Electrocatalytic water oxidation by an unsymmetrical dicopper complex with bridging imidazole-aldoxime ligands in neutral phosphate buffer

IF 3.3 3区化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR

Dalton Transactions Pub Date : 2025-09-26 DOI:10.1039/d5dt00962f

Swati Basak, Pranjal Das, Hemrupa Kuilya, Kripangkar Choudhury, Pradyumna Mazumdar, Diganta Choudhury, Apurba Kalita

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引用次数: 0

Abstract

Electrocatalytic water oxidation activity of an unsymmetrical dicopper complex, 1, [Cu₂(L₁H)(L₁)₂(OH₂)](ClO₄)₂, with a redox active imidazole-aldoxime ligand, L₁H, [L₁H = N-hydroxo(4-methyl-imidazol-5-yl)methanimine], has been investigated. Complex 1 exhibit turnover frequency of ∼302 s^-1 in neutral phosphate buffer at about 620 mV overpotential with ∼94% faradaic efficiency. Electrochemical analysis suggests that the ligand moiety participates in a proton-coupled electron transfer (PCET) step during the catalytic cycle, enabling the complex to accumulate high oxidizing equivalents at the reaction center. Additionally, the asymmetric bridging mode of the oxime ligands promote bimetallic cooperative catalysis in complex 1.

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中性磷酸盐缓冲液中咪唑-醛肟配体的不对称双铜络合物电催化水氧化

研究了不对称二铜配合物1，[Cu2(L1H)(L1)2(OH2)](ClO4)2与氧化还原活性咪唑-醛肟配体L1H， [L1H = n -羟基（4-甲基咪唑-5-酰基）甲亚胺]的电催化水氧化活性。配合物1在中性磷酸盐缓冲液中，过电位约为620 mV，法拉第效率约为94%，周转频率为~ 302 s-1。电化学分析表明，在催化循环中，配体部分参与了质子耦合电子转移（PCET）步骤，使配合物在反应中心积累了高氧化当量。此外，肟配体的不对称桥接模式促进了配合物1中的双金属协同催化。

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来源期刊

Dalton Transactions 化学-无机化学与核化学

CiteScore

6.60

自引率

7.50%

发文量

1832

审稿时长

1.5 months

期刊介绍： Dalton Transactions is a journal for all areas of inorganic chemistry, which encompasses the organometallic, bioinorganic and materials chemistry of the elements, with applications including synthesis, catalysis, energy conversion/storage, electrical devices and medicine. Dalton Transactions welcomes high-quality, original submissions in all of these areas and more, where the advancement of knowledge in inorganic chemistry is significant.