Electrocatalytic Hydrogen Evolution Using Cyano-Substituted Triaryl Corrole Antimony(III) Complexes.

Abstract

Developing molecular electrocatalysts with controllable and predictable properties remains a central challenge in hydrogen evolution reaction (HER) catalysis. Herein, four Sb(III) corrole complexes (<b>1</b>-<b>4</b>) bearing zero to three <i>p</i>-cyano-substituted <i>meso</i>-phenyl groups (-CN Ph) were synthesized to investigate the effect of electron-withdrawing substituents on their catalytic HER performance, in which complexes <b>2</b>-<b>4</b> are newly reported. All prepared complexes were well characterized via UV-vis, NMR, HRMS, and XPS. SEM-EDS and UV-vis analyses indicated their uniform dispersion and excellent stability under organic and neutral aqueous solvent electrolysis conditions. When using TsOH as the proton source in DMF, complex <b>4</b> exhibited the highest activity with a TOF of 42.19 s^-1 at an overpotential of 895 mV. In mixed aqueous-organic media, the Faradaic efficiency of complex <b>4</b> reached 85.5%. The HER activity increases with the increasing number of cyano groups, and this observation has been rationalized via DFT calculations, which indicates a ligand-centered reduction and supports a possible ECEC pathway for the HER. These results highlight that cyano functionalization can modulate the electronic properties of Sb(III) corroles, thereby enhancing HER performance. This is helpful for designing efficient Sb(III) corrole-based HER catalysts.