Metal-to-ligand charge transfer photochemistry: potential energy curves for the homolysis of the model system HMn(CO3)(α-diimine)
Abstract
The presence of a reactive 3LLCT (σ→π*) excited state interacting with the low-lying metal-to-ligand charge transfer (MLCT) states and leading to the primary products H + Mn(CO)3(α-diimine) in their ground state is responsible for the formation of the radical species in this family of molecules; the quantum yield and the time-scale of the homolysis will depend on factors capable of modifying the barrier energy height, namely the nature of the radical species to be produced, the metal centre, the π-acceptor ligand and the experimental conditions.