Ruthenium(II)-CO complexes of N-[(2-pyridyl)methyliden]-alpha(or beta)-aminonaphthalene: Synthesis, spectral studies, crystal structure, redox properties and DFT calculation

The characterization and properties of trans-(X)-[RuX2(CO)(2)(alpha/beta-NaiPy)] (1, 2) (alpha-NaiPy (a), beta-NaiPy (b); X = Cl (1), I (2)) are described in this work. The structures are confirmed by single crystal X-ray diffraction studies. Reaction of these compounds with Me3NO in MeCN has isolated monocarbonyl trans-(X)-RuX2(CO)(MeCN)(alpha/beta-NaiPy)] (3, 4). The complexes show intense emission properties. Quantum yields of 1 and 2 (phi= 0.02-0.08) are higher than 3 and 4 (phi = 0.006-0.015). Voltammogram shows higher Ru(III)/Ru(II) (1.3-1.5 V) potential of 1 and 2 than that of 3 and 4 (0.8-0.9 V) that may be due to coordination of two pi-acidic CO groups in former. The electronic spectra and redox properties of the complexes are compared with the results obtained by density functional theory (DFT) and time-dependent density functional theory (TD-DFT) using polarizable continuum model (CPCM).

N,N′-Bis(aryl)pyridine-2,6-dicarboxamide complexes of ruthenium: Synthesis, structure and redox properties

Reaction of five N,N′-bis(aryl)pyridine-2,6-dicarboxamides (H2L-R, where H2 denotes the two acidic protons and R (R = OCH3, CH3, H, Cl and NO2) the para substituent in the aryl fragment) with [Ru(trpy)Cl3](trpy = 2,2′,2″-terpyridine) in refluxing ethanol in the presence of a base (NEt3) affords a group of complexes of the type [RuII(trpy)(L-R)], each of which contains an amide ligand coordinated to the metal center as a dianionic tridentate N,N,N-donor along with a terpyridine ligand. Structure of the [RuII(trpy)(L-Cl)] complex has been determined by X-ray crystallography. All the Ru(II) complexes are diamagnetic, and show characteristic 1H NMR signals and intense MLCT transitions in the visible region. Cyclic voltammetry on the [RuII(trpy)(L-R)] complexes shows a Ru(II)–Ru(III) oxidation within 0.16–0.33 V versus SCE. An oxidation of the coordinated amide ligand is also observed within 0.94–1.33 V versus SCE and a reduction of coordinated terpyridine ligand within −1.10 to −1.15 V versus SCE. Constant potential coulometric oxidation of the [RuII(trpy)(L-R)] complexes produces the corresponding [RuIII(trpy)(L-R)]+ complexes, which have been isolated as the perchlorate salts. Structure of the [RuIII(trpy)(L-CH3)]ClO4 complex has been determined by X-ray crystallography. All the Ru(III) complexes are one-electron paramagnetic, and show anisotropic ESR spectra at 77 K and intense LMCT transitions in the visible region. A weak ligand-field band has also been shown by all the [RuIII(trpy)(L-R)]ClO4 complexes near 1600 nm.

Synthesis, structure and redox properties of (?-oxo)bis(?-carboxylato)diruthenium(III) complexes containing three different terminal ligands

Blue coloured, unstable, essentially diamagnetic and non-electrolytic diruthenium(III) complexes of the formation [Ru2O(O2CR)4(en)2(PPh3)2] were prepared by reacting [Ru2O(O2CR)4(PPh3)2] with 1,2-diaminoethane (en) in CH2Cl2 (R = C6H4-p-X; X = H, Me and OMe). The molecular structure of the complexes is proposed as [{(?1-O2CR)(?1-en)(PPH3)Ru}2(?-O)(?-O2CR)2] based on the 1H NMR spectral data. The electronic spectra of the complexes display a band near 569 nm with a shoulder at 630 nm. In CH2Cl2-0.1 M [Bun4N]ClO4, the complexes exhibit redox couples Ru2III,III/Ru2III,IV and Ru2III,IV/Ru2IV,IV near 0.1 and 1.2 V (vs SCE), respectively. The potentials are the lowest among diruthenium(III) complexes with a similar core structure.

Synthesis, x-ray structure and redox properties of [Ru2(?-O) (?-O2CMe)2(Me2NCH2CH2NH2)2(PPh3)2](ClO4)2

The title complex has been prepared from a reaction of [Ru2O(O22CMe)2 (MeCN)4(PPH3)2](ClO4)2 with N,N-dimethyl-1,2-diaminoethane (dmen) in MeOH. The crystal structure of [Ru2O(O2CMe)2(dmen)2(PPh3)2](ClO4)2.MeOH shows the presence of a [Ru2(mu-O)(mu-O2CMe)2]2+ core. The terminal ligands on each metal are a PPh3 and a bidentate chelating dmen. The Ru-Ru distance and Ru-O-Ru angle in the core are 3.271(2) angstrom and 120.9(4)-degrees. The more electron-donating site of the dmen ligand is bonded at the terminal sites trans to the mu-oxo ligand. The complex displays a visible absorption band at 566 nm (epsilon, 6960 M-1 cm-1) in MeCN and undergoes a nearly reversible one-electron oxidation at 1.02 V and an irreversible reduction at -0.52 V (vs SCE) in MeCN-0.1 M [NBu4n](ClO4).

Photophysical and electrochemical redox properties of fixed distance porphyrin-quinone systems

A few fixed distance covalently linked porphyrin-quinone molecules have been synthesized in which a benzoquinone is directly attached to a meso/beta-pyrrole position of tri(phenyl/pentafluorophenyl)/tetraphenylporphyrins. The choice of fluoroarylporphyrins permit modulation of Delta G(ET) values for photoinduced electron-transfer reactions in these systems. All short distance porphyrin-quinone molecules showed efficient quenching of the porphyrin singlet excited state. The electrochemical redox data coupled with the steady-state and time-resolved singlet emission data are analysed to evaluate the dependence of Delta G(ET) values on the rate of electron transfer (k(ET)) in these systems. The meso-trifluoroarylporphyrin-quinones are found to be sensitive probes of the surrounding dielectric environment. Varying solvent polarity on the mechanism of fluorescence quenching and k(ET) values revealed that short donor-acceptor distance and the solvent dielectric relaxation properties play a dominant role. (C) 1999 Elsevier Science S.A. All rights reserved.

Effect of alkyl group length on the conductivity in the 2,3,7,8,12,13,17,18-octakis(alkyl-thio)tetraazaporphyrins and redox properties of the metallooctakis(hexyl-thio)tetraazaporphyrins

A series of 2,3,7,8,12,13,17,18-octakis(alkyl-thio)tetraazaporphyrins (H(2)OATTAP) with different alkyl chain lengths have been synthesized. Cyclic voltammetry and differential pulse voltammetry have been used to investigate the effect of the controlled lengths of the eight peripheral thioether tails on the redox behavior of the molecules. The electrochemical reduction of octakis(hexyl-thio)tetraazaporphyrins, MOHTTAP (where M = Cu, Ni), was studied in 1,2-dichloroethane at a platinum electrode. The Cu derivative was oxidized in one single-electron-transfer step to yield a pi-cation radical and reduced in three single-electron-transfer steps to yield a pi-anion radical, dianion and trianion, respectively. For the Ni derivative, electron transfer reactions involving both the central metal atom and the macrocyclic ring were observed. Electron transfer pathways are proposed based upon voltammetric and in situ spectroelectrochemical results.

Electrochemical study of isopoly- and heteropoly-oxometallates film modified microelectrodes .6. Preparation and redox properties of 12-molybdophosphoric acid and 12-molybdosilicic acid modified carbon fiber microelectrodes

The redox behaviours of 12-molybdophosphoric acid (12-MPA) and 12-molybdosilicic acid (12-MSA) in aqueous acid media are characterized at the carbon fiber (CF) microelectrode. The preparation of CF microelectrode modified with 12-MPA or 12-MSA monolayer and the oxidation-reduction properties of the modified electrode in aqueous acid media or 50% (v/v) water-organic media containing some inorganic acids are studied by cyclic voltammetry. 12-MPA or 12-MSA monolayer modified CF microelectrode with high stability and redox reversibility in aqueous acidic media can be prepared by simple dip coating. The cyclic voltammograms of 12-MPA and 12-MSA and their modified CF microelectrodes in aqueous acid solution exhibit three two-electron reversible waves with the same half-wave potentials, which defines that the species adsorbed on the CF electrode surface are 12-MPA and 12-MSA themselves. The acidity of electrolyte solution, the organic solvents in the electrolyte solution, and the scanning potential range strongly influence on the redox behaviours and stability of 12-MPA or 12-MSA monolayer modified electrodes. On the other hand, the catalytic effects of the 12-MPA and 12-MSA and chlorate anions in aqueous acidic solution on the electrode reaction processes of 12-MPA or 12-MSA are described.

Effect of citrate on the redox properties of cytochrome C and its kinetic and binding behaviour with cytochrome oxidase /

Increasing citrate concentration, at constant ionic strength (30 mM) decreases the rate of cytochrome ~ reduction by ascorbate. This effect is also seen at both high (600 mM) and low (19 mM) ionic strengths, and the Kapp for citrate increases with increasing ionic strength. Citrate binds d both ferri -and ferrocytochrome ~, but with a lower affinity for the latter form (Kox . .red d = 2 mM, Kd = 8 mM) as shown by an equilibrium assay with N,N,N',N', Tetramethyl E- phenylenediamine. The reaction of ferricytochrome ~with cyanide is also altered in the presence of citrate: citrate increases the K~PP for cyanide. Column chromatography of cytochrome ~-cytochrome oxidase mixtures shows citrate increases the dissociation constant of the complex. These results are confirmed in kinetic assays for the "loose"site (Km = 20 pM) only. The effect of increasing citrate observable at the "tight" site (Km = 0.25 pM) is on the turnover number and not on the K . These results suggest a mechanism m where anion binding to cytochrome £ at the tight site affects the equilibrium between two forms of cytochrome c bound cytochrome oxidase: an active and an inactive one.

Ruthenium (III) complexes of tetradentate NSNO pyridylthioazophenolates: Synthesis, spectral studies, crystal structure and redox properties

A family of ruthenium (III) complexes of tetradentate monobasic NSNO donor chelators (HL) have been synthesized and isolated in their pure form. On chromatographic separation, trans-dichloro and cis-dichloro ruthenium (111) complexes of pyridylthioazophenolates are eluted using 19:1 and 7:3 (v/v) DCM-MeOH mixtures, respectively. Both cis and trans isomers of the dark brown colored ruthenium (111) complexes, having the general formula of [Ru(L)Cl-2], have been characterized by elemental analyses, spectroscopic and other physico-chemical tools. The magnetic moments of both the cis- and trans-[Ru(L)Cl-2] complexes are in the range of 1.71-1.79 BM. One of the complexes, trans-[Ru(L1)Cl-2] (2a), has been subjected to single-crystal X-ray analysis which confirms that the chlorines are in mutually trans positions in the molecule. The EPR spectra of the cis-[Ru(L)Cl-2] complexes (1) in DMF are consistent with the fact that the complexes are low-spin octahedral with one unpaired electron having three different g values (g(x) not equal g(y) not equal g(z)) complexes are monomeric with an octahedral coordination sphere. The electrochemical studies of [Ru(L)Cl,] in DMF show a quasi-reversible voltammogram. The reduction potentials for the cis-isomers are comparatively lower than those of the corresponding trans isomers. On reaction with the bidentate bipyridyl ligand in the presence of AgNO3, the cis-[Ru(L)Cl-2] complexes (1) produce a series of complexes with the general formula [Ru(L)(bpy)(2)](PF6)(2) (3). which have also been characterized by elemental analyses, spectroscopic and other physico-chemical tools. (c) 2006 Elsevier Ltd. All rights reserved.

Photochemical, photophysical and redox properties of novel fulgimide derivatives with attached 2,2 '-bipyridine (bpy) and [M(bpy)(3)](2+) (M = Ru and Os) moieties

Fulgimides monosubstituted with [M(bpy)(3)](2+) (M = Ru, Os; bpy = 2,2'-bipyridine) chromophore units and with a single bpy group were synthesized and investigated as components of conceivable dinuclear photochromic switches of luminescence. The E-, Z- and closed-ring (C) photoisomer forms of the bpy-bound fulgimide were successfully separated by semi-preparative HPLC. The same procedure failed, however, in the case of the [M(bpy)(3)](2+)-substituted fulgimides. Energy transfer from the excited photochromic unit to the metal-bpy centre competes with the fulgimide cyclization, reducing the photocyclization quantum yields by approximately one order of magnitude compared to the non-complexed fulgimide-bpy ligand (phi(EC) = 0.17, phi(EZ) = 0.071, phi(ZE) = 0.15 at lambda(exc) = 334 nm). The cycloreversion of the fulgimide-bpy ligand is less efficient (phi(CE) = 0.047 at lambda(exc) = 520 nm). The intensity of the (MLCT)-M-3-based luminescence of the metal-bpy chromophore (in MeCN, phi(deaer) = 6.6 x 10(-2) and tau(deaer) = 1.09 mu s for Ru; phi(deaer) = 6.7 x 10(-3) and tau(deaer) = 62 ns for Os) is not affected by the fulgimide photoconversion. These results and supporting spectro-electrochemical data reveal that the lowest triplet excited states of the photochromic fulgimide moiety in all its E-, Z- and closed-ring forms lie above the lowest 3MLCT levels of the attached ruthenium and osmium chromophores. The actual components are therefore unlikely to form a triad acting as functional switch of energy transfer from [Ru(bpy)(3)](2+) to [Os(bpy)(3)](2+) through the photochromic fulgimide bridge.

Photophysical and redox properties of dinuclear Ru and Os polypyridyl complexes with incorporated photostable spiropyran bridge

Aimed at creating a true photoswitchable energy transfer system, four dinuclear complexes containing ruthenium(II) and osmium(II) metal centers bridged by spiropyran-type linkers were designed and investigated. The bridge in its closed spiropyran form was shown to be a good insulator for energy transfer between the Ru-bpy donor and the Os-bpy acceptor (bpy = 2,2'-bipyridine). On the basis of properties of previously reported photochromic nitrospiropyrans substituted with a single polypyridine metal center, conversion of the bridge to the open merocyanine form was envisaged to result in efficient electronic energy transfer by a sequential ("hopping") mechanism. In contrast to the expectations, however, the studied closed-form dinuclear complexes remained stable independently of their photochemical or electrochemical activation. This difference in reactivity is attributed to the replacement of the nitro group by a second polypyridine metal center. We assume that these changes have fundamentally altered the excited-state and redox properties of the complexes, making the ring-opening pathways unavailable.

The syntheses, structures and redox properties of phosphine-gold(I) and triruthenium-carbonyl cluster derivatives of tolans

The syntheses of several ethynyl-gold(I) phosphine substituted tolans (1,2-diaryl acetylenes) of general form [Au(C=CC6H4C=CC6H4X)(PPh3)] are described [X = Me (2a), OMe (2b), CO2Me (2c), NO2 (2d), CN (2e)]. These complexes react readily with [Ru-3(CO) 10(mu-dppm)] to give the heterometallic clusters [Ru3(mu-AuPPh3)(mu-eta(1), eta(2)-C2C6H4C, CC6H4X)(CO)(7)(mu-dppm)] (3a-e). The crystallographically determined molecular structures of 2b, 2d, 2e and 3a-e are reported here, that of 2a having been described on a previous occasion. Structural, spectroscopic and electrochemical studies were conducted and have revealed little electronic interaction between the remote substituent and the organometallic end-caps. (C) 2007 Elsevier B. V. All rights reserved.

Tuning of redox potential and visible absorption band of ruthenium(II) complexes of (benzimidazolyl) derivatives: synthesis, characterization, spectroscopic and redox properties, X-ray structures and DFT calculations

Six ruthenium(II) complexes have been prepared using the tridentate ligands 2,6-bis(benzimidazolyl) pyridine and bis(2-benzimidazolyl methyl) amine and having 2,2'-bipyridine, 2,2':6',2 ''-terpyridine, PPh3, MeCN and chloride as coligands. The crystal structures of three of the complexes trans-[Ru(bbpH(2))(PPh3)(2)(CH3CN)I(ClO4)(2) center dot 2H(2)O (2), [Ru(bbpH(2))(bpy)Cl]ClO4 (3) and [Ru(bbpH(2))(terpy)](ClO4)(2) (4) are also reported. The complexes show visible region absorption at 402-517 nm, indicating that it is possible to tune the visible region absorption by varying the ancillary ligand. Luminescence behavior of the complexes has been studied both at RT and at liquid nitrogen temperature (LNT). Luminescence of the complexes is found to be insensitive to the presence of dioxygen. Two of the complexes [Ru(bbpH(2))(bpy)Cl]ClO4 (3) and [Ru(bbpH(2))(terpy]ClO4)(2) (4) show RT emission in the NIR region, having lifetime, quantum yield and radiative constant values suitable for their application as NIR emitter in the solid state devices. The DFT calculations on these two complexes indicate that the metal t(2g) electrons are appreciably delocalized over the ligand backbone. (C) 2006 Elsevier B.V. All rights reserved.

Synthesis, spectroscopic and redox properties of some ruthenium(II) thiosemicarbazone complexes: structural description of four of these complexes

Sixteen neutral mixed ligand thiosemicarbazone complexes of ruthenium having general formula [Ru(PPh3)(2)L-2], where LH = 1-(arylidine)4-aryl thiosemicarbazones, have been synthesized and characterized. All complexes are diamagnetic and hence ruthenium is in the +2 oxidation state (low-spin d(6), S = 0). The complexes show several intense peaks in the visible region due to allowed metal to ligand charge transfer transitions. The structures of four of the complexes have been determined by single-crystal X-ray diffraction and they show that thiosemicarbazone ligands coordinate to the ruthenium center through the hydrazinic nitrogen and sulfur forming four-membered chelate rings with ruthenium in N2S2P2 coordination environment. In dichloromethane solution, the complexes show two quasi-reversible oxidative responses corresponding to loss of electron from HOMO and HOMO - 1. The E-0 values of the above two oxidations shows good linear relationship with Hammett substituents constant (sigma) as well as with the HOMO energy of the molecules calculated by the EHMO method. A DFT calculation on one representative complex suggests that there is appreciable contribution of the sulfur p-orbitals to the HOMO and HOMO - 1. Thus, assignment of the oxidation state of the metal in such complexes must be made with caution. (c) 2005 Elsevier B.V. All rights reserved.