For post-transition metal electrocatalytic H2 evolution reaction (HER), the new porphycene antimony complexes, Sb(III) octaethyl porphycene (OEPo) and Sb(V)OEPo-Br2, were prepared and evaluated. Electrochemical and electro-spectro measurements revealed that the two-step one-electron reduction processes of Sb(III)OEPo were indicated to be both ligand-centered and the irreversible reduction process observed for Sb(V)OEPo-Br2 was assigned to be the reduction from Sb(V)OEPo-Br2 to Sb(III)OEPo. Electrocatalytic HER happened at -1.0 V (vs. Ag/AgCl) under acidic conditions via the ligand-centered reductions. The electron accepting nature of the porphycene ligand enabled the utilization of a main-group element as a central element for the ligand-centered HER at anodically shifted potentials.
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