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Article Citation - WoS: 16Citation - Scopus: 20Concise Synthesis, Electrochemistry and Spectroelectrochemistry of Phthalocyanines Having Triazole Functionality(Pergamon-elsevier Science Ltd, 2014) Karaca, Huseyin; Sezer, Serdar; Ozalp-Yaman, Seniz; Tanyeli, CihangirThe synthesis of novel metallophthalocyanines (M = Zn, Ni) bearing substituted benzyl protected 1,2,3-triazole moieties at peripheral positions is described for the first time via direct cyclotetramerization. These complexes have been characterized by a combination of FT-IR, H-1 NMR, HRMS and UVVis spectroscopy techniques and all the new compounds are highly soluble in most common organic solvents. In addition, the electrochemical and electrochromic behaviors of the complexes are investigated. Cyclic voltammetry and differential pulse voltammetry measurements demonstrate ligand base oxidations and reductions for both the Zn(II) and Ni(II) phthalocyanines by the transfer of one electron in each electrochemical step. The redox couples are identified in situ by monitoring the electronic absorption spectral changes during the electrolysis.Article Citation - Scopus: 2Electrochemistry of Acetate-, Carbonate-, Sulfate-, and Dihydrogenphosphate-Bridged Dirhodium(ii) Complexes(Verlag der Zeitschrift fur Naturforschung, 2003) Yaman,Ş.Ö.; Önal,A.M.; Isci,H.Complexes, [Rh2(B-B)4L2]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 [Rh2 (O2CCH3)4 (NCCH3)2] in acetonitrile yielded [Rh2 (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 σ- and π-bonding interactions. Spectroscopic and CV data indicate that the degree of σ-interaction is Cl- > Br- > SCN-, and that of π-interaction is Br- > SCN- > Cl-.Article Citation - WoS: 3Citation - Scopus: 5Spectroelectrochemical Studies of Nuclease-Active Zinc(ii) Coordination Compounds From the Ligands Hpyramol and Hpyrimol(Pergamon-elsevier Science Ltd, 2010) Ozalp-Yaman, Seniz; de Hoog, Paul; Maheswari, Palanisamy Uma; Casellas, Helene; Golobic, Amalija; Kozlevcar, Bojan; Reedijk, JanThe electrochemical oxidation of four zinc(II) coordination compounds from the ligands 4-methyl-2-(2-pyridylmethyl)aminophenol (Hpyramol()) and 4-methyl-2-(2-pyridylmethylene)aminophenol (Hpyrimol) with chloride or acetate as counter-ions has been studied by in situ spectroelectrochemistry in dimethylformamide (DMF) Low-temperature EPR studies of electrolyte solutions of all zinc compounds indicate the presence of a phenoxyl radical with a g-value in the range 2 070-2 099 which is illustrative for an electron delocalization over the metal centre The final product of this oxidative process is shown to be a benzoquinone methide derivative (C) 2010 Elsevier Ltd All rights reservedArticle Citation - WoS: 2Citation - Scopus: 3Spectroelectrochemical Investigations of Pyrimidine-2 Binuclear Platinum(iii) Complexes(Pergamon-elsevier Science Ltd, 2014) Ozbek, Ozge; Özalp Yaman, Şeniz; Ozalp-Yaman, Seniz; Ozkan, Ilker; Onal, Ahmet M.; Isci, Huseyin; Özalp Yaman, Şeniz; Chemical Engineering; Chemical EngineeringThe electrochemical behavior of the binuclear platinum(III-III) complexes [Pt-2(C4H3N2S)(4)X-2] (C4H3N2S- = pyrimidine-2-thionate; X- = Cl--,Cl- Br--,Br- I-) have been studied by cyclic voltammetry and insitu spectroelectrochemistry in an acetonitrile-tetrabutylammonium tetrafluoroborate solventelectrolyte couple. An irreversible metal based reduction appears during the cathodic scan for each of the three complexes. The changes in UV-Vis spectra observed in-situ during the reductive electrolysis indicate that all three complexes give the same product, [Pt-2(C4H3N2S)(4)], with a Pt(II)-Pt(II) system. The changes in the reduction potentials of the complexes on changing the axial ligands are interpreted by the changes in the energy of the LUMO level, which is determined by the degree of sigma- and it-interactions of the axial halide ligands with the metal atoms. DFT (B3LYP/LanL2DZ) calculations support our experimental data. (c) 2014 Elsevier Ltd. All rights reserved.Article Electrochemistry of Acetate-, Carbonate-, Sulfate-, and Dihydrogenphosphate-Bridged Dirhodium(ii) Complexes(Verlag der Zeitschrift fur Naturforschung, 2003) Yaman,Ş.Ö.; Önal,A.M.; Isci,H.Complexes, [Rh2(B-B)4L2]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 [Rh2 (O2CCH3)4 (NCCH3)2] in acetonitrile yielded [Rh2 (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 σ- and π-bonding interactions. Spectroscopic and CV data indicate that the degree of σ-interaction is Cl- > Br- > SCN-, and that of π-interaction is Br- > SCN- > Cl-.
