Photochemical reactivity of the cluster tetradecachlorohexamolybdate(2-): photosubstitution and photoredox processes

Photoreversible ligand substitution and ligand oxidation reactions have been observed in UV photolyses of Mo 6 Cl 14 2− in acetonitrile. The photosubstitution of the ligand detected in λ excit >300 nm takes place in competition with population of the low-lying states associated with Mo 6 Cl 14 2− phosphorescence and leads to the formation of intermediates that can be scavenged by excess cluster, Br − , or I − . The photoredox reaction, investigated by continuous and flash photolyses, has been detected for irradiation at wavelengths of the high energy charge transfer bands, λ excit <300 nm