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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.Article Citation - WoS: 20Citation - Scopus: 21Electrochemical Behaviour and Electrochemical Polymerization of Fluoro-Substituted Anilines(Wiley, 2002) Cihaner, A; Önal, AMThe electrochemical behaviour of three fluoro-substituted aniline monomers, 2-fluoroaniline (2FAN), 3-fluoroaniline (3FAN) and 4-fluoroaniline (4FAN), was investigated in aqueous acidic and organic media by means of cyclic voltammetry (CV) studies. Constant potential electrolysis (CPE) of the monomers in acetonitrile-water mixture (1: 1 by volume) using NaClO4 as supporting electrolyte yielded soluble polymers. The mechanism of electrochemical polymerization was investigated using in situ electron spin resonance (ESR) and in situ UV-VIS spectroscopic techniques for one of the monomers (4FAN). Both CV and in situ LTV-VIS measurements indicated that the polymers obtained are in the emeraldine base form. In situ ESR studies indicated that electrochemical polymerization involves a radical-cation as an intermediate. Characterization of polymer products have been carried out using FTIR and NMR spectroscopic techniques, and thermal behaviour was studied using differential scanning calorimetry (DSC). It was found that conductivity can be imparted to assynthesized polyfluoroanilines via iodine doping. (C) 2002 Society of Chemical Industry.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: 5Citation - Scopus: 5Electrochemical Polymerization of 4-Allylanisole(Pergamon-elsevier Science Ltd, 2001) Cihaner, A; Testereci, HN; Önal, AMElectrochemical polymerization of 3-allylanisole (4AA). via constant potential electrolysis, has been investigated in acetonitrile using two different supporting electrolytes. Redox behavior of the monomer was also studied in the same solvent-electrolyte couples at room temperature. Electrochemical polymerization of the monomer yielded insoluble polymer films on the electrode surface, which bears a very low conductivity, together with the low molecular weight polymers in the bulk of the solution. The decrease in the monomer concentration, during the electrochemical polymerization. was monitored by taking the cyclic voltammogram of the electrolysis solution. The effect of temperature on the rate of electrochemical polymerization was: also studied. The polymers were characterized by taking the H-1-NMR and FTIR spectra. Molecular weight of the soluble polymer was determined by vapor pressure osmometry. Thermal analysis of the polymer film and soluble polymer were done by DSC. (C) 2001 Elsevier Science Ltd. All rights reserved.Article Citation - WoS: 13Electrochemical and Quantum Chemical Studies on Mitomycin and Adriamycin(Elsevier, 2003) Özalp-Yaman, S; Önal, AM; Türker, LIn-situ spectroelectrochemical redox behaviour of two prominent chemotherapeutic agents, mitomycin and adriamycin were studied at constant potential. AM 1 (UHF) type quantum chemical calculations on the neutral as well as radical anion and cation forms of mitomycin and adriamycin were performed. (C) 2003 Elsevier Science B.V. All rights reserved.Article Citation - WoS: 14Citation - Scopus: 16Electrosynthesis of Polyfuran in Acetonitrile-Boron Trifluoride-Ethyl Ether Mixture and Its Device Application(John Wiley & Sons inc, 2007) Tirkes, Seha; Onal, Ahmet M.Electrochemical polymerization of furan was achieved in acetonitrile/boron trifluoride/ethyl ether (CH3 CN/BF3/EE) mixture in the presence of tetrabutylammonium tetrafluoroborate via constant potential electrolysis at 1.4 V versus Ag/AgCl. Electrochemical behavior of furan was investigated in the same solvent mixture of varying ratios, utilizing cyclic voltammetry. Free-standing polyfuran (PFu) films were obtained in CH3CN/BF3/EE mixture (2/4/4; v/v/v) and characterized using FTIR spectroscopic technique. Spectroelectrochemical behavior of the PFu film was investigated by recording the electronic absorption spectra, in sitn, in monomer-free solution. It is observed that PFu film can be reversibly cycled between -0.1 V (gray) and + 0.6 V versus Ag-wire (gray color); however, this behavior diminishes in the presence of water. Electrochromic device application of PFu film with poly(ethylene dioxythiophene) was also studied. (c) 2006 Wiley Periodicals, Inc.
