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

Xin LiLijuan WangMengjiao ShaoXueling SongLei Wang
Published in: Dalton transactions (Cambridge, England : 2003) (2024)
Ten copper-bipyridine-type catalysts, [(bpyR)Cu(OH) 2 ] 2+ , featuring diverse counteranions (OAc - , Cl - , SO 4 2- , NO 3 - , 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 - > SO 4 2- > NO 3 - > 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.
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