Buffer anion effects on water oxidation catalysis: The case of Cu(III) complex

Water oxidation is the bottleneck of artificial photosynthesis. Since first ruthenium-based molecular water catalyst, blue dimer, was reported by Meyer's group in 1982, catalysts based on transition metals have been widely employed to explore mechanism oxidation. Because requires harsh oxidative conditions, stability complexes under relevant catalytic conditions has always a challenge. In this work, we report redox properties Cu III complex (TAML-Cu ) with redox-active macrocyclic ligand (TAML) and its reactivity toward TAML-Cu displayed completely different electrochemical behavior from that TAML-Co previously our group. can only be oxidized one-electron form TAML •+ -Cu cannot achieve activation through ligand-centered proton-coupled electron transfer takes place case . The generated intermediate undergo further hydrolysis assistance borate anions, triggering formation heterogeneous B/CuO x nanocatalyst. Therefore, choice buffer solution significant influence catalysts. effect anions performance catalyst investigated. showed activity for buffer, where it triggered active species, , open-ring reaction.