Remarkable Enhancement of Catalytic Activity of Cu‐Complexes in the Electrochemical Hydrogen Evolution Reaction by Using Triply Fused Porphyrin**

Abstract

A bimetallic triply fused copper(II) porphyrin complex (1) was prepared, comprising two monomeric porphyrin units linked through β-β, meso-meso, β'-β' triple covalent linkages and exhibiting remarkable catalytic activity for the electrochemical hydrogen evolution reaction in comparison to the analogous monomeric copper(II) porphyrin complex (2). Electrochemical investigations in the presence of a proton source (trifluoroacetic acid) confirmed that the catalytic activity of the fused metalloporphyrin occurred at a significantly lower overpotential (≈320 mV) compared to the non-fused monomer. Controlled potential electrolysis combined with kinetic analysis of catalysts 1 and 2 confirmed production of hydrogen, with 96 and 71 % faradaic efficiencies and turnover numbers of 102 and 18, respectively, with an observed rate constant of around 10⁷ s^-1 for the dicopper complex. The results thus firmly establish triply fused porphyrin ligands as outstanding candidates for generating highly stable and efficient molecular electrocatalysts in combination with earth-abundant 3d transition metals.