Spectroelectrochemistry of potassium ethylxanthate, bis(ethylxanthato)nickel(II) and tetraethylammonium tris(ethylxanthato)nickelate(II)

Dag, O
Yaman, SO
Önal, Ahmet Muhtar
Isci, H
Electrochemical and chemical oxidation of S2COEt-, Ni(S2COEt)(2), and [Ni(S2COEt)(3)](-) have been studied by CV and in situ UV-VIS spectroscopy in acetonitrile. Cyclic voltammograms of S2COEt- and Ni(S2COEt)(2) display one (0.00 V) and two (0.35 and 0.80 V) irreversible oxidation peaks, respectively, referenced to an Ag/Ag+ (0.10 M) electrode. However, the cyclic voltammogram of [Ni(S2COEt)(3)](-) displays one reversible (- 0.15 V) and two irreversible (0.35, 0.80 V) oxidation peaks, referenced to an Ag/Ag+ electrode. The low temperature EPR spectrum of the oxidatively electrolyzed solution of (NEt4)[Ni(S2COEt)(3)] indicates the presence of [Ni-III(S2COEt)(3)], which disproportionates to Ni(S2COEt)(2), and the dimer of the oxidized ethylxanthate ligand, (S2COEt)(2) ((S2COEt)(2) = C2H5OC(S)SS(S)COC2H5), with a second order rate law. The final products of constant potential electrolysis at the first oxidation peak potentials of S2COEt-, Ni(S2COEt)(2), and [Ni(S2COEt)(3)](-) are (S2COEt)(2); Ni2+(sol) and (S2COEt)(2); and Ni(S2COEt)(2) and (S2COEt)(2), respectively. The chemical oxidation of S2COEt- to (S2COEt)(2), and [Ni(S2COEt)(3)](-) to (S2COEt)(2) and Ni(S2COEt)(2) were also achieved with iodine. The oxidized ligand in the dimer form can be reduced to S2COEt- with CN- in solution.


Electrochemical and chemical oxidation of K(C2H5OCS2),[Ni(C2H5OCS2)(2)] and [N(C2H5)(4)][Ni(C2H5OCS2)(3)]
Dag, O; Önal, Ahmet Muhtar; Isci, H (1996-06-26)
Electrochemical and chemical oxidation of (Et-Xan(-)), [Ni(Et-Xan)(2)] and [Ni(Et-Xan)(3)](-) (Et-Xan(-) = C2H5OCS2- have been studied by Cyclic Voltammetry and in situ UV-Vis spectroscopy in acetonitrile at room temperature. Cyclic Voltammograms (CV) of Et-Xan(-) and Ni(Et-Xan)(2) display one (0.00 V) and two (0.35 and 0.80 V) irreversible oxidation peaks, respectively, referenced to Ag/Ag+(0.10 M) electrode. However, CV of Ni(Et-Xan)(3)(-) displays one reversible (-0.15 V) and two irreversible (0.35, 0.80...
Spectroelectrochemical investigation of the anodic oxidation of dibenzo-18-crown-6
Cihaner, A; Önal, Ahmet Muhtar (Elsevier BV, 2004-10-01)
Poly(dibenzo-18-crown-6) (poly-DB18C6) was synthesized by electrochemical oxidation of dibenzo-18-crown-6 (DB18C6) using a mixture of acetonitrile and dichloromethane as the solvent and tetrabutylammonium tetrafluoroborate (TBABF(4)) or tetrabutylammonium hexafluorophosphate (TBAPF(6)) as supporting electrolyte. The anodic polymerization of DB18C6 was investigated using in situ ESR and in situ UV-Vis spectroscopic techniques. Spectroelectrochemical (SPEL), properties and thermal analysis of the resulting po...
Spectroelectrochemical and Photovoltaic Characterization of a Solution-Processable n-and-p Type Dopable Pyrrole-Bearing Conjugated Polymer
Baran, Derya; Balan, Abidin; Esteban, Beatriz-Meana; Neugebauer, Helmut; Sariciftci, Niyazi Serdar; Toppare, Levent Kamil (Wiley, 2010-12-15)
D-A-D-type polymers are of high interest in the field of photovoltaics and electrochromism. In this study we report the synthesis and electrochemical properties of PPyBT along with its photophysical properties and photovoltaic performance. PPyBT is soluble in common organic solvents and both n- and p-type dopable, which is a desired property for conjugated polymers. During electrochemistry studies, the onset potentials of the polymer were determined as +0.2V for oxidation and -1.4V for reduction. Using thes...
Electrochemical and optical properties of novel terthienyl based azobenzene, coumarine and fluorescein containing polymers: Multicolored electrochromic polymers
Yigit, Deniz; Udum, Yasemin Arslan; GÜLLÜ, Mustafa; Toppare, Levent Kamil (Elsevier BV, 2014-01-01)
Three electroactive terthienyl based monomers, namely 1-phenyl-2-[4-(2,2':5',2 ''-terthien-3'-ylmethoxy)phenyl]diazene (TTAz), 4-(2,2':5',2 ''-terthien-3'-ylmethoxy)-2H-chromen-2-one (TTCo) and methyl 2-[3-oxo-6-(2,2':5',2 ''-terthien-3'-ylmethoxy)-3H-xanthen-9-yl] benzoate (TTFlo), were synthesized with good yields and their conducting polymers were electrochemically prepared on ITO electrode surfaces. The effect of chromophore type on electrochemical and optical properties of the polymers was investigated...
Electrochemical behaviour and electrochemical polymerization of fluoro-substituted anilines
Cihaner, A; Önal, Ahmet Muhtar (2002-08-01)
The 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 reso...
Citation Formats
O. Dag, S. Yaman, A. M. Önal, and H. Isci, “Spectroelectrochemistry of potassium ethylxanthate, bis(ethylxanthato)nickel(II) and tetraethylammonium tris(ethylxanthato)nickelate(II),” JOURNAL OF THE CHEMICAL SOCIETY-DALTON TRANSACTIONS, pp. 2819–2824, 2001, Accessed: 00, 2020. [Online]. Available: https://hdl.handle.net/11511/47652.