Lu Zhongkai, Gao Yan, Chen Hu, Liu Zhao, Sun Licheng
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.
Dalton Trans. 2017 Jan 24;46(4):1304-1310. doi: 10.1039/c6dt04160d.
A new charge-neutral Ru(iii) complex RuL(pic) (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 and 5 min, 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 Ru-OH intermediate by high-resolution mass spectrometry revealed that complex 1 exchanged its 4-picoline ligand with water at the Ru state to form the authentic water oxidation catalyst. The kinetics studies suggested a reaction mechanism involving nucleophilic attack by a water molecule.
