Non-coordinating counteranion as a powerful tool to tune the activity of copper water oxidation catalysts.

ABSTRACT

Ten copper-bipyridine-type catalysts, [(bpyR)Cu(OH)2]2+, featuring diverse counteranions (OAc-, Cl-, SO42-, NO3-, OTf-) were synthesized. The observed substantial variations in turnover frequency (TOF) among these catalysts, coupled with insights gained from electrochemical investigations, underscore the pivotal influence of counteranions in fine-tuning the catalytic activity of metal complexes during water oxidation. The TOF value follows the trend of OAc- > Cl- > SO42- > NO3- > OTf-, which is the same as the change of coordinating ability index, a™. Density Functional Theory (DFT) calculations reveal that counteranion coordination plays an important role in influencing the catalytic performance of these complexes.