Solvent Effects on Nonradiative Relaxation Dynamics of Low-Energy Ligand-Field Excited States: A CuCl42- Complex

Abstract

Nonradiative relaxation dynamics of CuCl₄^2- complexes photoexcited into the highest-energy ligand-field electronic state (²A₁) is studied in acetonitrile, dichloromethane, and chloroform solvents, as well as in acetonitrile-water and in acetonitrile-deuterated water mixtures. Due to ultrafast internal conversion, this excited state directly converts to the electronic ground state in dichloromethane and chloroform. The nonradiative relaxation constant is similar in anhydrous acetonitrile. Addition of water to acetonitrile solutions efficiently quenches the excited ligand-field ²A₁ state. The quenching is proposed to be due to the diffusion-controlled formation of an electronically excited pentacoordinated [CuCl₄H₂O]^2- encounter complex or a short-lived exciplex of similar structure, in which the electronic excitation energy transfers into the O-H stretch of the coordinated H₂O molecule. This is followed by the dissociation of the pentacoordinated species, resulting in the reformation of the ground-state CuCl₄^2- and free H₂O molecules.