title: Self-Assembled Amphiphilic Water Oxidation Catalysts: Control of O-O Bond Formation Pathways by Different Aggregation Patterns.
abstract: The oxidation of water to molecular oxygen is the key step to realize water splitting from both biological and chemical perspective. In an effort to understand how water oxidation occurs on a molecular level, a large number of molecular catalysts have been synthesized to find an easy access to higher oxidation states as well as their capacity to make O-O bond. However, most of them function in a mixture of organic solvent and water and the O-O bond formation pathway is still a subject of intense debate. Herein, we design the first amphiphilic Ru-bda (H2 bda=2,2'-bipyridine-6,6'-dicarboxylic acid) water oxidation catalysts (WOCs) of formula [Ru(II) (bda)(4-OTEG-pyridine)2 ] (1, OTEG=OCH2 CH2 OCH2 CH2 OCH3 ) and [Ru(II) (bda)(PySO3 Na)2 ] (2, PySO3 (-) =pyridine-3-sulfonate), which possess good solubility in water. Dynamic light scattering (DLS), scanning electron microscope (SEM), critical aggregation concentration (CAC) experiments and product analysis demonstrate that they enable to self-assemble in water and form the O-O bond through different routes even though they have the same bda(2-) backbone. This work illustrates for the first time that the O-O bond formation pathway can be regulated by the interaction of ancillary ligands at supramolecular level.
authors.affiliation: Key Laboratory of Photochemical Conversion and Optoelectronic Materials, Technical Institute of Physics and Chemistry & University of Chinese Academy of Sciences, Chinese Academy of Sciences, Beijing, 100190, P.R. China.
authors.forename: Bing
authors.initials: B
authors.lastname: Yang
authors.affiliation: Key Laboratory of Photochemical Conversion and Optoelectronic Materials, Technical Institute of Physics and Chemistry & University of Chinese Academy of Sciences, Chinese Academy of Sciences, Beijing, 100190, P.R. China.
authors.forename: Xin
authors.initials: X
authors.lastname: Jiang
authors.affiliation: Key Laboratory of Photochemical Conversion and Optoelectronic Materials, Technical Institute of Physics and Chemistry & University of Chinese Academy of Sciences, Chinese Academy of Sciences, Beijing, 100190, P.R. China.
authors.forename: Qing
authors.initials: Q
authors.lastname: Guo
authors.affiliation: Key Laboratory of Photochemical Conversion and Optoelectronic Materials, Technical Institute of Physics and Chemistry & University of Chinese Academy of Sciences, Chinese Academy of Sciences, Beijing, 100190, P.R. China.
authors.forename: Tao
authors.initials: T
authors.lastname: Lei
authors.affiliation: Key Laboratory of Photochemical Conversion and Optoelectronic Materials, Technical Institute of Physics and Chemistry & University of Chinese Academy of Sciences, Chinese Academy of Sciences, Beijing, 100190, P.R. China.
authors.forename: Li-Ping
authors.initials: LP
authors.lastname: Zhang
authors.affiliation: Key Laboratory of Photochemical Conversion and Optoelectronic Materials, Technical Institute of Physics and Chemistry & University of Chinese Academy of Sciences, Chinese Academy of Sciences, Beijing, 100190, P.R. China.
authors.forename: Bin
authors.initials: B
authors.lastname: Chen
authors.affiliation: Key Laboratory of Photochemical Conversion and Optoelectronic Materials, Technical Institute of Physics and Chemistry & University of Chinese Academy of Sciences, Chinese Academy of Sciences, Beijing, 100190, P.R. China.
authors.forename: Chen-Ho
authors.initials: CH
authors.lastname: Tung
authors.affiliation: Key Laboratory of Photochemical Conversion and Optoelectronic Materials, Technical Institute of Physics and Chemistry & University of Chinese Academy of Sciences, Chinese Academy of Sciences, Beijing, 100190, P.R. China. lzwu@mail.ipc.ac.cn.
authors.forename: Li-Zhu
authors.initials: LZ
authors.lastname: Wu
keywords: amphiphilic complexes; catalysis; ruthenium complex; self-assembly; water oxidation