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 

作者机构：Key Laboratory of Photochemical Conversion and Optoelectronic MaterialsNew Cornerstone Science LaboratoryTechnical Institute of Physics and ChemistryChinese Academy of SciencesBeijing 100190 School of Future TechnologyUniversity of Chinese Academy of SciencesBeijing 100049 

出 版 物：《CCS Chemistry》 (中国化学会会刊（英文）)

年 卷 期：2024年第6卷第3期

页      面：623-630页

核心收录：

学科分类：081704[工学-应用化学] 07[理学] 070304[理学-物理化学(含∶化学物理)] 08[工学] 0817[工学-化学工程与技术] 0703[理学-化学] 

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 

主　　题：water oxidation photocatalysis homogeneous catalysis iron complexes dangling ligand intermediates characterization 

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 *** this regard,ironbased water oxidation catalysts are prone to hydrolysis and/or dissociate the ligands to form nanoparticles under a real catalytic ***,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,*** anticipated that the dynamically open and close coordination behaviors of the pyridyl ligand enabled balance of the reactivity and stability of catalyst *** our delight,the“open formof catalyst 1 provided a free coordination site,and the“close formguaranteed its molecular integrity,resulting in a water oxidation reaction with high efficiency and *** 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.