Evidence for metal to solvent charge transfer photooxidation of iron, cobalt, nickel and copper dithiocarbamato derivatives in poly(vinylchloride) matrices at ca. 90 K: New insights into the bonding of late transition metals with dithiocarbamate ligands through DFT modeling

Photolysis of FeL₃, CoL₃, NiL₂, CuL₂ and ZnL₂, where L = S₂CNEt₂, in PVC matrices at ca. 90 K results in photooxidation of the metal complexes through irreversible metal to solvent charge transfer. DFT quantum mechanical studies of the S₂CNMe₂ anion and the Ni, Cu and Zn derivatives were carried out, providing a more nuanced understanding of the bonding of the dithiocarbamate ligand than suggested by classical resonance arguments.