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Article Citation - WoS: 1Electrochemistry of Acetate-, Carbonate-, Sulfate-, and Dihydrogenphosphate-Bridged Dirhodium(ii) Complexes(verlag Z Naturforsch, 2003) Yaman, SO; Önal, AM; Isci, HComplexes, [Rh-2(B-B)(4)L-2](n) (B-B = CH3CO2-, L = CH3CN, H2O, Cl-, Br-, SCN-; B-B CO32-, SO42-, H2PO4-, L = H2O, Cl-, Br-, SCN-) were prepared and their cyclic voltammograms (CV) and electronic absorption spectra were measured in solution. The CV of the complexes exhibits a reversible one-electron transfer from a metal-based orbital. Constant potential electrolysis at the oxidation peak potential of [Rh-2(O2CCH3)(4)(NCCH3)(2)] in acetonitrile yielded [Rh-2(O2CCH3)(4)(NCCH3)(2)](+), a mixed valent Rh(II)-Rh(III) cation complex. The formation of the mixed valent complex was monitored by measuring electronic absorption spectra of the solution in situ during the oxidative electrolysis. The reductive electrolysis of the mixed valent complex solution, in the same electrolysis cell, yielded the original electronic absorption spectrum of the starting complex. The changes in the oxidation and reduction potentials of the complexes with different axial ligands, L = H2O, Cl-, Br-, SCN-, are correlated to the relative energy changes of HOMO and LUMO of the complexes, which indicates the metal-axial ligand sigma- and pi-bonding interactions. Spectroscopic and CV data indicate that the degree of a-interaction is Cl- > Br- > SCN-, and that of pi-interaction is Br- > SCN- > Cl-.Article Citation - WoS: 4Citation - Scopus: 4Electrical, Optical and Photoconductive Properties of Poly(dibenzo-18(Wiley-v C H verlag Gmbh, 2004) Qasrawi, AF; Cihaner, A; Önal, AMTo investigate the energy levels, absorption bands, band gap, dominant transport mechanisms, recombination mechanisms and the free carrier life time behavior of poly-dibenzo-18-crown-6, poly-DB18C6, films, the dark electrical conductivity in the temperature range of 200-550 K, the absorbance and photocurrent spectra, the photocurrent -illumination intensity and time dependence at 300 K were studied. The dark electrical conductivity measurements revealed the existence of three energy levels located at 0.93, 0.32 and 0.76 eV below the tails of the conduction band. The main transport mechanism in the dark was found to be due to the thermal excitation of charge carriers and the variable range hopping above and below 260 K, respectively. The photocurrent and absorbance spectra reflect a band gap of 3.9 eV. The photocurrent -illumination intensity dependence reflects the sublinear, linear and supralinear characters indicating the decrease, remaining constant and increase in the free electron life time that in turn show the bimolecular, strong and very strong recombination characters at the surface under the application of low, moderate and high illumination intensity, respectively. A response time of 25.6 s was calculated from the decay Of I-ph-time dependence. (C) 2004 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.Article Citation - WoS: 2Spectroelectrochemical Investigation of Pentacarbonyl(pyrazine)metal(0) (metal = Cr, Mo, W) Complexes of Group 6 Elements(Walter de Gruyter Gmbh, 2002) Yaman, SO; Esentürk, E; Kayran, C; Önal, AMThe electrochemical behaviour of pentacarbony l(pyrazine) metal (0) complexes of the group 6 elements was studied by cyclic voltammetry in dichloromethane-(n-Bu)(4)NBF4 solvent-electrolyte couple at -20 degreesC vs. Ag/Ag+ or SCE reference electrode. Constant potential electrolyses of the complexes were carried out at their first oxidation peak potentials and monitored in situ by UV-Vis spectrometry. Electrolysis of W(CO)(5)pz produces [W(CO)(5)pz](+) and a similar electrochemical mechanism is expected both for Cr(CO)(5)pz and Mo(CO)(5)pz complexes. In situ low temperature constant current ESR electrolysis also confirmed the production of [W(CO)(5)pz](+) after the electron transfer.
