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Bipyridine
Terms modified by Bipyridine Selected AbstractsThermal Decomposition Reactions as a Tool for the Synthesis of New Thermodynamic Metastable Modifications: Synthesis, Structures, and Properties of (Formato)nickel(II) Coordination Polymers Based on 4,4,-BipyridineEUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 12 2010Jan Boeckmann Abstract The reaction of nickel formate with 4,4,-bipyridine (bipy) in aqueous solution at room temperature leads to the formation of the hydrated compound [Ni(HCO2)2(H2O)(bipy)·4H2O]n (1) reported recently. On heating, compound 1 decomposes into the new anhydrous compound of composition [Ni(HCO2)2(bipy)]n (2II), which decomposes on further heating. Interestingly, if the anhydrous compound is prepared from solution, a new modification 2I is obtained. Investigations on the stability of both forms show that modification 2I presents the thermodynamically most stable form between room and decomposition temperature, whereas modification 2II, which can only be prepared by thermal decomposition, is metastable. In the crystal structure of 2I, the Ni2+ cations are coordinated by four ,2 - anti,anti bridging formato anions and two bridging ,2 -bipy ligands in a slightly distorted octahedralgeometry. The formato anions bridge the metal cations in zigzag chains, which are further connected by ,2 - anti,anti formato anions and bipy ligands to give a three-dimensional coordination network. IR spectroscopic investigations on the metastable form 2II also indicate that all formato anions act as bridging ligands. Magnetic measurements of the hydrated and anhydrous compounds reveal different behavior with a ferromagnetic ordering for compound 2I and an antiferromagnetic ordering for compound 1. For form 2II, only Curie,Weiss paramagnetism was found. [source] Complexation of 2,6-Bis(3-pyrazolyl)pyridine,Bis(thiocyanato)iron(II) with a Bridging 4,4,-Bipyridine: A New Example of a Dinuclear Spin Crossover ComplexEUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 7 2008Dalila Fedaoui Abstract Investigation of the coordination behavior of 2,6-bis(3-pyrazolyl)pyridine,bis(thiocyanato)iron(II) towards bridging ligands led to the discovery of a novel dinuclear complex showing spin-crossover. Chemical and structural characterization and a first report of physical properties are presented.(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2008) [source] Synthesis, Crystal Structure, and Second-Order Nonlinear Optical Properties of Ruthenium(II) Complexes with Substituted Bipyridine and Phenylpyridine LigandsEUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 15 2006Laurence Labat Abstract Two new ruthenium(II) complexes of formula [Ru(bpy)2(L1)][PF6] and [Ru(bpy)2(L2)][PF6]2 are reported. HL1 is a (nitrophenyl)ethenyl-substituted phenylpyridine ligand, and L2 is the bipyridine analogue of HL1. The X-ray crystal structure of [Ru(bpy)2(L1)][PF6] has been solved, and the compound is found to crystallize in the monoclinic C2/c space group. The electronic spectrum of the cyclometalated derivative [Ru(bpy)2(L1)][PF6] exhibits a low-lying transition that is red-shifted from 454 to 546 nm relative to that of the parent bipyridine-based complex, which reveals an important charge-transfer character. To support this assumption, the nonlinear optical properties were investigated by the hyper-Rayleigh scattering technique and indicate a molecular static hyperpolarizability (,0) equal to 230,×,10,30 cm5,esu,1. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2006) [source] Characterization by NMR Spectroscopy, X-ray Analysis and Cytotoxic Activity of the Ruthenium(II) Compounds [RuL3](PF6)2(L = 2-Phenylazopyridine or o -Tolylazopyridine) and [RuL'2L"](PF6)2(L', L" = 2-Phenylazopyridine, 2,2'-Bipyridine)EUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 13 2005Anna C. G. Hotze Abstract Tris(ligand) complexes [RuL3](PF6)2 (L = 2-phenylazopyridine or o -tolylazopyridine) and mixed ligand [RuL'2L"](PF6)2 (L' and L" are 2-phenylazopyridine or 2,2'-bipyridine) have been synthesized, structurally characterized and investigated for cytotoxic activity. These complexes are important to study the hypothesis that the compound ,-[Ru(azpy)2Cl2] (azpy = 2-phenylazopyridine) exhibits a high cytotoxicity due to its two cis chloride ligands, which might be exchanged for biological targets as DNA. Molecular structures of mer -[Ru(azpy)3](PF6)2 (1) and mer -[Ru(tazpy)3](PF6)2 (5) (tazpy = o -tolylazopyridine) have been determined by X-ray diffraction. Series of complexes [RuL3](PF6)2 and [RuL'2L"](PF6)2 show interesting NMR spectroscopic data; e.g. the spectrum of mer -[Ru(azpy)3](PF6)2 (1) shows extremely broadened resonances at room temp. but sharpened resonances at low temperature. In the 1H NMR spectra of compounds [Ru(azpy)2(bpy)]2+ and [Ru(bpy)2(azpy)]2+ (bpy = 2,2-bipyridine), respectively, less broadened (room temp.) or completely sharp resonances (room temp.) occur in comparison to 1 (under same conditions). By selecting the right temperature and/or concentration, NMR spectra of these series of compounds have been resolved using 2D COSY and NOESY NMR spectroscopy. Remarkably, the cytotoxicity data against a series of human tumor cell lines (A498, EVSA-T, H226, IGROV, M19, MCF-7 and WIDR) show a moderate cytotoxicity for these series of tris(ligand) complexes. So, even though no chloride ligands are present in these tris(ligand) complexes, a considerable cytotoxic activity is observed. This would imply that the 2-phenylazopyridine ruthenium(II) complexes act by a completely different mechanism than the well-known cisplatin. This finding is important, because an anticancer compound acting via a different mechanism is a prerequisite in designing new anticancer drugs. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005) [source] Columnar Mesomorphism in Hexacatenar Tetrahedral (2,2,-Bipyridine)zinc Complexes and Homologous Palladium DerivativesEUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 1 2005Giovanna Barberio Abstract The synthesis and characterisation of novel liquid crystals which display columnar mesomorphism induced upon complexation of a series of nonmesomorphic hexacatenar 4,4,-disubstituted 2,2,-bipyridines (Ln) are reported. The introduction of different metal centres (Zn, Pd) causes the appearance of mesomorphism in all complexes regardless of the geometry around the metal ion. We therefore report the first examples of mesomorphism in tetrahedral zinc derivatives. The nature of the columnar phases is related to the self-assembly of the half-disc shaped [LnMCl2] (M = Zn, Pd) complexes into full disc-shaped supramolecules. The molecular organisation in the mesophase is mainly driven by intermolecular attractive interactions, as shown by the crystal structure of the model compound [LPdCl2]. Preliminary measurements of photoconductivity have been performed on samples of [LnMCl2] complexes doped with C60 to increase absorption. Promising results were obtained. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005) [source] Photophysical Processes in ,Supramolecular Balls' Formed by Lanthanide Chloride with 2,2,-BipyridineHELVETICA CHIMICA ACTA, Issue 11 2009Abstract The europium complex [EuCl2(bpy)2(H2O)2]Cl,1.25,C2H6O,0.37,H2O, where bpy is 2,2,-bipyridine, was synthesized and investigated with the aim to relate its molecular geometry and crystal packing to the efficiency of energy-transfer processes. The presence of H-bonds between noncoordinated Cl, ions and coordinated H2O molecules leads to the formation of discrete trimers assembled by a number of CH,,,Cl and stacking interactions into ,supramolecular balls' which contain Cl, ions and solvate molecules (H2O and EtOH). The additional stabilization of the complex is due to intramolecular N,,,C interactions between two bpy ligands that causes some shortening of the EuN bonds. Deciphering the luminescence properties of the Eu complex was performed under consideration of both the composition of the inner coordination sphere and the peculiarities of the crystal packing. The influence of the latter and the bpy orientation on the energy of the ligand,Eu charge-transfer state (LMCT) was established, and an additional excited state induced by the , -stacking interaction (SICT) was identified. [source] Synthesis, DNA Binding, and DNA Photocleavage of the Ruthenium(II) Complexes [Ru(bpy)(btip)]2+ and [Ru(dmb)(btip)]2+ (bpy,=,2,2,-Bipyridine; btip,=,2-Benzo[b]thien-2-yl-1H -imidazo[4,5- f],[1,10]phenanthroline; dmb,=,4,4,-Dimethyl-2,2,-bipyridine)HELVETICA CHIMICA ACTA, Issue 1 2007Li-Feng Tan Abstract The new polypyridyl ligand btip (=,2-benzo[b]thien-2-yl-1H -imidazo[4,5- f],[1,10]phenanthroline) and its RuII complexes [Ru(bpy)2(btip)]2+ (1; bpy,=,2,2,-bipyridine) and [Ru(dmb)2(btip)]2+ (2; dmb,=,4,4,-dimethyl-2,2,-bipyridine) were synthesized and characterized by elemental analysis, MS, and 1H-NMR. The DNA-binding properties of the two complexes to calf-thymus DNA (CT-DNA) were investigated by different spectrophotometric methods and viscosity measurements. The results suggest that both complexes bind to CT-DNA through intercalation. Also, when irradiated at 400,nm, the two complexes promote the photocleavage of plasmid pBR-322 DNA. Thereby, under comparable experimental conditions, complex 1 cleaves DNA more effectively than complex 2 does. Mechanistic studies reveal that singlet oxygen (1O2) and hydroxyl radicals (OH.) play a significant role in the photocleavage. [source] Hexameric Palladium(II) Terpyridyl Metallomacrocycles: Assembly with 4,4,-Bipyridine and Characterization by TWIM Mass Spectrometry,ANGEWANDTE CHEMIE, Issue 37 2010Sujith Perera Dr. Groß und rund: Ein Makrocyclus mit 12 PdII -Terpyridyl-Einheiten wurde mithilfe von 4,4,-Bipyridyl-Liganden aufgebaut und durch NMR-Spektroskopie sowie TWIM-Massenspektrometrie charakterisiert (TWIM: traveling wave ion mobility). Der Makrocyclus (siehe Bild; C,grau, N,blau, Pd,orange) wurde auch durch Tandemmassenspektrometrie und Experimente mit stoßaktivierter Dissoziation (CAD) untersucht, und die resultierenden Fragmente wurden mit einem Flugzeitverfahren analysiert. [source] ChemInform Abstract: Two Novel Copper,Undecaniobates Decorated by Copper,Organic Cations [{Cu(H2O) L}2{CuNb11O35H4}]5- (L: 10-Phenanthroline, 2,2,-Bipyridine) Consisting of Plenary and Monolacunary Lindqvist-Type Isopolyniobate Fragments.CHEMINFORM, Issue 40 2010Jing-Yang Niu Abstract Compounds (III) and (IV) represent the first examples of copper undecaniobates. [source] ChemInform Abstract: Addition of Arylboronic Acids to Nitriles in Aqueous Media Catalyzed by a 2,2,-Bipyridine,Cyclopalladated Ferrocenylimine Complex.CHEMINFORM, Issue 17 2008Ajuan Yu Abstract ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 200 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a "Full Text" option. The original article is trackable via the "References" option. [source] Catalytic Hydrogenation of Halosteroidal Derivatives by Bipyridine or Phenanthroline Complexes of Copper(II) in Hydrazine Aqueous Media.CHEMINFORM, Issue 34 2006Huang-Chi Du Abstract ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 200 leading journals. To access a ChemInform Abstract, please click on HTML or PDF. [source] Luminescent Excited-State Intramolecular Proton-Transfer (ESIPT) Dyes Based on 4-Alkyne-Functionalized [2,2,-Bipyridine]-3,3,-diol DyesCHEMISTRY - A EUROPEAN JOURNAL, Issue 14 2008Gilles Ulrich Dr. Abstract Functionalized 6,6,-dimethyl-3,3,-dihydroxy-2,2,-bipyridine dyes (BP(OH)2) exhibit relatively intense fluorescence from the relaxed excited state formed by excited-state intramolecular proton transfer (ESIPT). Bromo functionalization of (BP(OH)2) species followed by palladium(0)-catalyzed reactions allows the connection (via alkyne tethers) of functional groups, such as the singlet-emitter diazaboraindacene (bodipy) group or a chelating module (terpyridine; terpy). The X-ray structure of the terpy-based compound confirms the planarity of the 3,3,-dihydroxy-bipyridine unit. The new dyes exhibit relatively intense emission on the nanosecond timescale when in fluid solution, in the solid state at 298,K, and in rigid glasses at 77,K. In some cases, the excitation wavelength luminescence was observed and attributed to 1),inefficiency of the ESIPT process in particular compounds when not enough vibrational energy is introduced in the Franck,Condon state, which is populated by direct light excitation or 2),the presence of an additional excited state that deactivates to the ground state without undergoing the ESIPT process. For some selected species, the effect of the addition of zinc salts on the absorption and luminescence spectra was investigated. In particular, significant fluorescence changes were observed as a consequence of probable consecutive formation of a 1:1 and 1:2 molecular ratio of ligand/zinc adducts owing to coordination of ZnII ions by the bipyridyldiol moieties, except when an additional terpyridine subunit is present. In fact, this latter species preferentially coordinates to the ZnII ion in a 1:1 molecular ratio and further inhibits ZnII interaction. In the hybrid Bodipy/BP(OH)2 species, complete energy transfer from the BP(OH)2 to the bodipy fluorophore occurs, leading to exclusive emission from the lowest-lying bodipy subunit. Des composés colorés à base de 6,6,-dimethyl-3,3,-dihydroxy-2,2,-bipyridine (BP(OH)2) ont été synthétisés et présentent une fluorescence relativement intense issue de la relaxation d,un état excité provenant d,un transfert de proton dans l,état excité (ESIPT). La bromation de dérivés (BP(OH)2) suivie d,un couplage croisé catalysé par du Pd0sous-ligandé permet de connecter (par l,intermédiaire de pont alcyne) des groupes fonctionnels comme un groupe émetteur singulet de type boradiazaindacène (Bodipy) ou un module chélatant universel (une terpyridine). Une structure par diffraction aux rayons X a été obtenu avec le dérivé terpyridine, celle ci confirme la planéité de l,unité 3,3,-dihydroxy-bipyridine. Les nouveaux fluorophores possèdent une émission relativement intense avec une durée de vie de l,ordre de la nanoseconde, en solution et à l,état solide à 298,K ainsi que dans un verre à 77,K. Dans certain cas, la luminescence dépend de la longueur d,onde d,excitation, ce phénomène est attribué à (i) l,inefficacité du processus ESIPT, quand trop peu d,énergie vibrationnelle est introduite dans l,état Franck-Condon peuplé directement par la lumière d,excitation (ii) la présence d,un état excité supplémentaire qui désactive l,état fondamental sans passer par un processus ESIPT. Pour certains composés, l,effet de l,addition de sels de Zinc sur les spectres d,absorption et d,émission a été étudié : en particulier, des changements significatifs de fluorescence ont été observés, probablement due à la formation consécutive de complexes ligand/zinc de st,chiométrie 1:1 et 1:2, provenant de la coordination des cations ZnIIpar l,unité bipyridyl-diol, sauf quand une fonction terpyridine est présente. En fait, dans cette dernière espèce le zinc est préférentiellement coordiné par la terpyridine dans un ratio 1:1, et toute coordination supplémentaire de Zinc semble inhibée. Dans le composé hybride Bodipy/BP(OH)2,un transfert d,énergie quantitatif est observé du BP(OH)2vers le fluorophore Bodipy, entraînant une émission exclusive de la sous-unité Bodipy. Composti basati sulla subunità 6,6,-dimetil-3,3,-dididrossi-2,2,-bipiridina (BP(OH)2), variamente funzionalizzati, presentano fluorescenza relativamente intensa da stati eccitati formati attraverso trasferimento protonico nello stato eccitato (ESIPT). Bromo-funzionalizzazione dei composti di tipo BP(OH)2, seguita da reazioni catalizzate da Pd(0), permettono di connettere (con legame alchinico) gruppi funzionali quali il diazaboroindacene (Bodipy) o un modulo chelante (terpiridina) al frammento BP(OH)2. La struttura ai raggi X del composto contenente la terpiridina conferma la planarità dell,unità 3,3,-diidrossi-bipiridina. Le nuove specie presentano intensa emissione nella scala dei nanosecondi, in soluzione fluida ed allo stato solido a 298,K ed in matrice rigida a 77,K. In alcuni casi, la luminescenza dipende dalla lunghezza d,onda di eccitazione: questo fenomeno è attribuito a (i) inefficienza del processo ESIPT, quando non sufficiente energia vibrazionale è introdotta nello stato Franck-Condon a seguito di eccitazione luminosa o (ii) alla presenza di uno stato eccitato addizionale che si disattiva allo stato fondamentale senza passare dallo stato eccitato prodotto attraverso il meccanismo ESIPT. Per composti selezionati è stato anche studiato l,effetto della presenza di sali di zinco sulle proprietà di assorbimento elettronico e di luminescenza: significativi cambiamenti della fluorescenza sono stati osservati, come conseguenza della consecutiva formazione di addotti 1:1 e 1:2 (rapporto molare BP(OH)2/zinco), dovuta alla coordinazione di cationi di ZnIIda parte del bipiridil-diolo, che si verifica in tutti i casi studiati tranne in presenza di una subunità terpiridinica. In quest,ultimo caso, infatti, si forma soltanto l,addotto 1:1, e ulteriore coordinazione di cationi di ZnIIappare inibita. Nella specie ibrida Bodipy/BP(OH)2si verifica un completo trasferimento di energia elettronica dal BP(OH)2 al Bodipy, che porta ad emissione esclusivamente dalla subunità Bodipy, a piû bassa energia. [source] Dipyrrolyl-Functionalized Bipyridine-Based Anion Receptors for Emission-Based Selective Detection of Dihydrogen PhosphateCHEMISTRY - A EUROPEAN JOURNAL, Issue 5 2007Patrick Plitt Dr. Abstract New cationic anion receptors, based on the use of pyrrole-substituted bipyridine and coordinated to transition metals, are described. Specifically, polypyridine,ruthenium and ,rhodium cores have been functionalized to generate an anion binding site. The design was chosen to probe the influence of the pyrrole-to-pyrrole separation on anion-binding affinities and selectivities; this distance is greater in the new systems of this report (receptors 1 and 2) relative to that present in related dipyrrolyl quinoxaline based receptors 3 and 4. Solution-phase anion-binding studies, carried out by means of 1H,NMR spectroscopic titrations in [D6]DMSO and isothermal titration calorimetry (ITC) in DMSO, reveal that 1 and 2 bind most simple anions with substantially higher affinity than either 3 or 4. In the case of chloride anion, structural studies, carried out by means of single-crystal X-ray diffraction analyses, are consistent with the solution-phase results and reveal that receptors 1 and 2 are both able to stabilize complexes with this halide anion in the solid state. [source] Transformation of a zinc inclusion complex to wurtzite ZnS microflowers under solvothermal conditionsCRYSTAL RESEARCH AND TECHNOLOGY, Issue 9 2010Liwei Mi Abstract Wurtzite zinc sulfide (ZnS) microflowers were synthesized successfully by a convenient solvothermal route in ethylene glycol (EG) and ethylenediamine (EN) using thiourea and zinc inclusion complex as starting materials. The inclusion complex {[Zn(bipy)2(H2O)2](4-Cl-3-NH2 -C6H3SO3)2(bipy) (H2O)2}n was achieved by the reaction of zinc oxide (ZnO) and 4-Cl-3-NH2 -C6H3SO3 with the bridging ligand bipy under moderate conditions, in which bipy is 4,4,-bipyridine and 4-Cl-3-NH2C6H3SO3NH is 4-Chloro-3-aminobenzene sulfonic acid. The phase purity of bulk products was confirmed by powder X-ray diffraction and element analysis. The factors that might affect the purity of the ZnS product during the synthesis were discussed in detail. It was found that the products were significantly affected by the mixed solvents and the starting materials. X-ray single crystal diffraction, scanning electron microscopy (SEM), energy-dispersive X-ray spectrometry (EDS), and X-ray diffraction (XRD) were used to characterize the products. (© 2010 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim) [source] Synthesis and crystal strcucture of two zinc inclusion complexesCRYSTAL RESEARCH AND TECHNOLOGY, Issue 8 2008Min-Le Han Abstract X-ray single crystals of these two inclusion complexes, [Zn(H2O)4L2]·(4-amino-1-naphthalene sulfonate)2 (L = 1,3-bis(4-pyridyl) propane), 1, and [Zn(H2O)(bipy)2]·(4-amino-1-naphthalene sulfonate)(NO3) (bipy = 4,4'-bipyridine), 2 were achieved by the reaction of Zn(NO3)2 and 4-amino-1-naphthalene sulfonate to 1,3-bis(4-pyridyl) propane and 4,4'-bipyridine, respectively. As inclusion complexes, the cationic components of 1 and 2 were formed by two infinite zigzag chains, while, 4-amino-1-naphthalene sulfonate made up the anionic parts of these two complexes. Thus, the whole molecules of these two complexes are neuter. Numous hydrogen bonds could be found in these two inclusion complexes, which help them to form three-dimensional solid-state packing structure architectures. (© 2008 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim) [source] Electrogenerated Chemiluminescence Sensor Based on Tris(2,2,-bipyridine)ruthenium(II)-Immobilized Natural Clay and Ionic LiquidELECTROANALYSIS, Issue 2 2010Ping Jiang Abstract A novel electrogenerated chemiluminescence (ECL) sensor based on natural clay and ionic liquid was fabricated. Tris(2,2,-bipyridine)ruthenium(II) (Ru(bpy)32+) was immobilized on natural clay surface through simple adsorption. An ECL sensor was prepared by mixing Ru(bpy)32+ -incorporated clay, graphite powder and an ionic liquid (1-butyl-3-methylimidazolium hexafluorophosphate) as the binder. The electrochemical behavior and ECL of the immobilized Ru(bpy)32+ was investigated. It was observed that the ECL of immobilized Ru(bpy)32+ was activated by the ionic liquid. The proposed ECL sensor showed high sensitivity to tri- n -propylamine (TPrA) and the detection limit was found to be 20,pM. In addition, the ECL sensor displayed good stability for TPrA detection and long-term storage stability. [source] Working Electrodes from Amalgam Paste for Electrochemical MeasurementsELECTROANALYSIS, Issue 4 2008Bogdan Yosypchuk Abstract Paste electrode with paste amalgam as an active electrode material is described here for the first time. Designed electrode from silver paste amalgam (AgA-PE) is solely metallic and does not contain any organic binder. Mechanical surface regeneration of AgA-PE is performed in the same way as for classical carbon paste electrodes and reproducibility of such regeneration is about 10%. Electrochemical surface regeneration appeared very efficient for most measurements. In dependence on paste metal content, the electrode surface can be liquid (resembling a film) or rather solid. The hydrogen overvoltage on AgA-PE is high, and the electrode allows measurements at highly negative potentials. AgA-PE is well suited for study of reduction or oxidation processes without an accumulation step. Anodic stripping voltammetry of some metals tested on the electrode is influenced by formation of intermetallic compounds. The measurement based on cathodic stripping voltammetry (adenine, cysteine) and on catalytic processes from adsorbed state (complex of osmium tetroxide with 2,2,-bipyridine) can be performed on AgA-PE practically under the same conditions as found earlier for HMDE and for silver solid amalgam electrode. The working electrode from paste amalgam combines the advantages of paste and metal electrodes. [source] Fabrication and Characterization of DNA/QPVP-Os Redox-Active Multilayer FilmELECTROANALYSIS, Issue 23 2004Jianyun Liu Abstract Calf thymus DNA was immobilized on functionalized glassy carbon, gold and quartz substrates, respectively, by the layer-by-layer (LBL) assembly method with a polycation QPVP-Os, a quaternized poly(4-vinylpyridine) partially complexed with osmium bis(2,2,-bipyridine) as counterions. UV-visible absorption and surface plasmon resonance spectroscopy (SPR) showed that the resulting film was uniform with the average thickness 3.4,nm for one bilayer. Cyclic voltammetry (CV) showed that the total surface coverage of the polycations increases as each QPVP-Os/DNA bilayer added to the electrode surface, but the surface formal potential of Os-centered redox reaction shifts negatively, which is mainly attributed to the intercalation of redox-active complex to DNA chain. The electron transfer kinetics of electroactive QPVP-Os in the multilayer film was investigated by electrochemical impedance experiment for the first time. The permeability of Fe(CN) in the solution into the multilayer film depends on the number of bilayers in the film. It is worth noting that when the multilayer film is up to 4 bilayers, the CV curves of the multilayer films display the typical characteristic of a microelectrode array. The nanoporous structure of the multilayer film was further confirmed by the surface morphology analysis using atomic force microscopy (AFM). [source] Biosensor for Hepatitis B Virus DNA PCR Product and Electrochemical Study of the Interaction of Di(2,2,-bipyridine)osmium(III) with DNAELECTROANALYSIS, Issue 19 2004Hongtao Zhao Abstract The strategy for electrochemical detection of HBV DNA PCR product (181,bps) was designed by covalently immobilizing single-stranded HBV DNA on preoxidized glassy carbon electrode surface. The immobilization of single stranded DNA was verified by AC impedance spectra. The following hybridization reaction on surface was evidenced by electrochemical methods using [Os(bpy)2Cl2]+ as an electroactive indicator. The interactions of [Os(bpy)2Cl2]+ with calf thymus single and double stranded DNA immobilized on preoxidized glassy carbon electrodes were studied. [Os(bpy)2Cl2]+ could bind preferentially to the duplex DNA by intercalating to base pairs. The intrinsic binding constant of [Os(bpy)2Cl2]+ with calf thymus DNA was calculated to be 1.21×104,M,1. Using [Os(bpy)2Cl2]+ as an electrochemical hybridization indicator, the HBV DNA sensor has been used to detect qualitatively target HBV DNA in solution with high sensitivity and selectivity. [source] Multilayer Assemblies Consisting of Tri-Vanadium-Substituted Heteropolyanions and Its Electrocatalytic PropertiesELECTROANALYSIS, Issue 14 2003Shengyong Zhai Abstract We describe the controlled fabrication of ultrathin multilayer films consisting of tri-vanadium- substituted heteropolytungstate anions (denoted as P2W15V3) and a cationic polymer of quaternized poly (4-vinylpyridine) partially complexed with osmium bis(2,2,-bipyridine) (denoted as QPVP-Os) on the 4-aminobenzoic acid (4-ABA) modified glassy carbon electrode (GCE) surface based on layer-by-layer assembly. Cyclic voltammetry and UV-vis absorption spectrometry have been used to easily monitor the thickness and uniformity of thus-formed multilayer films. The V-centered redox reaction of P2W15V3 in the multilayer films can effectively catalyze the reduction of BrO and NO. The resulting P2W15V3/QPVP-Os multilayer film modified electrode behaves as a much promising electrochemical sensor because of the low overpotential for the catalytic reduction of BrO and NO, and the catalytic oxidation of ascorbic acid. [source] Two-Surface Strategy in Electrochemical DNA Hybridization Assays: Detection of Osmium-Labeled Target DNA at Carbon ElectrodesELECTROANALYSIS, Issue 5-6 2003Miroslav Fojta Abstract Target DNAs, including a 71-mer oligonucleotide, a PCR product and a plasmid DNA, all containing oligo(A) stretches, were hybridized at magnetic Dynabeads oligo(dT)25 (DBT). The hybridization events were detected using a technique based on chemical modification of the target DNA with a complex of osmium tetroxide with 2,2,-bipyridine (Os,,bipy) and voltammetric detection at carbon electrodes. DNA was modified with Os,,bipy prior to capture at DBT, at the beads, or after release from the beads. In the latter case, DNA-Os,,bipy was detected in the reaction mixture using adsorptive transfer stripping voltammetry involving extraction of unreacted Os,,bipy from the electrode by organic solvents. Pre-labeling of the target plasmid DNA and the PCR product with Os,,bipy significantly increased the yield of DNA captured at the beads. Tens of femtomoles of both short (the 71-mer oligonucleotide) and long (the 3-kilobase plasmid) target DNAs in a 20-microliter hybridization sample can be easily detected by means of these techniques. Various carbon electrode materials, including pyrolytic graphite (PGE), highly oriented pyrolytic graphite (HOPGE), carbon paste (CPE), glassy carbon and pencil graphite, were tested regarding their suitability for the detection of osmium-labeled DNA. Among them, PGE and HOPGE appeared usable in the measurements of both purified DNA-Os,,bipy and its mixtures with unreacted Os,,bipy while CPE was suitable for the detection purified osmium-labeled DNA. [source] Synthesis and Photophysical Properties of LnIII,DOTA,Bipy Complexes and LnIII,DOTA,Bipy,RuII Coordination ConjugatesEUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 28 2010Miguel Vázquez López Abstract The synthesis and the systematic and comparative photophysical study of a series of visible (EuIII, TbIII) and NIR-emitting (NdIII, YbIII) lanthanide complexes (Ln2L) and ruthenium,lanthanide coordination conjugates (Ln2LRu) are reported. The GdIII complex, the GdIII,RuII coordination conjugate, as well as the RuII complex of the ligand H6L have also been synthesized and photophysically studied as control systems. The ligand H6L, composed of a central bipyridine binding unit and functionalized on each 5,-position with a DOTA macrocycle, has been successfully synthesized from cyclen, 5,5,-dimethyl-2,2,-bipyridine and 1,2-ethylendiamine in a nine-step process. Detailed luminescence studies of all complexes, including the determination of the quantum yield and lifetime, were carried out on finely powdered microcrystalline samples as well as in water, deuterated water and [D6]DMSO at ambient (295 K) and low temperature (77 K). The photophysical data corroborate the existence of energy transfer in the Ln2L complexes and in the Nd2LRu coordination conjugate. However, no (or at most, very little) energy transfer is takes place from the Ru(bipy)3 chromophore to the LnIII ion in the other Ln2LRu heteropolymetallic complexes. Moreover, the photophysical studies reveal that all the complexes and coordination conjugates adopt different conformations and hydration states in solution and in the solid state, which influences the efficiency of the energy transfer between the bipy and/or Ru(bipy)3 antennae and the LnIII ions. [source] A Dynamically Entangled Coordination Polymer: Synthesis, Structure, Luminescence, Single-Crystal-to-Single-Crystal Reversible Guest Inclusion and Structural TransformationEUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 24 2010Arshad Aijaz Abstract A ZnII coordination polymer {[Zn2(cpa)2(bpy)]·3H2O}n (1) (cpa2, = 4-(methoxycarbonyl)benzoate and bpy = 4,4,-bipyridine) has been synthesized under solvothermal condition and structurally characterized. This coordination polymer has nanotubular threefold entangled (2D,3D) structure with embedded water molecules; the water molecules can be partially exchanged in reversible single-crystal-to-single-crystal (SC-SC) fashion by different solvent molecules like methanol, ethanol and acetone giving rise to {[Zn2(cpa)2(bpy)]·(0.5MeOH)·(2.5H2O)}n (2), {[Zn2(cpa)2(bpy)]·(0.5EtOH)·(0.5H2O)}n (3) and {[Zn2(cpa)2(bpy)]·(0.5Me2CO)·(H2O)}n (4). Inclusion of EtOH or MeOH leaves the size of the voids in the framework unaltered. Inclusion of acetone, however, is accompanied by shrinking of the voids in the framework. Heating of 1 at 100 °C under vacuum for 4 h affords the de-solvated compound, {Zn2(cpa)2(bpy)}n (1,). Single-crystal X-ray structure of 1, shows sliding of the individual nanotubular components expanding the overall framework. Thus, the coordination polymer exhibits dynamic motion of the molecular components in SC-SC fashion. All compounds were further characterized via IR spectroscopy, PXRD, elemental and TGA analysis. When 1 is placed in benzene at 100 °C for 2 days, compound {[Zn2(cpa)2(bpy)]·(2.5H2O)}n (5) is formed in a SC-SC fashion where coordination number of ZnII ion increases from four to five. Compound 1 also exhibits reversible guest-dependent photoluminescence properties. [source] Dehydrogenation of Hydridoirida-,-diketones in Methanol: The Selective Formation of Mono- and Dinuclear Acyl ComplexesEUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 20 2010Roberto Ciganda Abstract The hydridoirida-,-diketone [IrH{(PPh2(o -C6H4CO))2H}Cl] (1) reacts with diimines (NN) or with pyridine (py) in refluxing methanol to undergo dehydrogenation. The reactions afford selectively the cis -acyl, trans -phosphane isomers of the cationic [Ir(PPh2(o -C6H4CO))2(NN)]+ {NN = 2,2,-bipyridine (2); R,N=C(CH3),C(CH3)=N,R, [R = R, = NH2 (3); R = R, = OH (4); R = OH, R, = NH2 (5)]} or neutral [IrCl(PPh2(o -C6H4CO))2(py)] (6) derivatives. The reactions are faster for ligands containing amino substituents. Refluxing 1 in MeOH affords the formation of an equimolar mixture of dimercationic species [Ir2(,-Cl)(,-PPh2(o -C6H4CO))2(PPh2(o -C6H4CO))2]+ (7a and 7b) containing two acyls and a chloride as bridging groups. The isomers could be separated by fractional precipitation. Compound [3]Cl, containing amino substituents in the imino functionalities, catalyses the hydrogen transfer from 2-propanol to cyclohexanone to afford cyclohexanol. All the complexes were fully characterised spectroscopically. Single crystal X-ray diffraction analysis was performed on complexes 6 and [7b]ClO4. [source] Studies in Solution and the Solid State of Coordination Compounds Derived from LiBH4, NaBH4, and Bidentate Aromatic AminesEUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 13 2010Milagros Aguilar-Martínez Abstract The mixture of 2,2,-bipyridylamine, 2,2,-bipyridine, 1,10-phenanthroline, 1,2-phenylendiamine, and 1,4-phenylendiamine each with LiBH4 and NaBH4 in a 1:1 molar ratio in THF yields seven new complexes of the type MBH4·L-THF and one complex of the type MBH4·L. These compounds were characterized by IR and NMR spectroscopy and X-ray single-crystal structure determinations. In the solid state, the [BH4], group is bidentate, as deduced from the stretching patterns observed in IR spectra and confirmed by X-ray single-crystal structure analysis. NMR spectroscopy showed that all amines act as bidentate ligands and are symmetrically coordinated to the metal cation. Complexes LiBH4 -2,2,-bipyridine-THF (1), NaBH4 -2,2,-bipyridine-THF (2), LiBH4 -1,10-phenanthroline-THF (3), and NaBH4 -1,10-phenanthroline-THF (4) have a discrete molecular structure, whereas the complexes LiBH4 -1,2-phenylendiamine-THF (5), NaBH4 -1,2-phenylendiamine-THF (6), LiBH4 -2,2,-dipyridilamine (7), and LiBH4 -1,4-phenylendiamine-THF (8) have polymeric structures in the solid state. N -borane-dipyridylamine adduct 9 was isolated from an aged solution of 7. IR spectroscopy of the new complexes showed that the structures of complexes 1, 3, 4, and 6 are maintained in the solid state and in solution. A rotational barrier for the [BH4], group of less than 38 KJ,mol,1 was estimated for some of the new complexes. [source] Thermal Decomposition Reactions as a Tool for the Synthesis of New Thermodynamic Metastable Modifications: Synthesis, Structures, and Properties of (Formato)nickel(II) Coordination Polymers Based on 4,4,-BipyridineEUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 12 2010Jan Boeckmann Abstract The reaction of nickel formate with 4,4,-bipyridine (bipy) in aqueous solution at room temperature leads to the formation of the hydrated compound [Ni(HCO2)2(H2O)(bipy)·4H2O]n (1) reported recently. On heating, compound 1 decomposes into the new anhydrous compound of composition [Ni(HCO2)2(bipy)]n (2II), which decomposes on further heating. Interestingly, if the anhydrous compound is prepared from solution, a new modification 2I is obtained. Investigations on the stability of both forms show that modification 2I presents the thermodynamically most stable form between room and decomposition temperature, whereas modification 2II, which can only be prepared by thermal decomposition, is metastable. In the crystal structure of 2I, the Ni2+ cations are coordinated by four ,2 - anti,anti bridging formato anions and two bridging ,2 -bipy ligands in a slightly distorted octahedralgeometry. The formato anions bridge the metal cations in zigzag chains, which are further connected by ,2 - anti,anti formato anions and bipy ligands to give a three-dimensional coordination network. IR spectroscopic investigations on the metastable form 2II also indicate that all formato anions act as bridging ligands. Magnetic measurements of the hydrated and anhydrous compounds reveal different behavior with a ferromagnetic ordering for compound 2I and an antiferromagnetic ordering for compound 1. For form 2II, only Curie,Weiss paramagnetism was found. [source] Designing the Host-Guest Properties of Tetranuclear Arene Ruthenium Metalla-Rectangles to Accommodate a Pyrene MoleculeEUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 5 2010Nicolas P. E. Barry Abstract Cationic tetranuclear arene ruthenium complexes of the general formula [Ru4(p -cymene)4(N,N)2(dhnq)2]4+ comprising rectangular structures are obtained in methanol from the reaction of the dinuclear arene ruthenium precursor [Ru2(p -cymene)2(dhnq)2Cl2] (dhnq = 5,8-dihydroxy-1,4-naphthoquinonato) with pyrazine or bipyridine linkers [N,N = pyrazine, 1; 4,4,-bipyridine, 2; 1,2-bis(4-pyridyl)ethylene, 3] in the presence of AgCF3SO3. All complexes 1,3, isolated in good yield as triflate salts, have been characterised by NMR and IR spectroscopy. The interaction of these rectangular complexes with pyrene as a guest molecule has been studied in solution by various NMR techniques (1D, DOSY, ROESY). In [D3]acetonitrile, the pyrazine-containing metalla-rectangle 1 shows no meaningful interactions with pyrene. On the other hand, the 4,4,-bipyridine- and 1,2-bis(4-pyridyl)ethylene-containing metalla-rectangles 2 and 3 clearly interact with pyrene in [D3]acetonitrile. DOSY measurements suggest that, in the case of [Ru4(p -cymene)4(4,4,-bipyridine)2(dhnq)2]4+ (2), the interactions occur on the outside of the rectangular assembly, while in the case of [Ru4(p -cymene)4{1,2-bis(4-pyridyl)ethylene}2(dhnq)2]4+ (3), the pyrene molecule is found inside the hydrophobic cavity of the metalla-rectangle, thus giving rise to a host-guest system. [source] Structural, Spectroscopic, and Proton-Coupled Electron-transfer Behavior of Pyrazolyl-3,5-bis(benzimidazole)-Bridged Homo- and Heterochiral RuIIRuII, OsIIOsII, and OsIIRuII 2,2,-Bipyridine ComplexesEUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 4 2010Sujoy Baitalik Abstract The homo- and heterobimetallic complexes [(bpy)2MII(H2pzbzim)M,II(bpy)2](ClO4)3·nH2O (1, 3, 5) and their corresponding deprotonated complexes [(bpy)2MII(pzbzim)M,II(bpy)2](ClO4)·nH2O (2, 4, 6) [where MII, M,II = Ru (1, 2) = Os (3, 4); MII = Os and M,II = Ru (3, 5); bpy = 2,2,-bipyridine; H3pzbzim = pyrazole-3,5-bis(benzimidazole)] were synthesized, separated to their heterochiral (a, ,,/,,) and homochiral (b, ,,/,,) diastereoisomers, and characterized by elemental analyses, ESI-MS, and 1H NMR spectroscopy. The X-ray structures of 1a, 3a, and 5a show the involvement of two pyridine rings of two bpy ligands in strong intramolecular nonbonded ,,, interaction. The occurrence of a C,H···, interaction between an aromatic C,H and the ,-cloud of a pyridine ring leads to strong electronic shielding of this proton (1H NMR). In all cases, the two diastereoisomers show practically no differences in their absorption spectra, redox potentials, and pK values. The large shifts in the E1/2 values to less positive potentials and substantial redshifts in the MLCT bands that occur on deprotonation of 1, 3, and 5 are energetically correlated. From the profiles of E1/2(1), (2) vs. pH over the pH range 1,12, the equilibrium constants and standard redox potentials for all the complex species in the metal oxidation states II·II, II·III, and III·III and the bridged ligand in the protonation states H2pzbzim,, Hpzbzim2,, and pzbzim3, have been evaluated. Using these values the bond dissociation free energies for the benzimidazole N,H bonds have been estimated. Spectroelectrochemical studies have been carried out for 1a, 3a, and 5a in the range 400,1100 nm. With stepwise oxidation of the metal centers replacement of MLCT bands by LMCT bands occur gradually with the observation of sharp isosbestic points. In the case of 1a, a band observed at ,max = 910 nm for the RuIIRuIII species has been ascribed to intervalence charge transfer (IVCT) transition. [source] Nucleophilic Addition of Water and Alcohols to Dicyanonitrosomethanide: Ligands with Diverse Bonding Modes in Magnetically Coupled d-Block ComplexesEUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 1 2010Anthony S. R. Chesman Abstract Ligands resulting from the transition-metal-promoted nucleophilic addition of water or an alcohol to dicyanonitrosomethanide ions (dcnm) have been utilised in the formation of a large series of polynuclear complexes. Addition of water to dcnm results in formation of carbamoylcyanonitrosomethanide (ccnm); deprotonation of this ligand gives amidocarbonyl(cyano)nitrosomethanide (acnm), which has been incorporated into the trinuclear complex [Cu3(acnm)2(dmae)2(H2O)2] [dmae = 2-(dimethylamino)ethoxide] (1) which shows strong antiferromagnetic coupling with an exchange coupling constant, J = ,500 cm,1. [Cu(acnm)(NH3)2], (2) marks the first instance of acnm facilitating the formation of a coordination polymer, namely a 1D chain with intramolecular hydrogen bonding. Attempts to synthesise 2 through different reaction conditions instead resulted in the mononuclear [Cu(acnm)(NH3)2(py)] (py = pyridine) (3). The addition of ethanol to dcnm results in cyano[imino(ethoxy)methyl]nitrosomethanide (cenm) which features in the mononuclear [Cu(cenm)2(H2O)2] (4) and polymeric {[Cu(cenm)2]2·H2O}, (5). The latter is the first example of the cenm ligand in a coordination polymer and has a highly unusual coordination mode through the nitrile groups and extremely weak antiferromagnetic coupling. {[Mn3(ccnm)2(EtOH)2(OAc)4]·2EtOH}, (6) and (Et4N)2[Cu(ccnm)4] (7) contain previously unobserved coordination modes of the ccnm ligand while the complex [Mn(cmnm)3Mn(bipy)(MeOH)](ClO4) (8) {cmnm = cyano[imino(methoxy)methyl]nitrosomethanide, bipy = 2,2,-bipyridine} displays weak antiferromagnetic coupling between manganese atoms with J = ,1.44 cm,1. A change in the solvent systems used in the synthesis of 7 results in the formation of the mononuclear complexes [Mn(bipy)2(dcnm)2] (9) or [Mn(bipy)2(H2O)(dcnm)](dcnm)·H2O (10) and [Mn(bipy)2(dcnm)(H2O)](dcnm) (11). The addition of ethlyene glycol monomethyl ether to dcnm gives cyano[imino(2-methoxyethoxy)methyl]nitrosomethanide (cgnm) and the formation of [Cu(cgnm)2(H2O)2] (12). [source] Synthesis, Structure, and Reactivity of Rhodium Bipyridine Compounds: Formation of a RhII Hydrido Cluster and a RhIII Peroxido ComplexEUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 29-30 2009Anna Penner Abstract Treatment of [Rh(,-Cl)(coe)2]2 (coe = cyclooctene) with 4,4,-di- tert -butyl-2,2,-bipyridine (tbbpy) gives the bipyridine complex [Rh(Cl)(tbbpy)(coe)] (1). A subsequent reaction with dihydrogen results in the formation of the cluster [{Rh(Cl)(H)(tbbpy)}]4 (2). The reaction of [Rh(,-Cl)(coe)2]2 with tbbpy in thf followed by the addition of CNtBu affords [Rh(Cl)(tbbpy)(CNtBu)] (3). The latter reacts with O2 or 18O2 to yield the peroxido complexes [Rh(Cl)(O2)(tbbpy)(CNtBu)] (4a) and [Rh(Cl)(18O2)(tbbpy)-(CNtBu)] (4b), respectively. Complexes 1,4 were characterized by X-ray crystallography. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009) [source] | ||||||||||||||||||||||||||||