Self-Assembled Amphiphilic Water Oxidation Catalysts: Control of O−O Bond Formation Pathways by Different Aggregation Patterns

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• 作者：Bing Yang ; Xin Jiang ; Qing Guo ; Tao Lei ; Prof. Dr. Li-Ping Zhang ; Dr. Bin Chen ; Prof. Dr. Chen-Ho Tung and Prof. Dr. Li-Zhu Wu
• 刊名：Angewandte Chemie International Edition
• 出版年：2016
• 出版时间：May 17, 2016
• 年：2016
• 卷：55
• 期：21
• 页码：6229-6234
• 全文大小：1200K
• ISSN：1521-3773

文摘

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 (H₂bda=2,2′-bipyridine-6,6′-dicarboxylic acid) water oxidation catalysts (WOCs) of formula [Ru^II(bda)(4-OTEG-pyridine)₂] (1, OTEG=OCH₂CH₂OCH₂CH₂OCH₃) and [Ru^II(bda)(PySO₃Na)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 bda²⁻ 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.