Time resolved studies of the photoinduced electron transfer in aqueous solutions of chloro- and cyanocuprate(I) complexes

Add time:08/12/2019    Source:sciencedirect.com

Laser flash and continuous photolysis studies of equilibrated solutions of CuCl−2CuCl−32, Cu(CN)−2Cu(CN)32− and Cu(CN)−2Cu(CN)2Cl2− systems were carried out in the UV region. Neutral aqueous solutions of the complexes produce hydrated electrons when they absorb pulses of laser light at 266 nm. The electrons are scavenged by the ground-state copper(I) species itself. The second-order rate constants of these reactions are determined at various ionic strengths and concentrations. Illumination of chlorocuprate complexes in strong acidic media leads to formation of hydrogen (H2) via electron scavenging by H+. In solutions of cyanocuprates, methylviologen (MV2+) was added to scavenge the electron in a reaction resulting in a reducing intermediate MV.+. The formation of an oxidizing intermediate is demonstrated using NO3− and N2O as electron scavengers. Continuous photolysis of the complexes reveals the dependence of quantum yield on concentration of Cl− ligand in CuCl2−CuCl32− and Cu(CN)2−Cu(CN)2Cl2− systems, and the action spectra of Cu(CN)2− and Cu(CN)2Cl2− indicate an efficient excitation band at 265 nm for both complexes (the quantum yields are 0.37 and 0.21 respectively).

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