Primary processes in photophysics and photochemistry of a potential light-activated anti-cancer dirhodium complex

Photophysics and photochemistry of a potential light-activated cytotoxic dirhodium complex [Rh₂(µ-O₂CCH₃)₂(bpy)(dppz)](O₂CCH₃)₂, where bpy = 2,2'-bipyridine, dppz = dipyrido[3,2-a:2',3'-c]phenazine (Complex 1 or Rh2) in aqueous solutions was studied by means of stationary photolysis and time-resolved methods in time range from hundreds of femtoseconds to microseconds. According to the literature, Complex 1 demonstrates both oxygen-dependent (due to singlet oxygen formation) and oxygen-independent cytotoxicity. Photoexchange of an acetate ligand to a water molecule was the only observed photochemical reaction, which rate was increased by oxygen removal from solutions. Photoexcitation of Complex 1 results in the formation of the lowest triplet electronic excited state, which lifetime is less than 10 ns. This time is too short for diffusion-controlled quenching of the triplet state by dissolved oxygen resulting in ¹O₂ formation. We proposed that singlet oxygen is produced by photoexcitation of weakly bound van der Waals complexes [Rh2…O₂], which are formed in solutions. If this is true, no oxygen-independent light-induced cytotoxicity of Complex 1 exists. Residual cytotoxicity deaerated solutions are caused by the remaining [Rh2…O₂] complexes.