxide, namely NiO/Co3O4. The XRD and SEM analysis confirm the formation of the mixed metal oxide. The nanostructured NiO/Co3O4 demonstrated good catalytic activity and selectivity in the epoxidation of cyclooctene in the presence of tert-butyl hydroperoxide (TBHP) as oxidant.

  8. Study on DNA binding behavior and light switch effect of new coumarin-derived Ru(II) complexes (United States)

    Liu, Xue-Wen; Shen, You-Ming; Li, Zhi-Xin; Zhong, Xiao; Chen, Yuan-Dao; Zhang, Song-Bai


    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.

  9. 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


    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.

  10. Strongly luminescing ruthenium(II)/ruthenium(II) and ruthenium(II)/platinum(II) binuclear complexes

    Energy Technology Data Exchange (ETDEWEB)

    Sahai, R.; Baucom, D.A.; Rillema, D.P.


    Two strongly luminescing complexes, ruthenium(II)/ruthenium(II) homobinuclear complex and ruthenium(II)/platinum(II) heterobinuclear complex, have been prepared and characterized. The organic part of the complex is 4,4'-dimethyl-2,2' bipyridine dimer. The luminescence behavior of the homobinuclear and heterobinculear complexes was found to be comparable to that of Ru(bpy)/sub 3//sup 2 +/, although the luminescence maxima were shifted from 615 to 620 nm. These complexes exhibit good stability due to the bidentate chelating capability of the bridging ligand. These new complexes can provide the opportunity for detailed photophysical studies related to donor-acceptor interactions and to the possibility of two simultaneous single-electron transfer events. 17 references, 2 figures.

  11. Hybrid Tungstocuprate [Cu(2,2'-bpy)3]2H4[CuW12O40]·6H2O Based on Keggin Polyoxoanion [CuW12O40]6-with CuⅡas Heteroatom

    Institute of Scientific and Technical Information of China (English)

    WANG Jing-ping; MA Peng-tao; LI Jie; NIU Jing-yang


    A novel hybrid tungstocuprate(Ⅱ) [Cu(2,2'-bpy)3]2H4[CuW12O40]·6H2O(2,2'-bpy=2,2'-bipyridine) was synthesized via hydrothermal method and characterized using elemental analyses, IR, UV, XPS, TG-DSC, EPR, and X-ray single crystal diffraction. The structural analysis shows that the complex consists of an unusual Keggin-type polyoxoanion [CuW12O40]6- and a pair of chiral complex cations [Cu(2,2'-bpy)3]+ together with four protons and six crystallization water molecules, and the Keggin polyoxoanion is connected with [Cu(2,2'-bpy)3]+ via multiple C-H…O hydrogen bonds resulting in a dimer.

  12. Integration of [(Co(bpy)₃]²⁺ electron mediator with heterogeneous photocatalysts for CO₂ conversion. (United States)

    Lin, Jinliang; Hou, Yidong; Zheng, Yun; Wang, Xinchen


    An efficient chemical system for electron generation and transfer is constructed by the integration of an electron mediator ([Co(bpy)3](2+); bpy=2,2'-bipyridine) with semiconductor photocatalysts. The introduction of [Co(bpy)3](2+) remarkably enhances the photocatalytic activity of pristine semiconductor photocatalysts for heterogeneous CO2 conversion; this is attributable to the acceleration of charge separation. Of particular interest is that the excellent photocatalytic activity of heterogeneous catalysts can be developed as a universal photocatalytic CO2 reduction system. The present findings clearly demonstrate that the integration of an electron mediator with semiconductors is a feasible process for the design and development of efficient photochemical systems for CO2 conversion.

  13. 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


    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.

  14. A solid-state electrochemiluminescence biosensing switch for detection of DNA hybridization based on ferrocene-labeled molecular beacon

    Energy Technology Data Exchange (ETDEWEB)

    Wang Xiaoying [School of Public Health, Southeast University, Nanjing 210009 (China); He Pingang, E-mail: [Department of Chemistry, East China Normal University, Shanghai 200062 (China); Fang Yuzhi, E-mail: [Department of Chemistry, East China Normal University, Shanghai 200062 (China)


    A solid-state electrochemiluminescence (ECL) biosensing switch incorporating quenching of ECL of ruthenium(II) tris-(bipyridine) (Ru(bpy){sub 3}{sup 2+}) 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 ({Delta}I{sub ECL}) 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.

  15. A Heteroleptic Ferrous Complex with Mesoionic Bis(1,2,3-triazol-5-ylidene) Ligands: Taming the MLCT Excited State of Iron(II)

    DEFF Research Database (Denmark)

    Liu, Yizhu; Kjær, Kasper Skov; Fredin, Lisa A.;


    Strongly sigma-donating N-heterocyclic carbenes (NHCs) have revived research interest in the catalytic chemistry of iron, and are now also starting to bring the photochemistry and photophysics of this abundant element into a new era. In this work, a heteroleptic Fe-II complex (1) was synthesized...... based on sequentially furnishing the Fe-II center with the benchmark 2,2-bipyridine (bpy) ligand and the more strongly sigma-donating mesoionic ligand, 4,4-bis(1,2,3-triazol-5-ylidene) (btz). Complex1 was comprehensively characterized by electrochemistry, static and ultrafast spectroscopy, and quantum...... chemical calculations and compared to [Fe(bpy)(3)](PF6)(2) and (TBA)(2)[Fe(bpy)(CN)(4)]. Heteroleptic complex1 extends the absorption spectrum towards longer wavelengths compared to a previously synthesized homoleptic Fe-II NHC complex. The combination of the mesoionic nature of btz and the heteroleptic...

  16. Synthesis of Polyketone STCO Promoted by Rare Earth Catalyst

    Institute of Scientific and Technical Information of China (English)

    GUO Jintang; ZHENG Yonghui; WANG Bo; TIAN Jing


    To lower the cost of polyketone synthesis, rare earth coordinate catalyst was introduced to the copolymerization of carbon monoxide (CO) and styrene (ST) to synthesize aliphatic polyketone STCO.The catalytic system was composed of rare earth neodymium acetate, yttrium acetate,2,2'-bipyridine, p-toluensulfonic acid, cupric p-toluensulfonate, and 1,4-benzoquinone.The catalyst and the copolymer were characterized by infrared spectrum and X-ray photoelectron spectroscopy respectively.The effects of each component of catalytic system and the kinds of rare earth acetates on catalytic activity of copolymerization were investigated.The results show that the proposed rare earth has distinct catalytic activity in the copolymerization of CO and ST and the maximum activity can reach 303.3 gSTCO/(mol·h).

  17. Synthesis, characterization, DFT and Td-dfT study of the [Fe(mnt(L(t-BuNC 2] octahedral complex (L = phen, bipy

    Directory of Open Access Journals (Sweden)

    Milton K. MorigakiI


    Full Text Available FeBr2 has reacted with an equivalent of mnt2- (mnt = cis-1,2-dicyanoethylene-1,2-dithiolate and the α-diimine L (L = 1,10'-phenantroline, 2,2'-bipyridine in THF solution, and followed by adding of t-butyl-isocyanide to give [Fe(mnt(L(t-BuNC2] neutral compound. The products were characterized by infrared, UV-visible and Mössbauer spectroscopy, besides thermogravimetric and conductivity data. The geometry in the equilibrium was calculated by the density functional theory and the electronic spectrum by the time-dependent. The experimental and theoretical results in good agreement have defined an octahedral geometry with two isocyanide neighbours. The π→π* intraligand electronic transition was not observed for cis-isomers in the near-IR spectral region.

  18. Manipulating charge transfer excited state relaxation and spin crossover in iron coordination complexes with ligand substitution

    DEFF Research Database (Denmark)

    Zhang, Wenkai; Kjær, Kasper Skov; Alonso-Mori, Roberto


    state lifetime of iron based complexes due to spin crossover-the extremely fast intersystem crossing and internal conversion to high spin metal-centered excited states. We revitalize a 30 year old synthetic strategy for extending the MLCT excited state lifetimes of iron complexes by making mixed ligand...... iron complexes with four cyanide (CN-;) ligands and one 2,2′-bipyridine (bpy) ligand. This enables MLCT excited state and metal-centered excited state energies to be manipulated with partial independence and provides a path to suppressing spin crossover. We have combined X-ray Free-Electron Laser (XFEL......-visible measurement probes allowed electronic transitions between valence states making it sensitive to ligand-centered electronic states such as MLCT states, whereas the Kβ fluorescence spectroscopy provides a sensitive measure of changes in the Fe spin state characteristic of metal-centered excited states. We...

  19. Tracking excited-state charge and spin dynamics in iron coordination complexes

    DEFF Research Database (Denmark)

    Zhang, Wenkai; Alonso-Mori, Roberto; Bergmann, Uwe


    to spin state, can elucidate the spin crossover dynamics of [Fe(2,2'-bipyridine)(3)](2+) on photoinduced metal-to-ligand charge transfer excitation. We are able to track the charge and spin dynamics, and establish the critical role of intermediate spin states in the crossover mechanism. We anticipate......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...... 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...

  20. 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


    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.

  1. Synthesis and Characterization of Zinc β-Diketonate Complex Extended to the Macromolecular Polymers

    Directory of Open Access Journals (Sweden)

    Mohammed A. Al-Anber


    Full Text Available A mononuclear complex of [Zn(tta2(H2O2] (3 (tta = deprotonated of 1-thenoyl-4,4,4-trifluoro­acetone (1 has been prepared by the reaction of 1-thenoyl-4,4,4-trifluoro­acetone (H-tta: 1 with Zn(OAc2.4H2O (OAc = O2CMe in a 2:1 molar ratio. Complex 3 can be extended to form a coordination polymers of general formula [Zn(tta2(X]n (X = 4,4'-bipy (4, pz (5 by the reaction of zinc atom in 3 with s-donor ligand such as 4,4-bipyridine (4,4'-bipy and pyrazin (pz. The reaction completion was controlled via FTIR and elemental analysis.

  2. 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


    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.

  3. 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


    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.

  4. Bis(o-methylserotonin)-containing iridium(III) and ruthenium(II) complexes as new cellular imaging dyes: synthesis, applications, and photophysical and computational studies. (United States)

    Núñez, Cristina; Silva López, Carlos; Faza, Olalla Nieto; Fernández-Lodeiro, Javier; Diniz, Mario; Bastida, Rufina; Capelo, Jose Luis; Lodeiro, Carlos


    We report the synthesis, characterization, and scope of a new versatile emissive molecular probe functionalized with a 1,10-phenanthroline moiety containing methylserotonin groups as binding sites for metal ion recognition. The synthesis, characterization, and evaluation of the in vitro imaging capability of the iridium(III) and ruthenium(II) complexes [Ir(ppy)2(N-N)](+) and [Ru(bpy)2(N-N)](2+), in which ppy is 2-phenylpyridine, bpy is 2,2'-bipyridine, and N-N is a 1,10-phenanthroline ligand functionalized with two methylserotonin groups to serve as binding sites for metal ion recognition, is reported. The uptake of these compounds by living freshwater fish (Carassius auratus) was studied by fluorescence microscopy, and the cytotoxicity of ligand N-N and [Ru(bpy)2(N-N)](2+) in this species was also investigated.

  5. Synthesis, characterization, photophysical, and computational studies of rhenium(I) tricarbonyl complexes containing the derivatives of bipyrazine. (United States)

    Kirgan, Robert; Simpson, Megan; Moore, Curtis; Day, Jeff; Bui, Loan; Tanner, Clayton; Rillema, D Paul


    The chloro and pyridinate derivatives of rhenium(I) tricarbonyl complexes containing the diimine ligands 2,2'-bipyrazine (bpz) and 5,5'-dimethyl-2,2'-bipyrazine (Me2bpz) are reported. Absorption maxima occur in the visible and ultraviolet regions of the spectrum; emission is structureless at room temperature and at 77 K; the infrared spectrum consists of three carbonyl stretches; electrochemically, a reversible reduction, an irreversible reduction, and an irreversible oxidation take place. Some ring protons are shielded and others deshielded in the presence of the methyl substituents attached to the bpz ring. DFT and TDDFT calculations provide insight into interpreting electronic and vibrational properties of the complexes. When compared to similar rhenium(I) tricarbonyl complexes of 2,2'-bipyridine (bpy) and 2,2'-bipyrimidine (bpm), the Me2bpz complexes are comparable to bpm derivatives and their properties are intermediate between those of bpy and bpz complexes.

  6. Synthesis, characterization, X-ray crystal structure, DFT calculation, DNA binding, and antimicrobial assays of two new mixed-ligand copper(II) complexes (United States)

    Ebrahimipour, S. Yousef; Sheikhshoaie, Iran; Mohamadi, Maryam; Suarez, Sebastian; Baggio, Ricardo; Khaleghi, Moj; Torkzadeh-Mahani, Masoud; Mostafavi, Ali


    Two new Cu(II) complexes, [Cu(L)(phen)] (1), [Cu(L)(bipy)] (2), where L2- = (3-methoxy-2oxidobenzylidene)benzohydrazidato, phen = 1,10 phenanthroline, and bipy = 2,2‧ bipyridine, were prepared and fully characterized using elemental analyses, FT-IR, molar conductivity, and electronic spectra. The structures of both complexes were also determined by X-ray diffraction. It was found that, both complexes possessed square pyramidal coordination environment in which, Cu(II) ions were coordinated by donor atoms of HL and two nitrogens of heterocyclic bases. Computational studies were performed using DFT calculations at B3LYP/6-311+G(d,p) level of theory. DNA binding activities of these complexes were also investigated using electronic absorption, competitive fluorescence titration and cyclic voltammetry studies. The obtained results indicated that binding of the complexes to DNA was of intercalative mode. Furthermore, antimicrobial activities of these compounds were screened against microorganisms.

  7. Design, synthesis, and characterization of a novel class of tunable chromophores for second- and third-order NLO applications (United States)

    Attias, Andre-Jean; Leclerc, Nicolas; Chen, Qiying; Sargent, Edward H.; Schull, Guillaume; Charra, Fabrice


    We describe a general approach for the synthesis of 6,6'-(disubstituted)-3,3'-bipyridine based chromophores. This combinatorial type strategy is based on (i) the synthesis of a library of conjugated building blocks end-capped with electron donor or acceptor groups, and (ii) their homo- or cross-coupling. The compounds are either dipolar (push-pull molecules) or apolar (symmetric D-A-A-D) molecules. Depending on the building blocks, we are able to tune both the structural and NLO properties of the chromophores. For example, the D-A-A-D structure possesses ultrafast nonresonant nonlinearity around 1550 nm with excellent figures of merit, as well as TPA in the visible and NIR ranges.

  8. 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


    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.

  9. In Vitro Polarized Resonance Raman Study of N719 and N719-TBP in Dye Sensitized Solar Cells

    DEFF Research Database (Denmark)

    Hassing, Søren; Jernshøj, Kit Drescher; Nguyen, Phuong Tuyet;


    the adsorption of the dye on TiO2 can be obtained. Furthermore it is found that the polarization fluorescence anisotropy is very different for adsorbed and non-adsorbed dye molecules. This information is automatically obtained when processing the Raman data. The conclusion is that if the polarization properties......Abstract: The working efficiency of dye-sensitized solar cells (DSCs) depends on the long-term stability of the dye itself and on the microscopic structure of the dye-semiconductor interface. Previous experimental studies of DSCs based on ruthenium dye with bipyridine ligands (N719) adsorbed...... on N719/TiO2 – DSCs that by combining an analysis of the wave number dependent polarization of these modes with the small shifts observed in the visible absorption spectra of adsorbed, non-adsorbed molecules and degradation products new and more reliable information about dye stability and about...

  10. Chlorine adlayer-templated growth of a hybrid inorganic-organic layered structure on Au(111) (United States)

    Rzeźnicka, I. I.; Horino, H.; Yagyu, K.; Suzuki, T.; Kajimoto, S.; Fukumura, H.


    Growth of a hybrid inorganic-organic layered structure on the Au(111) surface using a one-step solution growth is reported. The hybrid structure is consist of 4,4‧-bipyridine [4,4‧-BiPyH2]2 + cations, Cl anions and Au adatoms, provided from substrate by means of the adsorbate-induced surface phase transition of a surface reconstruction. Its surface and bulk structures were characterized by scanning tunneling microscopy (STM), secondary ion mass spectrometry (SIMS), and Raman spectroscopy. STM results reveal growth of the first [4,4‧-BiPyH2]2 + layer on top of the p(√{ 3} ×√{ 3})" separators=", R 30 ° chlorine overlayer formed on the Au(111) surface. These two layers are found to provide a platform for a following three-dimensional growth facilitated by hydrogen bonding, aurophilic and π-π stacking interactions.

  11. Heteroaromatic donors in donor-acceptor-donor based fluorophores facilitate zinc ion sensing and cell imaging. (United States)

    Sreejith, Sivaramapanicker; Divya, Kizhumuri P; Jayamurthy, Purushothaman; Mathew, Jomon; Anupama, V N; Philips, Divya Susan; Anees, Palappuravan; Ajayaghosh, Ayyappanpillai


    The excited state intra molecular charge transfer (ICT) property of fluorophores has been extensively used for the design of fluorescent chemosensors. Herein, we report the synthesis and properties of three donor–π-acceptor–π-donor (D–π-A–π-D) based molecular probes BP, BT and BA. Two heteroaromatic rings, pyrrole (BP), and thiophene (BT) and a non-heteroaromatic ring N-alkoxy aniline (BA) were selected as donor moieties which were linked to a bipyridine binding site through a vinylic linkage. The heteroaromatic systems BP and BT perform selective and ratiometric emission signalling for zinc ions whereas the non-heteroaromatic probe BA does not. The advantages of the D–π-A–π-D design strategy in the design of ICT based probes for the selective fluorescent ratiometric signalling of zinc ions in biological media is discussed. Further, the use of BP, BT and BA for imaging Zn(2+) ions from MCF-7 cell lines is demonstrated.

  12. Evaluating the Critical Thickness of TiO 2 Layer on Insulating Mesoporous Templates for Efficient Current Collection in Dye-Sensitized Solar Cells

    KAUST Repository

    Chandiran, Aravind Kumar


    In this paper, a way of utilizing thin and conformal overlayer of titanium dioxide on an insulating mesoporous template as a photoanode for dye-sensitized solar cells is presented. Different thicknesses of TiO2 ranging from 1 to 15 nm are deposited on the surface of the template by atomic layer deposition. This systematic study helps unraveling the minimum critical thickness of the TiO2 overlayer required to transport the photogenerated electrons efficiently. A merely 6-nm-thick TiO2 film on a 3-μm mesoporous insulating substrate is shown to transport 8 mA/cm 2 of photocurrent density along with ≈900 mV of open-circuit potential when using our standard donor-π-acceptor sensitizer and Co(bipyridine) redox mediator. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  13. Synthesis, structure and spectroscopic properties of rare earth complexes with a new aryl amide 2,2'-bipydine derivative (United States)

    Song, Xue-Qin; Zheng, Jiang-Rong; Liu, Wei-Sheng; Ju, Zheng-Hua


    Solid complexes of rare earth nitrates and picrates with a new aryl amide ligand 3.3'-bis(benzylamido)-2,2'-bipyridine ( L) were synthesized and characterized by elemental analysis, IR and molar conductivity measurements. The molecular structures of the complex [TbL 2(NO 3) 3H 2O]·2H 2O have been determined by single-crystal X-ray diffraction. The fluorescent properties of the Eu(III) and Tb(III) nitrates and picrates complexes in solid state were also investigated in detail. Under the excitation, these complexes exhibited characteristic emissions of europium and terbium ions. It is worth noting that the nature of the anion has a great effect upon the composition of the complexes as well as emission properties of them.

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

    Directory of Open Access Journals (Sweden)

    Hiroshi Kajiro


    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.

  15. Investigation of the effect of pore size on gas uptake in two metal-organic frameworks. (United States)

    Wang, Rongming; Meng, Qingguo; Zhang, Liangliang; Wang, Haifeng; Dai, Fangna; Guo, Wenyue; Zhao, Lianming; Sun, Daofeng


    Two porous metal–organic frameworks (1 and 2) with a fsc topology based on mixed ligands have been assembled and characterized. The different pillared ligands (pyrazine for 1 and 4,4′-bipyridine for 2) significantly influence the pore size of the frameworks. Gas uptake measurements reveal that complex 1 possesses higher H2, CO2, and CH4 uptake capacities than 2, although the surface area of 1 is lower than that of complex 2. These results further experimentally prove that the pore size plays an important role in gas uptake in porous MOFs, and the slit pore with a size of ~6 Å exhibits stronger interactions with gas molecules.

  16. Two-step spin-switchable tetranuclear Fe(II) molecular solid: Ab initio theory and predictions (United States)

    Maldonado, Pablo; Kanungo, Sudipta; Saha-Dasgupta, Tanusri; Oppeneer, Peter M.


    Using density functional theory supplemented with on-site Coulomb U interaction in combination with ab initio molecular dynamics simulations, we investigate the spin-crossover (SCO) properties of a Fe(II) based cyanide-bridged square molecular system, [FeII4(μ-CN)4(bpy)4(tpa)2](PF6)4 (where bpy = 2,2'-bipyridine and tpa = tris(2-pyridylmethyl)amine], exhibiting a two-step SCO transition. The ab initio calculated SCO temperatures are found to show remarkably good agreement with experimentally measured spin conversion temperatures [M. Nihei , Angew. Chem., Int. Ed.1433-785110.1002/anie.200502216 44, 6484 (2005)]. Our theoretical study predicts further chemo switching of the spin state by introduction of guest molecules such as CO2, CS2, and H2O into the porous topology of the system, which would add another dimensionality to this interesting material.

  17. A trinuclear ruthenium complex as a highly efficient molecular catalyst for water oxidation. (United States)

    Zhang, L L; Gao, Y; Liu, Z; Ding, X; Yu, Z; Sun, L C


    A trinuclear ruthenium complex, 3, was designed and synthesized with the ligand 2,2'-bipyridine-6,6'-dicarboxylic acid (bda) and we found that this complex could function as a highly efficient molecular catalyst for water oxidation in homogeneous systems. This trinuclear molecular water oxidation catalyst, 3, displayed much higher efficiencies in terms of turnover numbers and initial oxygen evolution rate than its counterparts, a binuclear catalyst, 2, and a mononuclear catalyst, 1, in both chemically driven and photochemically driven water oxidation based on either the whole catalytic molecules or just the active Ru centers. The reasons for the superior performance of catalyst 3 were discussed and we believe that multiple Ru centers in a single molecule are indeed beneficial for increasing the probability of the formation of O-O bonds through an intramolecular radical coupling pathway.

  18. Control of excitation and quenching in multi-colour electrogenerated chemiluminescence systems through choice of co-reactant. (United States)

    Barbante, Gregory J; Kebede, Noah; Hindson, Christopher M; Doeven, Egan H; Zammit, Elizabeth M; Hanson, Graeme R; Hogan, Conor F; Francis, Paul S


    We demonstrate a new approach to manipulate the selective emission in mixed electrogenerated chemiluminescence (ECL) systems, where subtle changes in co-reactant properties are exploited to control the relative electron-transfer processes of excitation and quenching. Two closely related tertiary-amine co-reactants, tri-n-propylamine and N,N-diisopropylethylamine, generate remarkably different emission profiles: one provides distinct green and red ECL from [Ir(ppy)3] (ppy=2-phenylpyridinato-C2,N) and a [Ru(bpy)3](2+) (bpy=2,2'-bipyridine) derivative at different applied potentials, whereas the other generates both emissions simultaneously across a wide potential range. These phenomena can be rationalized through the relative exergonicities of electron-transfer quenching of the excited states, in conjunction with the change in concentration of the quenchers over the applied potential range.

  19. Bioinspired Tungsten Dithiolene Catalysts for Hydrogen Evolution: A Combined Electrochemical, Photochemical, and Computational Study. (United States)

    Gomez-Mingot, Maria; Porcher, Jean-Philippe; Todorova, Tanya K; Fogeron, Thibault; Mellot-Draznieks, Caroline; Li, Yun; Fontecave, Marc


    Bis(dithiolene)tungsten complexes, W(VI)O2 (L = dithiolene)2 and W(IV)O (L = dithiolene)2, which mimic the active site of formate dehydrogenases, have been characterized by cyclic voltammetry and controlled potential electrolysis in acetonitrile. They are shown to be able to catalyze the electroreduction of protons into hydrogen in acidic organic media, with good Faradaic yields (75-95%) and good activity (rate constants of 100 s(-1)), with relatively high overpotentials (700 mV). They also catalyze proton reduction into hydrogen upon visible light irradiation, in combination with [Ru(bipyridine)3](2+) as a photosensitizer and ascorbic acid as a sacrificial electron donor. On the basis of detailed DFT calculations, a reaction mechanism is proposed in which the starting W(VI)O2 (L = dithiolene)2 complex acts as a precatalyst and hydrogen is further formed from a key reduced W-hydroxo-hydride intermediate.

  20. Conversion of agonist site to metal-ion chelator site in the beta(2)-adrenergic receptor

    DEFF Research Database (Denmark)

    Elling, C E; Thirstrup, K; Holst, Birgitte


    in the mutant receptors not by normal catecholamine ligands but instead either by free zinc ions or by zinc or copper ions in complex with small hydrophobic metal-ion chelators. Chelation of the metal ions by small hydrophobic chelators such as phenanthroline or bipyridine protected the cells from the toxic......Previously metal-ion sites have been used as structural and functional probes in seven transmembrane receptors (7TM), but as yet all the engineered sites have been inactivating. Based on presumed agonist interaction points in transmembrane III (TM-III) and -VII of the beta(2)-adrenergic receptor......, in this paper we construct an activating metal-ion site between the amine-binding Asp-113 in TM-III-or a His residue introduced at this position-and a Cys residue substituted for Asn-312 in TM-VII. No increase in constitutive activity was observed in the mutant receptors. Signal transduction was activated...


    Institute of Scientific and Technical Information of China (English)

    Jin-ying Yuan; Cai-yuan Pan


    Poly(methyl acrylate)-b-poly(5,6-benzo-2-methylene-1,3-dioxepane) (PMA-b-PBMDO) was synthesized by twostep atom transfer radical polymerization (ATRP). Firstly, ATRP of methyl acrylate (MA) was realized using ethyl α-bromobutyrate (EBrB) as initiator in the presence of CuBr/2,2'-bipyridine. After isolation, poly(methyl acrylate) with terminal bromine (PMA-Br) was synthesized. Secondly, the resulting PMA-Br was used as a macromolecular initiator in the ATRP of BMDO. The structure of block copolymer was characterized by 1H-NMR spectroscopy. Molecular weight and molecular weight distribution were determined on a gel permeation chromatograph (GPC).

  2. The layered compound poly[mu2-4,4'-bipyridyl-di-mu2-chlorido-mercury(II)]. (United States)

    Xie, Yi-Ming; Wu, Ji-Huai


    The title compound, [HgCl2(C(10)H(8)N(2))]n, features two-dimensional [HgCl2(4,4'-bipy)]n neutral networks (4,4'-bipy is 4,4'-bipyridine), based on an octahedral Hg atom coordinated by four mu2-Cl atoms and two mu2-4,4'-bipy ligands in trans positions, yielding a HgCl(4)N(2) octahedron. The structure has mmm symmetry about the Hg atoms, with most of the atoms on at least one mirror plane, but the unsubstituted C atoms of the 4,4'-bipy rings are disordered across a mirror plane. Photoluminescent investigations reveal that the title compound displays a strong emission in the green region, which probably originates from a ligand-to-ligand charge-transfer transition.

  3. Synthesis, characterization, and anticancer activity of ruthenium-pyrazole complexes. (United States)

    David, Solene; Perkins, Richard S; Fronczek, Frank R; Kasiri, Sahba; Mandal, Subhrangsu S; Srivastava, Radhey S


    A series of new water soluble Ru(III) pyrazole complexes mer-[RuCl(3)(DMSO-S)(pyz)(2)] 1, mer-[RuCl(3)(DMSO-S)(DMSO-O)(pyz)] 2, mer-[RuCl(3)(bpy)(dmpyz)] 3, and mer-[RuCl(3)(DMSO-S)(dmpyz)(2)] 4 (pyz=pyrazole; dmpyz=3,5-dimethylpyrazole, bpy=2,2'-bipyridine) have been synthesized and characterized by use of a combination of spectroscopy (IR and UV-visible), X-ray diffraction, and cyclic voltammetry. The molecular X-ray structure of all reported compounds (1-4) revealed distorted octahedral coordination around ruthenium. The cytotoxicity assay on human breast cancer cells (MCF7) demonstrated that compounds 1 and 4 affect cell viability, whereas compounds 2 and 3 do not show appreciable activity. The IC(50) values for 1 and 4 lie within the range of 71-32μM in MCF7 cells.

  4. Selective Alcohol Oxidation by a Copper TEMPO Catalyst: Mechanistic Insights by Simultaneously Coupled Operando EPR/UV-Vis/ATR-IR Spectroscopy. (United States)

    Rabeah, Jabor; Bentrup, Ursula; Stößer, Reinhard; Brückner, Angelika


    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 .

  5. Preparation of gradient polyacrylate brushes in microchannels. (United States)

    Lee, Seongyeol; Youm, Sang Gil; Song, Yeari; Yi, Whikum; Sohn, Daewon


    Gradient poly(2-hydroxyethyl methacrylate) brushes were synthesized by surface-initiated atom transfer radical polymerization (ATRP) confined within a microfluidic system on a silicon wafer. For ATRP, surface initiator, 11-((2-bromo, 2-methyl) propionyloxy) undecyltrichlorosilane (BUC), was synthesized, and allowed to self-assemble in a monolayer on the Si wafer, as analyzed by XPS to confirm the presence of an ester group of BUC. A solution containing 2-hydroxyethylmethacrylate, Cu catalyst, and bipyridin was allowed to flow in a microchannel and polymerize, resulting in the brushes with a gradient of thickness on the Si wafer. Using ellipsometry and ATR-IR, we verified the gradients of well established brushes on the Si wafer. AFM and contact angle data showed that wettability of the brushes did not exhibit a linear relationship with hydrophilicity.

  6. Allosteric activation of membrane-bound glutamate receptors using coordination chemistry within living cells (United States)

    Kiyonaka, Shigeki; Kubota, Ryou; Michibata, Yukiko; Sakakura, Masayoshi; Takahashi, Hideo; Numata, Tomohiro; Inoue, Ryuji; Yuzaki, Michisuke; Hamachi, Itaru


    The controlled activation of proteins in living cells is an important goal in protein-design research, but to introduce an artificial activation switch into membrane proteins through rational design is a significant challenge because of the structural and functional complexity of such proteins. Here we report the allosteric activation of two types of membrane-bound neurotransmitter receptors, the ion-channel type and the G-protein-coupled glutamate receptors, using coordination chemistry in living cells. The high programmability of coordination chemistry enabled two His mutations, which act as an artificial allosteric site, to be semirationally incorporated in the vicinity of the ligand-binding pockets. Binding of Pd(2,2‧-bipyridine) at the allosteric site enabled the active conformations of the glutamate receptors to be stabilized. Using this approach, we were able to activate selectively a mutant glutamate receptor in live neurons, which initiated a subsequent signal-transduction pathway.

  7. Extending the Newns-Anderson model to molecules with floppy degrees of freedom. Validation by electronic structure calculations

    CERN Document Server

    Baldea, Ioan


    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.

  8. 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: [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)


    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.

  9. 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


    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.

  10. Magnetic susceptibility and Mössbauer studies of [FeX3](ClO4)2.H2O with X = bpz, bpy, phen or tpy (United States)

    Ho, J. C.; Hamdeh, H. H.; Kirgan, R.; Rillema, D. P.


    Magnetic studies have been made on several tris-chelated iron complex compounds [FeX3](ClO4)2.H2O with aromatic nitrogen heterocycle ligands X = bpz (2,2'-bipyrazine), bpy (2,2'-bipyridine), phen (1,10-phenanthroline) or tpy (2,2':6,2''-terpyridine). SQUID data (2-300 K and 0.01-1 T) yielded small effective magnetic moments, which are characteristic of low-spin Fe(II), in agreement with the isomer shift and quadrupole splitting values from Mössbauer measurements (4-300 K, 0-5 T). Meanwhile, apart from the expected diamagnetism, a positive term of temperature-independent paramagnetic susceptibility prevails in most cases.

  11. Infinite Three-Dimensional Coordination Polymers: Synthesis and Structures of [Cd (4,4'-bpy)2 (H2O)2]n (pic)2n, [Zn (4,4'-bpy)2 (H2O)2 ]n-(pic)2n (H2O)2n, and [Zn (4,4'-bpy)2 (H2O)2]n (4,4'-bpy)n (H2O)n (pic)2n

    Institute of Scientific and Technical Information of China (English)


    Three Complexes of the formula [ Cd (4,4'-bpy)2 (H2O)2 ]n (pic)2n (1), [ Zn (4,4'-bpy)2 (H2O)2 ]n-(pic)2n (H2O)2n (2) and [ Zn (4,4'-bpy)2 (H2O)2 ]n (4,4'-bpy)n (pic)2n (H2O)n (3) ( 4,4'-bpy = 4,4'-bipyridine; pic = picric anion ) have been synthesized and characterized by elemental analysis and single-crystal x-ray diffraction. They all have infinite three-dimensional network structure, crystallizing in the monoclinic space group C2/c (1) and Cc (2,3).

  12. Five Coordinate Platinum(II in [Pt(bpy(cod(Me][SbF6]: A Structural and Spectroscopic Study

    Directory of Open Access Journals (Sweden)

    Axel Klein


    Full Text Available The five coordinate organoplatinum complex [Pt(bpy(cod(Me][SbF6] (cod = 1,5-cyclooctadiene, bpy = 2,2’-bipyridine was obtained reacting [Pt(cod(MeCl] with Ag[SbF6] and bpy and characterized by multiple spectroscopy (IR and NMR and single crystal XRD. Although the application of the τ values for the discrimination between trigonal bipyramidal vs. square pyramidal coordination fails, the molecular structure can be unequivocally described as basally-distorted trigonal bipyramidal. Detailed multinuclear NMR spectroscopy in solution at ambient temperature gives strong evidence for the same structure; corresponding low-temperature measurements down to −70 °C revealed no marked dynamic processes.


    Institute of Scientific and Technical Information of China (English)

    Jin-ying Yuan; Cai-yuan Pana


    Polymerization of three cyclic ketene acetals: i.e., 5,6-benzo-2-methylene-1,3-dioxepane (BMDO), 2-methylene-4-phenyl-1,3-dioxolane (MPDO) and 4,7-dimethyl-2-methylene-1,3-dioxepane (DMMDO) were carried out in the presence of ethyl α-bromobutyrate/CuBr/2,2'-bipyridine respectively. The structures ofpoly(BMDO), poly(MPDO) and poly(DMMDO)were characterized by 1H and 13C-NMR spectra. The effects of monomer structure on the behavior of atom transfer free radical ring-opening polymerization were investigated and the mechanism of controlled free radical ring-opening polymerization was discussed.

  14. Evaluating the Effect of Catalyst Nuclearity in Ni-Catalyzed Alkyne Cyclotrimerizations. (United States)

    Pal, Sudipta; Uyeda, Christopher


    An evaluation of catalyst nuclearity effects in Ni-catalyzed alkyne oligomerization reactions is presented. A dinuclear complex, featuring a Ni-Ni bond supported by a naphthyridine-diimine (NDI) ligand, promotes rapid and selective cyclotrimerization to form 1,2,4-substituted arene products. Mononickel congeners bearing related N-donor chelates (2-iminopyridines, 2,2'-bipyridines, or 1,4,-diazadienes) are significantly less active and yield complex product mixtures. Stoichiometric reactions of the dinickel catalyst with hindered silyl acetylenes enable characterization of the alkyne complex and the metallacycle that are implicated as catalytic intermediates. Based on these experiments and supporting DFT calculations, the role of the dinuclear active site in promoting regioselective alkyne coupling is discussed. Together, these results demonstrate the utility of exploring nuclearity as a parameter for catalyst optimization.

  15. Halloysite Nanotubes as a New Adsorbent for Solid Phase Extraction and Spectrophotometric Determination of Iron in Water and Food Samples (United States)

    Samadi, A.; Amjadi, M.


    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).

  16. Electrochemical characterisation of an Os (II) conjugated polymer in aqueous electrolytes

    Energy Technology Data Exchange (ETDEWEB)

    McCormac, Timothy [CREATE ' Centre for Research in Electroanalytical Technology' , Department of Applied Science, Institute of Technology Tallaght, Tallaght, Dublin 24 (Ireland)]. E-mail:; Cassidy, John F. [School of Chemistry, Dublin Institute of Technology, Kevin Street, Dublin 8 (Ireland); Crowley, Karl [School of Chemistry, Dublin Institute of Technology, Kevin Street, Dublin 8 (Ireland); Trouillet, Lise [Laboratoire d' Electrochimie Moleculaire et Structures des Interfaces, UMR 5819 CEA-CNRS-University Grenoble 1, CEA-Grenoble, 17 rue des Martyrs, 38054 Grenoble Cedex 09 (France); Lafolet, Frederic [Laboratoire d' Electrochimie Moleculaire et Structures des Interfaces, UMR 5819 CEA-CNRS-University Grenoble 1, CEA-Grenoble, 17 rue des Martyrs, 38054 Grenoble Cedex 09 (France); Guillerez, Stephane [Laboratoire d' Electrochimie Moleculaire et Structures des Interfaces, UMR 5819 CEA-CNRS-University Grenoble 1, CEA-Grenoble, 17 rue des Martyrs, 38054 Grenoble Cedex 09 (France)


    The electrochemical behaviour of an Os (II) complex of the structurally well-defined conjugated polymer alternating regioregularly alkylated thiophene and 2,2'-bipyridine units (P4Os) has been elucidated in aqueous solution. In typical aqueous electrolyte systems, the cyclic voltammogram of the resulting P4Os film exhibits a one-electron reversible process corresponding to the Os{sup 3+/2+} redox system. However, the observance of this reversible couple did depend upon the concentration of the supporting electrolyte. It was found that the Os{sup 3+} form did form ion-pairs with an anion from the electrolyte solution. Preliminary investigations into the homogeneous charge transport dynamics associated with this redox couple have been undertaken. The technique of cyclic voltammetry, and hence the Randles-Sevick expression, in conjunction with platinum microelectrodes have been employed to determine the D{sub CT}C value.

  17. Synthesis, spectral characterizations and biological studies of transition metal mixed ligand complexes: X-ray crystal structures of [Cu(oda)(Bipy)(H 2O)]·4H 2O and [VO(oda)(Bipy)]·2H 2O (United States)

    Siddiqi, Zafar A.; Sharma, Prashant K.; Shahid, M.; Khalid, Mohd.; Kumar, Sarvendra


    The ternary complexes of stoichiometries [M(oda)(Bipy)H 2O]· xH 2O [M = Cu ( 1), x = 4; Co ( 2), x = 2; Ni ( 3), x = 4 or Cr ( 4), x = 3] and [VO(oda)(Bipy)]·2H 2O ( 5), where H 2oda = oxydiacetic acid and Bipy = 2,2'-bipyridine, were prepared and characterized employing elemental, FAB-Mass, FT-IR, EPR, 1H and 13C NMR spectroscopic analyses. X-ray crystallography of ( 1) and ( 5) indicated a six coordinate distorted geometry. The antimicrobial activities of the complexes were investigated against Escherichia coli(k-12), Bacillus subtilis (MTC-121), Staphylococcus aureus (IOASA-22), Salmonella typhymurium (MTCC-98), Candida albicans, Aspergillus fumigatus and Penicillium marneffei. The superoxide dismutase (SOD) mimic activity of the Cu(II) complex ( 1) was assessed employing NBT assay.

  18. Core–shell Ag@SiO{sub 2} nanoparticles of different silica shell thicknesses: Preparation and their effects on photoluminescence of lanthanide complexes

    Energy Technology Data Exchange (ETDEWEB)

    Kang, Jie; Li, Yuan; Chen, Yingnan; Wang, Ailing; Yue, Bin; Qu, Yanrong; Zhao, Yongliang; Chu, Haibin, E-mail:


    Highlights: • Ag@SiO{sub 2} nanoparticles of different silica shell thicknesses were prepared via the Stöber process. • Sm and Dy complexes with benzoate, 1,10-phenanthroline and 2,2′-bipyridine were synthesized. • The complex-doped Ag@SiO{sub 2} composites show stronger luminescent intensities than pure complexes. • The luminescent intensities of the composites strongly depend on the SiO{sub 2} shell thickness. - Abstract: Three kinds of almost spherical core–shell Ag@SiO{sub 2} nanoparticles of different silica shell thicknesses (10, 25 and 80 nm) were prepared via the Stöber process. The Ag core nanoparticles were prepared by reducing silver nitrate with sodium citrate. The size, morphology and structure of core–shell Ag@SiO{sub 2} nanoparticles were characterized by transmission electron microscopy. Subsequently, eight kinds of lanthanide complexes with benzoate, 1,10-phenanthroline and 2,2′-bipyridine were synthesized. The composition of the lanthanide complexes was characterized by elemental analysis, IR and UV spectra. Finally, lanthanide complexes were attached to the surface of Ag@SiO{sub 2} nanoparticles to form lanthanide-complex-doped Ag@SiO{sub 2} nanocomposites. The results show that the complex-doped Ag@SiO{sub 2} nanocomposites display much stronger luminescence intensities than the lanthanide complexes. Furthermore, the luminescence intensities of the lanthanide-complex-doped Ag@SiO{sub 2} nanocomposites with SiO{sub 2} shell thickness of 25 nm are stronger than those of the nanocomposites with SiO{sub 2} shell thickness of 10 and 80 nm.

  19. Synthesis and luminescent properties of novel lanthanide(III) beta-diketone complexes with nitrogen p,p'-disubstituted aromatic ligands. (United States)

    Bellusci, Anna; Barberio, Giovanna; Crispini, Alessandra; Ghedini, Mauro; La Deda, Massimo; Pucci, Daniela


    Tris-beta-diketonate lanthanide(III) complexes (Ln = Eu, Er, Yb, Tb), of general formula [Ln(acac)3 L(m)], with chelating ligands such as 4,7-disubstituted-1,10-phenanthrolines and 4,4'-disubstituted-2,2'-bipyridines, have been synthesized and fully characterized. The inductive effects of the para-substituents on the aromatic N-donor ligands have been investigated both in the solid and in the solution states. Single-crystal X-ray structures have been determined for the diethyl 1,10-phenanthroline-4,7-dicarboxylate europium and 4,4'-dimethoxy-2,2'-bipyridine erbium derivatives, revealing a distorted square antiprismatic geometry around the lanthanide atom in both cases. The influence exerted by the p,p'-substituents with respect to the nitrogen coordinating atoms on the Ln-N bond distances is discussed comparing the geometrical parameters with those found for the crystal structures containing the fragments [Ln(III)(phen)] and [Ln(III)(bipy)] obtained from the Cambridge Structural Database. The influence exerted by the electron-attracting groups on the coordination ability of the ligands, that in some cases becomes lack of coordination of the lanthanide ions, has been also detected in solution where the loss of the ligand has been followed by UV-vis spectroscopy. Moreover, the use of relatively long alkoxy chains as substituents on the 1,10-phenanthroline ligand led to the formation of a promesogenic lanthanide complex, whose thermal behavior is encouraging for the synthesis of new lanthanide liquid-crystalline species.

  20. A novel porous anionic metal–organic framework with pillared double-layer structure for selective adsorption of dyes

    Energy Technology Data Exchange (ETDEWEB)

    Sheng, Shu-Nan; Han, Yi; Wang, Bin; Zhao, Cui; Yang, Fan; Zhao, Min-Jian; Xie, Ya-Bo, E-mail:; Li, Jian-Rong


    A novel porous anionic metal–organic framework, (Me{sub 2}NH{sub 2}){sub 2}[Zn{sub 2}L{sub 1.5}bpy]·2DMF (BUT-201; H{sub 4}L=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(NO{sub 3}){sub 2}·6H{sub 2}O 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 (CH{sub 3}){sub 2}NH{sub 2}{sup +}, 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 LiNO{sub 3}. - Graphical abstract: A porous anionic metal–organic framework (BUT-201) can selectively adsorb the cationic dyes by cationic guest molecule substitution, and the adsorbed dyes can be gradually released in the methanol solution of LiNO{sub 3}. - Highlights: • An anionic metal-organic framework (BUT-201) has been synthesized and characterized. • BUT-201 has a three-dimensional (3D) pillared double-layer structure. • BUT-201 can selectively and rapidly adsorb cationic dyes. • The adsorbed dyes can be gradually released in the methanol solution of LiNO{sub 3}.

  1. Five inorganic-organic hybrids based on Keggin polyanion [SiMo12O40]4-: From 0D to 2D network (United States)

    Yu, Xiao-Yang; Cui, Xiao-Bing; Lu, Jing; Luo, Yu-Hui; Zhang, Hong; Gao, Wei-Ping


    Five new inorganic-organic hybrids based on 4,4‧-bipyridine and Keggin-type polyoxometalate [SiMo12O40]4-, (SiMo12O40)(H2bipy)2·2H2O (1), [Cu(Hbipy)4(HSiMo12O40)(SiMo12O40)](H2bipy)0.5·7H2O (2), [Cu2(Hbipy)6(bipy)(SiMo12O40)3](Hbipy)2·6H2O (3), [Cu(bipy)2(SiMo12O40)](H2bipy)·2H2O (4) and [Cu2(bipy)4(H2O)4](SiMo12O40)·13H2O (5) (bipy=4,4‧-bipyridine), have been hydrothermally synthesized. 1 consists of H2bipy2+ and [SiMo12O40]4- units. In 2, two [SiMo12O40]4- are bridged by [Cu(Hbipy)4]6+ to form a [Cu(Hbipy)4(SiMo12O40)2]2- dimmer. In 3, [SiMo12O40]4- polyanions acting as bidentated bridging ligands and monodentated auxiliary ligands connect [Cu2(Hbipy)6(bipy)]8+ units into a 1D zigzag chain. In 4, [SiMo12O40]4- polyanions bridge neighboring 1D [Cu(bipy)2]2+ double chains into a 2D extended layer. In 5, [SiMo12O40]4- polyanions acting as templates site alternately upon the grids from both sides of the square grid [Cu2(bipy)4(H2O)4]4+ layer. In addition, the electrochemical behaviors of 1, 3 and 4 and the photocatalysis property of 1 have been investigated.

  2. Asymmetric Ruthenium(II and Osmium(II Complexes with New Bidentate Polyquinoline Ligands. Synthesis and NMR Characterization

    Directory of Open Access Journals (Sweden)

    Antonino Mamo


    Full Text Available A series of Ru(II and Os(II tris-chelate complexes with new bidentate 2-pyridylquinoline ligands have been synthesized and fully characterized by EA,1H-NMR and FAB-MS techniques. The new ligands are: L1 = 4-p-methoxyphenyl-6-bromo-2-(2′- pyridylquinoline (mphbr-pq and L2 = 4-p-hydroxyphenyl-6-bromo-2-(2′-pyridyl-quinoline (hphbr-pq. The complexes studied are: [Ru(bpy2L1](PF62 (C1, [Ru(bpy2L2](PF62 (C2, [Os(bpy2L1](PF62 (C3, [Os(bpy2L2](PF62 (C4 (bpy = 2,2′-bipyridine, [Ru(dmbpy2L1](PF62 (C5, [Ru(dmbpy2L2](PF62 (C6, [Os(dmbpy2L1](PF62 (C7, and [Os(dmbpy2L2](PF62 (C8 (dmbpy = 4,4′-dimethyl-2,2′-bipyridine. Moreover, new functionalized complexes C9-C12 were obtained by the basecatalyzed direct alkylation of C2, C4, C6, and C8 with 6-bromo-1-hexene. The complete assignment of the 1H-NMR spectra for the two new ligands (L1 and L2, and their Ru(II or Os(II complexes has been accomplished using a combination of one- and two-dimensional NMR techniques. The JH,H values have been determined for the majority of the resonances.

  3. Asymmetric ruthenium(II) and osmium(II) complexes with new bidentate polyquinoline ligands. Synthesis and NMR characterization. (United States)

    Mamo, Antonino; Aureliano, Alessandro; Recca, Antonino


    A series of Ru(II) and Os(II) tris-chelate complexes with new bidentate 2-pyridylquinoline ligands have been synthesized and fully characterized by EA,1H-NMR and FAB-MS techniques. The new ligands are: L1 = 4-p-methoxyphenyl-6-bromo-2-(2'- pyridyl)quinoline (mphbr-pq) and L2 = 4-p-hydroxyphenyl-6-bromo-2-(2'-pyridyl)-quinoline (hphbr-pq). The complexes studied are: [Ru(bpy)2L1](PF6)2 (C1), [Ru(bpy)2L2](PF6)2 (C2), [Os(bpy)2L1](PF6)2 (C3), [Os(bpy)2L2](PF6)2 (C4) (bpy = 2,2'-bipyridine), [Ru(dmbpy)2L1](PF6)2 (C5), [Ru(dmbpy)2L2](PF6)2 (C6), [Os(dmbpy)2L1](PF6)2 (C7), and [Os(dmbpy)2L2](PF6)2 (C8) (dmbpy = 4,4'-dimethyl-2,2'-bipyridine). Moreover, new functionalized complexes C9-C12 were obtained by the base-catalyzed direct alkylation of C2, C4, C6, and C8 with 6-bromo-1-hexene. The complete assignment of the 1H-NMR spectra for the two new ligands (L1 and L2), and their Ru(II) or Os(II) complexes has been accomplished using a combination of one- and two-dimensional NMR techniques. The JH,H values have been determined for the majority of the resonances.

  4. Multimetallic catalysed cross-coupling of aryl bromides with aryl triflates (United States)

    Ackerman, Laura K. G.; Lovell, Matthew M.; Weix, Daniel J.


    The advent of transition-metal catalysed strategies for forming new carbon-carbon bonds has revolutionized the field of organic chemistry, enabling the efficient synthesis of ligands, materials, and biologically active molecules. In cases where a single metal fails to promote a selective or efficient transformation, the synergistic cooperation of two distinct catalysts--multimetallic catalysis--can be used instead. Many important reactions rely on multimetallic catalysis, such as the Wacker oxidation of olefins and the Sonogashira coupling of alkynes with aryl halides, but this approach has largely been limited to the use of metals with distinct reactivities, with only one metal catalyst undergoing oxidative addition. Here, we demonstrate that cooperativity between two group 10 metal catalysts--(bipyridine)nickel and (1,3-bis(diphenylphosphino)propane)palladium--enables a general cross-Ullmann reaction (the cross-coupling of two different aryl electrophiles). Our method couples aryl bromides with aryl triflates directly, eliminating the use of arylmetal reagents and avoiding the challenge of differentiating between multiple carbon-hydrogen bonds that is required for direct arylation methods. Selectivity can be achieved without an excess of either substrate and originates from the orthogonal reactivity of the two catalysts and the relative stability of the two arylmetal intermediates. While (1,3-bis(diphenylphosphino)propane)palladium reacts preferentially with aryl triflates to afford a persistent intermediate, (bipyridine)nickel reacts preferentially with aryl bromides to form a transient, reactive intermediate. Although each catalyst forms less than 5 per cent cross-coupled product in isolation, together they are able to achieve a yield of up to 94 per cent. Our results reveal a new method for the synthesis of biaryls, heteroaryls, and dienes, as well as a general mechanism for the selective transfer of ligands between two metal catalysts. We anticipate that this

  5. Study on the Additive for Electroless Copper Plating Taking the Potassium Sodium Tartrate as the Main Complexing Agent%以酒石酸钾钠为主络合剂的化学镀铜添加剂研究

    Institute of Scientific and Technical Information of China (English)

    肖友军; 许永章


    It studied the additive for electroless copper plating taking potassium sodium tartrate as complexing agen, and discussed the effect of CH3OH, K4[Fe(CN)6] ? 3H2O,2,2 -bipyridine on the stability of plating bath, the quality of electroplating layer, the deposition rate of plating, to determine the amount of additive. The results indicate that the optimal conditions of the electroless copper plating system as follows: CH3OH is 14 ml/L, K4 [Fe(CN)6] ? 3H2O is 30 mg/L,2,2'-bipyridine is 5 mg/L,plating 30 min in the bath, the copper deposition rate reaches 4. 6 μm/h,e-lectroplating layer appears shiny pale pink, and stability of plating bath is optimal, electroplating layer has good adhesion.%研究了以酒石酸钾钠为主络合剂的化学镀铜添加剂,讨论了甲醇、亚铁氰化钾、2,2'-联吡啶三种添加剂对镀液稳定性、镀层质量、沉积速率的影响,通过正交试验确定了各添加剂的用量.实验结果表明:在酒石酸钾钠为主络合剂的化学镀铜液中添加14mL/L甲醇、30mg/L亚铁氰化钾和5mg/L2,2’-联吡啶,化学铜沉积30min后,沉积速率可达到4.6μm/h.在此工艺条件下,镀层呈现带光泽的淡粉红色,镀液稳定性佳,镀层附着力好.

  6. Design, synthesis, DNA-binding affinity, cytotoxicity, apoptosis, and cell cycle arrest of Ru(II) polypyridyl complexes. (United States)

    Venkat Reddy, Putta; Reddy, Mallepally Rajender; Avudoddi, Srishailam; Praveen Kumar, Yata; Nagamani, Chintakuntla; Deepika, Nancherla; Nagasuryaprasad, K; Singh, Surya Satyanarayana; Satyanarayana, Sirasani


    A novel polypyridyl ligand CNPFIP (CNPFIP=2-(5(4-chloro-2-nitrophenyl)furan-2-yl)-1H-imidazo[4,5f][1,10]phenanthroline) and its mononuclear Ru(II) polypyridyl complexes of [Ru(phen)2CNPFIP](2+)(1) (phen=1,10-phenanthroline), [Ru(bpy)2CNPFIP](2+)(2) (bpy=2,2'-bipyridine), and [Ru(dmb)2CNPFIP](2+)(3) (dmb=4,4'-dimethyl-2,2'-bipyridine) have been synthesized successfully and characterized thoroughly by elemental analysis, UV/Vis, IR, NMR, and ESI-MS. The interaction of the Ru(II) complexes with calf thymus DNA (CT-DNA) was investigated by absorption titration, fluorescence, viscosity measurements. The experimental results suggest that three complexes bind to CT-DNA through an intercalative mode and the DNA-binding affinity of complex 1 is greater than that of complexes 2 and 3. The photocleavage of plasmid pBR322 DNA by ruthenium complexes 1, 2, and 3 was investigated. We have also tested three complexes for their antimicrobial activity against Escherichia coli (Gram-negative) and Staphylococcus aureus (Gram-positive) bacteria. The in vitro cytotoxicity of these complexes was evaluated by MTT assay, and complex 1 shows higher cytotoxicity than 2 and 3 on HeLa cells. The induced apoptosis and cell cycle arrest of HeLa cells were investigated by flow cytometry for 24h. The molecular docking of ruthenium complexes 1, 2, and 3 with the active site pocket residues of human DNA TOP1 was performed using LibDock.

  7. Substitution of Ethynyl-Thiophene Chromophores on Ruthenium Sensitizers: Influence on Thermal and Photovoltaic Performance of Dye-Sensitized Solar Cells

    Directory of Open Access Journals (Sweden)

    Malapaka Chandrasekharam


    Full Text Available A new high molar extinction coefficient ruthenium(II bipyridyl complex, “Ru(2,2-bipyridine-4,4′-dicarboxylic acid(4,4′-bis((3-hexylthiophen-2-ylethynyl-2,2′-bipyridine(NCS2 (N(C4H94, MC101” was synthesized and fully characterized by 1H-NMR, ESI-MASS, FT-IR, UV-Vis., and fluorescence spectroscopes. The dye showed relatively high molar extinction coefficient of 25.0 × 103 M-1 cm-1 at λ maximum of 544 nm, while the reference C101 has shown 15.8 × 103 M-1cm-1 at λ maximum 528 nm. The monochromatic incident photon-to-collected electron conversion efficiency of 44.1% was obtained for MC101 over the entire visible range, while the C101 sensitized solar cell fabricated and evaluated under identical conditions exhibited 40.1%. The DSSCs fabricated with 0.54 cm2 active area TiO2 electrodes and high efficient electrolyte (E01, from the sensitizers MC101 and C101 exhibited energy conversion efficiencies of 3.25% (short-circuit current density (JSC = 7.32 mA/cm2, VOC = 610 mV, ff = 0.725 and 2.94% (JSC = 6.60 mA/cm2; VOC = 630 mV; ff = 0.709, respectively, under air mass of 1.5 sunlight.

  8. Comparative analysis of biofilm formation by Bacillus cereus reference strains and undomesticated food isolates and the effect of free iron. (United States)

    Hayrapetyan, Hasmik; Muller, Lisette; Tempelaars, Marcel; Abee, Tjakko; Nierop Groot, Masja


    Biofilm formation of Bacillus cereus reference strains ATCC 14579 and ATCC 10987 and 21 undomesticated food isolates was studied on polystyrene and stainless steel as contact surfaces. For all strains, the biofilm forming capacity was significantly enhanced when in contact with stainless steel (SS) as a surface as compared to polystyrene (PS). For a selection of strains, the total CFU and spore counts in biofilms were determined and showed a good correlation between CFU counts and total biomass of these biofilms. Sporulation was favoured in the biofilm over the planktonic state. To substantiate whether iron availability could affect B. cereus biofilm formation, the free iron availability was varied in BHI by either the addition of FeCl3 or by depletion of iron with the scavenger 2,2-Bipyridine. Addition of iron resulted in increased air-liquid interface biofilm on polystyrene but not on SS for strain ATCC 10987, while the presence of Bipyridine reduced biofilm formation for both materials. Biofilm formation was restored when excess FeCl3 was added in combination with the scavenger. Further validation of the iron effect for all 23 strains in microtiter plate showed that fourteen strains (including ATCC10987) formed a biofilm on PS. For eight of these strains biofilm formation was enhanced in the presence of added iron and for eleven strains it was reduced when free iron was scavenged. Our results show that stainless steel as a contact material provides more favourable conditions for B. cereus biofilm formation and maturation compared to polystyrene. This effect could possibly be linked to iron availability as we show that free iron availability affects B. cereus biofilm formation.

  9. Synthesis and Structural Characterization of Gd(Ⅱ) Coordination Polymer [Gd2(μ-phth)3(b-pd)(H2O)5]n

    Institute of Scientific and Technical Information of China (English)


    A new Gd(Ⅱ) complex [Gd2(μ-phth)3(b-pd)(H2O)5]n (phth = o-phthalato, b-pd = N,N- bipyridine) has been synthesized by the reaction of GdO2 with o-phthalate, H2O and 2,2′-bipyridine. The crystal structure has been determined by single-crystal X-ray diffraction. The crystal is of triclinic, space group P with a = 11.82920(10), b = 13.53550(10), c = 13.7381(2)(A), α = 88.99, β = 66.9120(10), γ = 66.2370(10)°, V = 1826.02(3)(A)3, Dc = 1.915 g/cm3, C34H30N2O17Gd2, Mr = 1053.10, F(000) = 1024, μ = 3.680 mm-1, Z = 2, R = 0.0612 and wR = 0.1320 for 6259 observed reflections (I > 2σ(I)). In the title complex, the Gd(II) ions are bridged by o-phthalate ligands in a bidentate mode, producing a 1D infi- nite chain structure. Each eight-coordinated Gd(Ⅱ) center is coordinated by eight oxygen atoms from phth to give a distorted dodecahedral geometry, and each nine-coordinated Gd(Ⅱ) center is coordi- nated by two N atoms from b-pd and seven oxygen atoms from phth to give a distorted geometry of capped square antiprism. The chains are linked by π-π interactions and hydrogen bonds between oxy- gen atoms of carboxylate groups and H2O molecules and hydrogen atoms of H2O, b-pd and o-phth molecules, forming an unusual three-dimensional coordination polymer.

  10. Membraneless glucose/oxygen enzymatic fuel cells using redox hydrogel films containing carbon nanotubes. (United States)

    MacAodha, Domhnall; Ó Conghaile, Peter; Egan, Brenda; Kavanagh, Paul; Leech, Dónal


    Co-immobilisation of three separate multiple blue copper oxygenases, a Myceliophthora thermophila laccase, a Streptomyces coelicolor laccase and a Myrothecium verrucaria bilirubin oxidase, with an [Os(2,2'-bipyridine)2 (polyvinylimidazole)10Cl](+/2+) redox polymer in the presence of multi-walled carbon nanotubes (MWCNTs) on graphite electrodes results in enzyme electrodes that produce current densities above 0.5 mA cm(-2) for oxygen reduction at an applied potential of 0 V versus Ag/AgCl. Fully enzymatic membraneless fuel cells are assembled with the oxygen-reducing enzyme electrodes connected to glucose-oxidising anodes based on co-immobilisation of glucose oxidase or a flavin adenine dinucleotide-dependent glucose dehydrogenase with an [Os(4,4'-dimethyl-2,2'-bipyridine)2(polyvinylimidazole)10Cl](+/2+) redox polymer in the presence of MWCNTs on graphite electrodes. These fuel cells can produce power densities of up to 145 μW cm(-2) on operation in pH 7.4 phosphate buffer solution at 37 °C containing 150 mM NaCl, 5 mM glucose and 0.12 mM O2. The fuel cells based on Myceliophthora thermophila laccase enzyme electrodes produce the highest power density if combined with glucose oxidase-based anodes. Although the maximum power density of a fuel cell of glucose dehydrogenase and Myceliophthora thermophila laccase enzyme electrodes decreases from 110 μW cm(-2) in buffer to 60 μW cm(-2) on testing in artificial plasma, it provides the highest power output reported to date for a fully enzymatic glucose-oxidising, oxygen-reducing fuel cell in artificial plasma.

  11. Photoelectrochemical Sensors for the Rapid Detection of DNA Damage Induced by Some Nanoparticles

    Directory of Open Access Journals (Sweden)

    M. Jamaluddin Ahmed


    Full Text Available Photoelectrochemcal sensors were developed for the rapid detection of oxidative DNA damage induced by titanium dioxide and polystyrene nanoparticles. Each sensor is a multilayer film prepared on a tin oxide nanoparticle electrode using layer- by-layer self assembly and is composed of separate layer of a photoelectrochemical indicator, DNA. The organic compound and heavy metals represent genotoxic chemicals leading two major damaging mechanisms, DNA adduct formation and DNA oxidation. The DNA damage is detected by monitoring the change of photocurrent of the indicator. In one sensor configuration, a DNA intercalator, Ru(bpy2 (dppz2+ [bpy=2, 2′ -bipyridine, dppz=dipyrido( 3, 2-a: 2′ 3′-c phenazine], was employed as the photoelectrochemical indicator. The damaged DNA on the sensor bound lesser Ru(bpy2 (dppz2+ than the intact DNA, resulting in a drop in photocurrent. In another configuration, ruthenium tris(bipyridine was used as the indicator and was immobilized on the electrode underneath the DNA layer. After oxidative damage, the DNA bases became more accessible to photoelectrochemical oxidation than the intact DNA, producing a rise in photocurrent. Both sensors displayed substantial photocurrent change after incubation in titanium dioxide / polystyrene solution in a time – dependent manner. According to the data, damage of the DNA film was completed in 1h in titanium dioxide / polystyrene solution. In addition, the titanium dioxide induced much more sever damage than polysterene. The results were verified independently by gel electrophoresis and UV-Vis absorbance experiments. The photoelectrochemical reaction can be employed as a new and inexpensive screening tool for the rapid assessment of the genotoxicity of existing and new chemicals.

  12. Synthesis, Crystal Structure and Luminescent Property of Cd (II Complex with N-Benzenesulphonyl-L-leucine

    Directory of Open Access Journals (Sweden)

    Xishi Tai


    Full Text Available A new trinuclear Cd (II complex [Cd3(L6(2,2-bipyridine3] [L = N-phenylsulfonyl-L-leucinato] has been synthesized and characterized by elemental analysis, IR and X-ray single crystal diffraction analysis. The results show that the complex belongs to the orthorhombic, space group P212121 with a = 16.877(3 Å, b = 22.875(5 Å, c = 29.495(6 Å, α = β = γ = 90°, V = 11387(4 Å3, Z = 4, Dc= 1.416 μg·m−3, μ = 0.737 mm−1, F (000 = 4992, and final R1 = 0.0390, ωR2 = 0.0989. The complex comprises two seven-coordinated Cd (II atoms, with a N2O5 distorted pengonal bipyramidal coordination environment and a six-coordinated Cd (II atom, with a N2O4 distorted octahedral coordination environment. The molecules form one dimensional chain structure by the interaction of bridged carboxylato groups, hydrogen bonds and p-p interaction of 2,2-bipyridine. The luminescent properties of the Cd (II complex and N-Benzenesulphonyl-L-leucine in solid and in CH3OH solution also have been investigated.

  13. Using inclusion complexes with cyclodextrins to explore the aggregation behavior of a ruthenium metallosurfactant. (United States)

    Iza, Nerea; Guerrero-Martínez, Andrés; Tardajos, Gloria; Ortiz, María José; Palao, Eduardo; Montoro, Teresa; Radulescu, Aurel; Dreiss, Cécile A; González-Gaitano, Gustavo


    The aggregation behavior of a chiral metallosurfactant, bis(2,2'-bipyridine)(4,4'-ditridecyl-2,2'-bipyridine)ruthenium(II) dichloride (Ru2(4)C13), synthesized as a racemic mixture was characterized by small-angle neutron scattering, light scattering, NMR, and electronic spectroscopies. The analysis of the SANS data indicates that micelles are prolate ellipsoids over the range of concentrations studied, with a relatively low aggregation number, and the micellization takes place gradually with increasing concentration. The presence of cyclodextrins (β-CD and γ-CD) induces the breakup of the micelles and helps to establish that micellization occurs at a very slow exchange rate compared to the NMR time scale. The open structure of this metallosurfactant enables the formation of very stable complexes of 3:1 stoichiometry, in which one CD threads one of the hydrocarbon tails and two CDs the other, in close contact with the polar head. The complex formed with β-CD, more stable than the one formed with the wider γ-CD, is capable of resolving the Δ and Λ enantiomers at high CD/surfactant molar ratios. The chiral recognition is possible due to the very specific interactions taking place when the β-CD covers-via its secondary rim-part of the diimine moiety connected to the hydrophobic tails. A SANS model comprising a binary mixture of hard spheres (complex + micelles) was successfully used to study quantitatively the effect of the CDs on the aggregation of the surfactant.

  14. CdS nanoparticles modified to chalcogen sites: new supramolecular complexes, butterfly bridging, and related optical effects. (United States)

    Ni, Tong; Nagesha, Dattatri K; Robles, Juvencio; Materer, Nicholas F; Müssig, Stefan; Kotov, Nicholas A


    All present approaches to surface modification of nanoparticles (NPs) with organic ligands exploit metal (cadmium) sites as anchor points. To obtain efficient interaction of NP surface with p-orbitals of organic chromophores, we utilize the chalcogen (sulfur) sites on the NP surface. These sites present several advantages stemming from a stronger interaction of their atomic orbitals with both modifier and NP core. The chalcogen modification of CdS was achieved by using a mixed ligand (2,2'-bipyridyl-N,N')(malonato-O,O')-copper(II) monohydrate complex. The weak monodentate ligands (water) are replaced by a copper-sulfur bond during the modification reaction. The structure of the product was investigated by optical spectroscopy, electron spin resonance, and nuclear magnetic resonance. The modified NP can be described as a few tens (malonato-O,O')-copper units attached to the CdS core. Steady-state and time-resolved luminescence measurements, molecular orbital calculations, and UPS data indicate that delocalized surface states enveloping the surface chalcogen atoms of NP, transition metal, and p-orbitals of the bipyridine ligand are present in the synthesized species. The delocalized states are made possible due to the bridging of p-levels of sulfur and pi-orbitals of bipyridine by butterfly d-orbitals of the transition metal atom placed between them. Chalcogen-modified NP can be considered as a new member of the family of supramolecular compounds based on transition metal complexes. Both NP and metal complex parts of the prepared supramolecules are very versatile structural units, and new molecular constructs of similar design, in which quantum effects of NPs are combined with optical properties of transition metal complexes, can be obtained with different NPs and metal complexes.

  15. Synthesis, spectroscopic characterization, crystallographic studies and antibacterial assays of new copper(II) complexes with sulfathiazole and nimesulide (United States)

    Nunes, Julia Helena Bormio; de Paiva, Raphael Enoque Ferraz; Cuin, Alexandre; da Costa Ferreira, Ana Maria; Lustri, Wilton Rogério; Corbi, Pedro Paulo


    New ternary copper(II) complexes of sulfathiazole (SFT, C9H8N3O2S2) or nimesulide (NMS, C13H11N2O5S) and 2,2‧-bipyridine (bipy) were synthesized, and characterized by chemical and spectroscopic techniques. Elemental analyses indicated a 2:1:1 sulfonamide/copper/bipy composition for both complexes. Mass spectrometric measurements permitted identifying the molecular ions [Cu(SFT)2(bipy)+H]+ and [Cu(NMS)2(bipy)+H]+ at m/z 728 and 835, respectively, confirming the proposed compositions. Crystal structure of the [Cu(SFT)2(bipy)] complex was solved by powder X-ray diffraction analysis (PXRD), attesting that the Cu(II) ion is hexacoordinated in a distorted octahedral geometry. Each SFT molecule coordinates to the metal ion by the nitrogen atoms of the SO2-N group and of the heterocyclic ring. The coordination sphere is completed by a bipyridine. Electronic paramagnetic resonance (EPR) studies were carried out for the [Cu(NMS)2(bipy)] complex, indicating a tetragonal environment around the metal ion. It was suggested that NMS coordinates to Cu(II) by the nitrogen and oxygen atoms of the SO2-N group, which was confirmed by infrared spectroscopic studies. Biological studies showed the antibacterial activity of both Cu-SFT and Cu-NMS complexes, with the minimum inhibitory concentration (MIC) values ranging from 0.10 to 0.84 mmol L-1 against Gram-negative bacteria for [Cu(SFT)2(bipy)], and from 1.50 to 3.00 mmol L-1 against Gram-positive and -negative bacteria for [Cu(NMS)2(bipy)].

  16. Heteroleptic complexes of Zn(II) based on 1-(5-bromo-2-hydroxybenzylidene)-4-phenylthiosemicarbazide: Synthesis, structural characterization, theoretical studies and antibacterial activity (United States)

    Azarkish, Mohammad; Akbari, Alireza; Sedaghat, Tahereh; Simpson, Jim


    Four new ternary complexes, [ZnL (2,2‧-bipy)] (1), Zn2L2(4,4‧-bipy)] (2), [ZnL(Imd)]·H2O (3) and [ZnL3(MeImd)] (4), have been synthesized from the reaction of Zn(II) acetate with 1-(5-bromo-2-hydroxybenzylidene)-4-phenylthiosemicarbazide (H2L) in the presence of a heterocyclic base, 2,2‧-bipyridine, 4,4‧-bipyridine, imidazole or 2-methylimidazole, as an auxiliary ligand. The complexes have been investigated by elemental analysis and FT-IR, UV-Vis and 1HNMR spectroscopy. These data show that the thiosemicarbazone acts as a tridentate dianionic ligand and coordinates via the thiol group, imine nitrogen, and phenolic oxygen. The coordination sphere was completed by the nitrogen atom(s) of the secondary ligand. The structure of 1 was also confirmed by X-ray crystallography and shown to be a five coordinate complex with coordination geometry between the square-pyramidal and trigonal-bipyramidal. Density functional theory (DFT) calculations including geometry optimization, vibrational frequencies and electronic absorptions have been performed for 1 with the B3LYP functional at the TZP(6-311G*) basis set using the Gaussian 03 or ADF 2009 packages. The optimization calculation showed that the crystallographically determined geometry parameters can be reproduced with that basis set. Experimental IR frequencies and calculated vibration frequencies also support each other. The in vitro antibacterial activities of the ligand and complexes have been evaluated against Gram-positive (B. subtilis and S. aureus) and Gram-negative (P. aeruginosa) bacteria and compared with the standard antibacterial drugs. The results reveal that all of the complexes show much better activity in comparison to the individual thiosemoicarbazone ligand (H2L), against all bacterial strains used, with complex 3 showing the most promising results.

  17. Influence of Different Organic Carboxylate Anions on the Crystal Structure of Silver(Ⅰ)Coordination Polymers

    Institute of Scientific and Technical Information of China (English)

    WANG Chong-Chen; WANG Peng; GUO Guang-Liang


    The reaction of AgNO3 , 4,4′-bipyridine (bpy) and 2,2′-bipyridine-3,3′-dicarboxylic acid (H2bpdc)/2,2′-biquinoline-4,4′-dicarboxylic acid (H2bqdc)/1,3-benzenedicarboxylic acid (H2bdc) gave rise to block-like crystals of [Ag4(bpy)2(bpdc)2]·13H2O(1), [Ag2(bpy)(bqdc)(H2O)]·4.5H2O(2) and [Ag2(bpy)2(H2O)2](bdc)·3H2O(3) by slow evaporation. All the three complexes contain sandwich-like crystal structures, in which anionic sheets built up from different anions (bpdc2- , bqdc2- and bdc2- ) and lattice water molecules via rich hydrogen-bonding interactions are inserted between the cationic silver complex layers, and the abundant Ag···Ag, Ag···N and π-π stacking interactions further strengthen the 3D frameworks. The lattice water molecules are situated among the framework of crystal structure and stabilized by rich hydrogen-bonding interactions, and lattice water molecules may play a role in the orientation of organic anions in the crystal packing. Additionally, the thermal properties of 1, 2 and 3 were also discussed in detail.

  18. Reversible Sigma C-C Bond Formation Between Phenanthroline Ligands Activated by (C5Me5)2Yb

    Energy Technology Data Exchange (ETDEWEB)

    Nocton, Gr& #233; gory; Lukens, Wayne W.; Booth, Corwin H.; Rozenel, Sergio S.; Medling, Scott A.; Maron, Laurent; Andersen, Richard A.


    The electronic structure and associated magnetic properties of the 1,10-phenanthroline adducts of Cp*2Yb are dramatically different from those of the 2,2?-bipyridine adducts. The monomeric phenanthroline adducts are ground state triplets that are based upon trivalent Yb(III), f13, and (phen ) that are only weakly exchange coupled, which is in contrast to the bipyridine adducts whose ground states are multiconfigurational, open-shell singlets in which ytterbium is intermediate valent ( J. Am. Chem. Soc 2009, 131, 6480; J. Am. Chem. Soc 2010, 132, 17537). The origin of these different physical properties is traced to the number and symmetry of the LUMO and LUMO+1 of the heterocyclic diimine ligands. The bipy has only one 1 orbital of b1 symmetry of accessible energy, but phen has two orbitals of b1 and a2 symmetry that are energetically accessible. The carbon p-orbitals have different nodal properties and coefficients and their energies, and therefore their populations change depending on the position and number of methyl substitutions on the ring. A chemical ramification of the change in electronic structure is that Cp 2Yb(phen) is a dimer when crystallized from toluene solution, but a monomer when sublimed at 180190 C. When 3,8-Me2phenanthroline is used, the adduct Cp*2Yb(3,8-Me2phen) exists in the solution in a dimer monomer equilibrium in which G is near zero. The adducts with 3-Me, 4-Me, 5-Me, 3,8-Me2, and 5,6-Me2-phenanthroline are isolated and characterized by solid state X-ray crystallography, magnetic susceptibility and LIII-edge XANES spectroscopy as a function of temperature and variable-temperature 1H NMR spectroscopy.

  19. Fe2 and Fe4 clusters encapsulated in vacant polyoxotungstates: hydrothermal synthesis, magnetic and electrochemical properties, and DFT calculations. (United States)

    Pichon, Céline; Dolbecq, Anne; Mialane, Pierre; Marrot, Jérôme; Rivière, Eric; Goral, Monika; Zynek, Monika; McCormac, Timothy; Borshch, Serguei A; Zueva, Ekaterina; Sécheresse, Francis


    While the reaction of [PW(11)O(39)](7-) with first row transition-metal ions M(n+) under usual bench conditions only leads to monosubstituted {PW(11)O(39)M(H(2)O)} anions, we have shown that the use of this precursor under hydrothermal conditions allows the isolation of a family of novel polynuclear discrete magnetic polyoxometalates (POMs). The hybrid asymmetric [Fe(II)(bpy)(3)][PW(11)O(39)Fe(2) (III)(OH)(bpy)(2)]12 H(2)O (bpy=bipyridine) complex (1) contains the dinuclear {Fe(micro-O(W))(micro-OH)Fe} core in which one iron atom is coordinated to a monovacant POM, while the other is coordinated to two bipyridine ligands. Magnetic measurements indicate that the Fe(III) centers in complex 1 are weakly antiferromagnetically coupled (J=-11.2 cm(-1), H=-JS(1)S(2)) compared to other {Fe(micro-O)(micro-OH)Fe} systems. This is due to the long distances between the iron center embedded in the POM and the oxygen atom of the POM bridging the two magnetic centers, but also, as shown by DFT calculations, to the important mixing of bridging oxygen orbitals with orbitals of the POM tungsten atoms. The complexes [Hdmbpy](2)[Fe(II)(dmbpy)(3)](2)[(PW(11)O(39))(2)Fe(4) (III)O(2)(dmbpy)(4)]14 H(2)O (2) (dmbpy=5,5'-dimethyl-2,2'-bipyridine) and H(2)[Fe(II)(dmbpy)(3)](2)[(PW(11)O(39))(2)Fe(4) (III)O(2)(dmbpy)(4)]10 H(2)O (3) represent the first butterfly-like POM complexes. In these species, a tetranuclear Fe(III) complex is sandwiched between two lacunary polyoxotungstates that are pentacoordinated to two Fe(III) cations, the remaining paramagnetic centers each being coordinated to two dmbpy ligands. The best fit of the chi(M)T=f(T) curve leads to J(wb)=-59.6 cm(-1) and J(bb)=-10.2 cm(-1) (H=-J(wb)(S(1)S(2)+S(1)S(2*)+S(1*)S(2)+S(1*)S(2*))-J(bb)(S(2)S(2*))). While the J(bb) value is within the range of related exchange parameters previously reported for non-POM butterfly systems, the J(wb) constant is significantly lower. As for complex 1, this can be justified considering Fe

  20. Slow hydrogen atom transfer reactions of oxo- and hydroxo-vanadium compounds: the importance of intrinsic barriers. (United States)

    Waidmann, Christopher R; Zhou, Xin; Tsai, Erin A; Kaminsky, Werner; Hrovat, David A; Borden, Weston Thatcher; Mayer, James M


    Reactions are described that interconvert vanadium(IV) oxo-hydroxo complexes [V(IV)O(OH)(R(2)bpy)(2)]BF(4) (1a-c) and vanadium(V) dioxo complexes [V(V)O(2)(R(2)bpy)(2)]BF(4) (2a-c) [R(2)bpy = 4,4'-di-tert-butyl-2,2'-bipyridine ((t)Bu(2)bpy), a; 4,4'-dimethyl-2,2'-bipyridine (Me(2)bpy), b; 2,2'-bipyridine (bpy), c]. These are rare examples of pairs of isolated, sterically unencumbered, first-row metal-oxo/hydroxo complexes that differ by a hydrogen atom (H(+) + e(-)). The V(IV)-(t)Bu(2)bpy derivative 1a has a useful (1)H NMR spectrum, despite being paramagnetic. Complex 2a abstracts H(*) from organic substrates with weak O-H and C-H bonds, converting 2,6-(t)Bu(2)-4-MeO-C(6)H(2)OH (ArOH) and 2,2,6,6-tetramethyl-N-hydroxypiperidine (TEMPOH) to their corresponding radicals ArO(*) and TEMPO, hydroquinone to benzoquinone, and dihydroanthracene to anthracene. The equilibrium constant for 2a + ArOH 1a + ArO(*) is (4 +/- 2) x 10(-3), implying that the VO-H bond dissociation free energy (BDFE) is 70.6 +/- 1.2 kcal mol(-1). Consistent with this value, 1a is oxidized by 2,4,6-(t)Bu(3)C(6)H(2)O(*). All of these reactions are surprisingly slow, typically occurring over hours at ambient temperatures. The net hydrogen-atom pseudo-self-exchange 1a + 2b 2a + 1b, using the (t)Bu- and Me-bpy substituents as labels, also occurs slowly, with k(se) = 1.3 x 10(-2) M(-1) s(-1) at 298 K, DeltaH(double dagger) = 15 +/- 2 kcal mol(-1), and DeltaS(double dagger) = 16 +/- 5 cal mol(-1) K. Using this k(se) and the BDFE, the vanadium reactions are shown to follow the Marcus cross relation moderately well, with calculated rate constants within 10(2) of the observed values. The vanadium self-exchange reaction is ca. 10(6) slower than that for the related Ru(IV)O(py)(bpy)(2)(2+)/Ru(III)OH(py)(bpy)(2)(2+) self-exchange. The origin of this dramatic difference has been probed with DFT calculations on the self-exchange reactions of 1c + 2c and on monocationic ruthenium complexes with pyrrolate or