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2 Polish Journal of Chemistry

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Cyclic Voltammetry and Electronic Absorption Spectroscopy in Investigations of the Nature of the Electrochemical reduction of Phenyldiazonium and Phenyl-bis-diazonium Cations

Koval'chuk E., Kozlovs'ka Z., Jackowska K., Roshal A., Wróblewska A., Reshetnyak O., Błażejowski J.

Polish Journal of Chemistry

2004

Vol. 78 / nr 1

139-147

The electrochemical reduction of phenyldiazonium and phenyl-bis-diazonium cations on mercury drop and platinum cathodes exhibits a multistep nature, as demonstrate the results of polarographic and cyclic voltammetry measurements. The primarily formed radicals participate in various secondary processes, as a result of which occur species absorbing UV-VIS radiation. Electronic absorption in the visible region can be ascribed to entities forming from the recombination of two azophenyl or azophenyl and phenyl radicals, originating from the one- or two-electron reduction of primarily or secondary formed cations.

Spectral Properties of Phenylbenzopyrylium Salts in Solutions as a Result of Their Nucleophilic Solvation

Roshal A., Minayev D. Y., Pedash Y. F., Novikov A. I.

Polish Journal of Chemistry

2002

Vol. 76 / nr 9

1301-1321

A dependence of spectral properties of 2-phenylbenzopyrylium (PBP) salts in solutions on the solvent nucleophilicity is presented.Asimple solvate complex model for quantum chemical estimation of the nucleophilic solvation influence on band positions in absorption and fluorescence PBP salt spectra is proposed. Quantum yield changes of the PBP salts in solvents of different nucleophilicity are explained as due to the influence of nucleophile solvation on the efficiency of the intersystem crossing in PBP cations. Two ways of this influence are proposed: the direct one, due to energy changes in S1 and Ti levels, and the indirect one, due to an increase or decrease of spin-orbital interaction efficiency, caused by changes of the structural rigidity of solvated PBP cations.