Geminate-pair scavenging mechanism in photochemical reactions of chlorocuprate(II) complexes in acetonitrile solutions containing alcohols

Abstract

The quantum yield of the photoinduced redox reaction of chlorocuprate(II) complexes in acetonitrile solutions can be enhanced by addition of aliphatic alcohols as scavengers for the chlorine atom or Cl 2 − ion radical. The quantum yield Φ Cu I shows a linear dependence on the square root of alcohol (scavenger) concentration C S within the range where the scavenging reaction competes with the secondary recombination. Thus, for these systems the validity of the Noyes geminate-pair scavenging mechanism is justified. The scavenging rate constants were estimated, and they depend on the carbon number of the alcohols applied.