Strong Proton‐Electron Coupling in π‐Planar Metal Complex with Redox‐Active Ligands

Abstract

Proton-coupled electron transfer (PCET) of metal complexes has been widely studied, especially in biochemistry and catalytic chemistry. Although metal complexes bearing redox-active ligands play a part in these research areas, those with π-planar structure remain entirely unexplored, which are vital for future development of iono-electronics. Here, proton-electron coupling of a π-planar nickel complex bearing redox-active N, S-ligands, Ni(itsq)2, was investigated by combining experimental and theoretical approaches. Strong proton-electron coupling was manifested in a large potential shift, which is twice greater than that of a typical PCET-type π-planar metal complex with redox-inactive ligands, [Ni(dcpdt)₂]²⁻. Theoretical calculations affirmed that the stabilization of frontier orbitals by protonation is greater in Ni(itsq)2 than that in [Ni(dcpdt)₂]²⁻. These results indicate that π-planar metal complexes with redox-active ligands are promising for developing novel PCET-type materials.