Dangling Ligand Enables an Iron Hexa-Coordinated Molecular Catalyst for Water Oxidation by Photocatalysis  

作　　者：Bing Yang Qi Liu Xiang-Zhu Wei Tao Lei Qing-Qing Yang Xu-Zhe Wang Jing-Xin Jian Xin Jiang Chen-Ho Tung Li-Zhu Wu 

机构地区：[1]Key Laboratory of Photochemical Conversion and Optoelectronic Materials,New Cornerstone Science Laboratory,Technical Institute of Physics and Chemistry,Chinese Academy of Sciences,Beijing 100190 [2]School of Future Technology,University of Chinese Academy of Sciences,Beijing 100049

出　　处：《CCS Chemistry》2024年第3期623-630,共8页中国化学会会刊（英文）

基　　金：support from the National Key Research and Development Program of China(grant nos.2022YFA1502900,2022YFA0911900,2021YFA1500800,and 2022YFB3803600);the National Natural Science Foundation of China(grant nos.20231001,22201288,21933007,22193013,and 22088102);the Strategic Priority Research Program of the Chinese Academy of Science(grant no.XDB17000000);the New Cornerstone Science Foundation.

摘　　要：Photocatalytic water oxidation reaction by transition metal complexes remains a challenge because of their poor stability under irradiation,especially for earth-abundant metal catalysts.In this regard,ironbased water oxidation catalysts are prone to hydrolysis and/or dissociate the ligands to form nanoparticles under a real catalytic condition.Herein,we describe a unique hexa-coordinated catalyst 1[Fe^(II)(Py_(3)tacn)Cl_(2)]and its reference 2[Fe^(II)(PhPy_(2)tacn)Cl_(2)]with a dangling pyridyl ligand and a phenyl group,respectively.We anticipated that the dynamically open and close coordination behaviors of the pyridyl ligand enabled balance of the reactivity and stability of catalyst 1.To our delight,the“open form”of catalyst 1 provided a free coordination site,and the“close form”guaranteed its molecular integrity,resulting in a water oxidation reaction with high efficiency and robustness.The turnover number and turnover frequency values of 2332 and 60 s^(−1)are the highest known to date among iron-based homogeneous water oxidation systems under visible light irradiation.

关 键 词：water oxidation PHOTOCATALYSIS homogeneous catalysis iron complexes dangling ligand intermediates characterization 

分 类 号：O64[理学—物理化学]