The electrochemical properties of β-octaethylporphycene iridium complex (Ir-OEPo) were determined. Based on the electro-spectro measurement results, the reduction of Ir-OEPo did not occur at the central metal but at the ligand, while the reduction of β-octaethylporphyrin iridium complex (Ir-OEPor) occurred at the central iridium. A catalytic current was observed during the cyclic voltammetry (CV) measurements with trifluoroacetic acid (TFA) under a reductive condition, indicating the catalytic reactivity of Ir-OEPo for the hydrogen evolution reaction (HER). By constant potential electrolysis, hydrogen gas was detected by gas chromatography (GC) and the catalytic reactivity of Ir-OEPo was confirmed. The HER mechanism via ligand reduction of macrocyclic aromatic complexes could be one of the concepts for the development of new catalysts.
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