Structural modification of nickel tetra(thiocyano)corroles during electrochemical water oxidation

Abstract

In this study, we present two fully characterized nickel tetrathiocyanocorroles, representing a novel class of 3d-metallocorroles. These nickel(II) ions form square planar complexes, exhibiting a d⁸-electronic configuration. These anionic complexes are stabilized by the electron-withdrawing SCN groups on the bipyrrole unit of the corrole. The reduced aromaticity in these anionic nickel(II) corrole complexes is evidenced by single crystal X-ray diffraction (XRD) data and a markedly altered absorption profile, with stronger Q bands compared to Soret bands. Notably, the UV-Vis and electrochemical data exhibit significant differences from previously reported nickel(II) corrole radical cation and nickel(II) porphyrin complexes. While these electrochemical data bear a resemblance to those of the anionic nickel(II) corrole by Gross et al., the UV-Vis data show substantial distinctions. Additionally, we explore the utilization of nickel(II)-corrole@CC (where CC denotes carbon cloth) as an electrocatalyst for the oxygen evolution reaction (OER) in an alkaline medium. During electrochemical water oxidation, the molecular catalyst is partially converted to nickel (oxy)hydroxide, Ni(O)OH. The structure reveals the coexistence of the molecular complex and Ni(O)OH in the active catalyst, achieving a turnover frequency (TOF) of 3.32 × 10⁻² s⁻¹. The synergy between the homogeneous and heterogeneous phases improves the OER activity, providing more active sites and edge sites and enhancing interfacial charge transfer.