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 liga

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.