Fan Xi, Wang Junhui, Wu Kaifeng, Zhang Lei, Zhang Jian
State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, 350002, Fuzhou, P. R. China.
State Key Laboratory of Molecular Reaction Dynamics, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, 116023, Dalian, P. R. China.
Angew Chem Int Ed Engl. 2019 Jan 28;58(5):1320-1323. doi: 10.1002/anie.201809961. Epub 2018 Dec 20.
Phase isomerism is a common and important phenomenon in inorganic materials, but the molecular isomerism of their nanocluster models is still rare. In this work, we report the first pair of isomeric titanium-oxo clusters. Through combining pentagonal {Ti(Ti )} building units in corner-sharing or edge-sharing forms, the two obtained Ti -oxo clusters take vertical and horizontal core configurations, respectively, which are both functionalized by the same organic ligands. More interestingly, the vertical type Ti -oxo core contains an identical {Ti O } moiety as anatase, making it the first molecular model of anatase TiO . As a result, the vertical type cluster exhibits better photocatalytic H evolution activity, higher photocurrent response and faster charge transfer to external acceptors than its horizontal isomer. Thus, this work provides a cluster isomer method to understand the structure-property relationship of import titanium oxide materials.
相异构现象在无机材料中是一种常见且重要的现象，但其纳米团簇模型的分子异构现象仍然罕见。在这项工作中，我们报道了第一对异构的钛氧簇。通过以角共享或边共享的形式组合五角形{Ti(Ti)}构建单元，得到的两个钛氧簇分别具有垂直和水平的核心构型，它们都由相同的有机配体官能化。更有趣的是，垂直型钛氧核心包含与锐钛矿相同的{TiO}部分，使其成为锐钛矿TiO的第一个分子模型。结果，垂直型簇比其水平异构体表现出更好的光催化析氢活性、更高的光电流响应以及更快的电荷转移到外部受体。因此，这项工作提供了一种簇异构方法来理解重要的钛氧化物材料的结构-性能关系。
