Cyclic voltammetry and spectroelectrochemistry of rhodium phthalocyanines

Abstract

The electrochemistry of Rh^III(pc)(pc = phthalocyanine dianion) complexes containing chloride, pyridine, dimethyl sulfoxide (dmso) and cyanide as axial ligands was investigated by cyclic voltammetry and UV/VIS spectroelectrochemistry. The compounds were K[Rh(pc)(CN)₂], [Rh(pc)(Cl)(py)] and [Rh(pc)Cl(dmso)]. For all of these the first oxidation occurs at the phthalocyanine ligand with the formation of a π-cation radical species. The addition of one electron to the complexes leads to one of two different reduction products depending on the nature of the axial ligands. The first reduction of [Rh(pc)Cl(py)] and [Rh(pc)Cl(dmso)] occurs at the metal, followed by rapid dimerization of the reduced species. The first and subsequent reductions of K[Rh(pc)(CN)₂] occur at the ring.