Photochemistry of copper(II) polyfluorocarboxylates and copper(II) acetate as their hydrocarbon analogues

Photochemistry of copper(II) acetate and polyfluorocarboxylates in liquid and frozen alcohol solutions has been investigated. The photolysis of copper(II) acetate leads to the metal copper as a final product. The mechanism of photolysis, including the intramolecular electron transfer as the initial stage of process, has been proposed. ESR spectra of free radicals were registered at the low-temperature (77 K) photolysis of copper(II) acetate in isopropanol solution, being the indirect evidence for the validity of proposed mechanism. Photochemical transformations of copper(II) perfluorocarboxylates have been found to occur in two stages. The first one includes the changes in the coordination sphere of Cu(II) ion. The second stage results in the reduction process, leading to metal copper and the precipitate CuF. The 'dark' contact of the precipitate with methanol solution, obtained after irradiation, yields the complex Cu(PFC)x2CH(3)OH, where PFC is the perfluorocarboxylate anion. The mechanisms for the observed photochemical and dark reactions have been proposed. (C) 2000 Elsevier Science S.A. All rights reserved.