Amphiphilic Oxo-Bridged Ruthenium “Green Dimer” for Water Oxidation
Qing-Qing Yang,
Xin Jiang,
Bing Yang,
Yang Wang,
Chen-Ho Tung,
Li-Zhu Wu
Affiliations
Qing-Qing Yang
Key Laboratory of Photochemical Conversion and Optoelectronic Materials, Technical Institute of Physics and Chemistry, The Chinese Academy of Sciences, Beijing 100190, P. R. China; School of Future Technology, University of Chinese Academy of Sciences, Beijing 100190, P. R. China
Xin Jiang
Key Laboratory of Photochemical Conversion and Optoelectronic Materials, Technical Institute of Physics and Chemistry, The Chinese Academy of Sciences, Beijing 100190, P. R. China; School of Future Technology, University of Chinese Academy of Sciences, Beijing 100190, P. R. China
Bing Yang
Key Laboratory of Photochemical Conversion and Optoelectronic Materials, Technical Institute of Physics and Chemistry, The Chinese Academy of Sciences, Beijing 100190, P. R. China; School of Future Technology, University of Chinese Academy of Sciences, Beijing 100190, P. R. China
Yang Wang
Key Laboratory of Photochemical Conversion and Optoelectronic Materials, Technical Institute of Physics and Chemistry, The Chinese Academy of Sciences, Beijing 100190, P. R. China; School of Future Technology, University of Chinese Academy of Sciences, Beijing 100190, P. R. China
Chen-Ho Tung
Key Laboratory of Photochemical Conversion and Optoelectronic Materials, Technical Institute of Physics and Chemistry, The Chinese Academy of Sciences, Beijing 100190, P. R. China; School of Future Technology, University of Chinese Academy of Sciences, Beijing 100190, P. R. China
Li-Zhu Wu
Key Laboratory of Photochemical Conversion and Optoelectronic Materials, Technical Institute of Physics and Chemistry, The Chinese Academy of Sciences, Beijing 100190, P. R. China; School of Future Technology, University of Chinese Academy of Sciences, Beijing 100190, P. R. China; Corresponding author
Summary: In 1982, an oxo-bridged dinuclear ruthenium(III) complex, known as “blue dimer,” was discovered to be active for water oxidation. In this work, a new amphiphilic ruthenium “green dimer” 2, obtained from an amphiphilic mononuclear Ru(bda) (N-OTEG) (L1) (1; N-OTEG = 4-(2-(2-(2-methoxyethoxy)ethoxy)ethoxy)-pyridine; L1 = vinylpyridine) is reported. An array of mechanistic studies identifies “green dimer” 2 as a mixed valence of RuII-O-RuIII oxo-bridged structure. Bearing the same bda2- and amphiphilic axial ligands, monomer 1 and green dimer 2 can be reversibly converted by ascorbic acid and oxygen, respectively, in aqueous solution. More importantly, the oxo-bridged “green dimer” 2 was found to take water nucleophilic attack for oxygen evolution, in contrast to monomer 1 via radical coupling pathway for O-O bond formation. This is the first report of an amphiphilic oxo-bridged catalyst, which possesses a new oxygen evolution pathway of Ru-bda catalysts. : Inorganic Chemistry; Catalysis; Materials Chemistry Subject Areas: Inorganic Chemistry, Catalysis, Materials Chemistry
