title: Water oxidation catalyzed by a charge-neutral mononuclear ruthenium(iii) complex.
abstract: A new charge-neutral Ru(iii) complex RuL(pic)3(1) (H3L = 3,6-di-tert-butyl-9H-carbazole-1,8-dicarboxylic acid, pic = 4-picoline) was synthesized and fully characterized. This complex promoted chemical and photochemical water oxidation efficiently with turnover frequencies of 0.28 s-1and 5 min-1, respectively. In particular, for photochemical water oxidation, complex 1 showed excellent stability and good activity. The X-ray crystal structure, electrochemical results, and the detection of the RuIV-OH intermediate by high-resolution mass spectrometry revealed that complex 1 exchanged its 4-picoline ligand with water at the RuIIIstate to form the authentic water oxidation catalyst. The kinetics studies suggested a reaction mechanism involving nucleophilic attack by a water molecule.
authors.affiliation: State Key Laboratory of Fine Chemicals, Institute of Artificial Photosynthesis, DUT-KTH Joint Education and Research Center on Molecular Devices, Dalian University of Technology (DUT), Dalian 116024, China. dr.gaoyan@dlut.edu.cn.
authors.forename: Zhongkai
authors.initials: Z
authors.lastname: Lu
authors.affiliation: State Key Laboratory of Fine Chemicals, Institute of Artificial Photosynthesis, DUT-KTH Joint Education and Research Center on Molecular Devices, Dalian University of Technology (DUT), Dalian 116024, China. dr.gaoyan@dlut.edu.cn.
authors.forename: Yan
authors.identifier: http://orcid.org/0000-0001-9895-4088
authors.initials: Y
authors.lastname: Gao
authors.affiliation: State Key Laboratory of Fine Chemicals, Institute of Artificial Photosynthesis, DUT-KTH Joint Education and Research Center on Molecular Devices, Dalian University of Technology (DUT), Dalian 116024, China. dr.gaoyan@dlut.edu.cn.
authors.forename: Hu
authors.initials: H
authors.lastname: Chen
authors.affiliation: State Key Laboratory of Fine Chemicals, Institute of Artificial Photosynthesis, DUT-KTH Joint Education and Research Center on Molecular Devices, Dalian University of Technology (DUT), Dalian 116024, China. dr.gaoyan@dlut.edu.cn.
authors.forename: Zhao
authors.initials: Z
authors.lastname: Liu
authors.affiliation: State Key Laboratory of Fine Chemicals, Institute of Artificial Photosynthesis, DUT-KTH Joint Education and Research Center on Molecular Devices, Dalian University of Technology (DUT), Dalian 116024, China. dr.gaoyan@dlut.edu.cn and Department of Chemistry, School of Chemical Science and Engineering, KTH Royal Institute of Technology, 100 44 Stockholm, Sweden.
authors.forename: Licheng
authors.initials: L
authors.lastname: Sun