Shi Yong-Fang, Li Xiao-Fang, Zhang Yu-Xiao, Lin Hua, Ma Zuju, Wu Li-Ming, Wu Xin-Tao, Zhu Qi-Long
State Key Laboratory of Structural Chemistry , Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences , Fuzhou 350002 , China.
University of Chinese Academy of Sciences , Beijing 100049 , China.
Inorg Chem. 2019 May 20;58(10):6588-6592. doi: 10.1021/acs.inorgchem.9b00653. Epub 2019 May 10.
Mixed-anion compounds play an essential part in modern structural chemistry. In this Communication, an unprecedented hexanary oxysulfide, [(BaCl)(GaSiOS)] (FJ-1), was synthesized at 1073 K by a standard solid-state method, which is a new phase in the AE/M/M/O/Q/X (AE = alkaline-earth metal; M = group 13 metal; M = group 14 metal; Q = chalcogen; X = halogen) system. FJ-1 adopts a new structure type and crystallizes in the orthorhombic system with space group Cmcm. In the structure, unique two-dimensional [GaSiOS] layers formed by the familiar [SiO] species and unusual heteroligand [GaOS] and [GaOS] tetrahedra extend the intralayer linking. Significantly, a photoelectrochemical test revealed that FJ-1 is photoresponsive under ultraviolet illumination. Moreover, density functional theory calculations were employed to gain insight into the relationship between the electronic structure and optical properties. Such work will be conducive to the structural diversity of gallium coordination chemistry by exploration of the new mixed-anion functional chalcohalides.
混合阴离子化合物在现代结构化学中起着至关重要的作用。在本通讯中，通过标准固态方法在1073 K下合成了一种前所未有的六元氧硫化物[(BaCl)(GaSiOS)]（FJ - 1），它是AE/M/M/O/Q/X（AE = 碱土金属；M = 第13族金属；M = 第14族金属；Q = 硫族元素；X = 卤素）体系中的一个新相。FJ - 1采用一种新的结构类型，结晶于正交晶系，空间群为Cmcm。在该结构中，由常见的[SiO]物种以及不寻常的杂配体[GaOS]和[GaOS]四面体形成的独特二维[GaSiOS]层扩展了层内连接。值得注意的是，光电化学测试表明FJ - 1在紫外光照下具有光响应性。此外，采用密度泛函理论计算来深入了解电子结构与光学性质之间的关系。通过探索新型混合阴离子功能硫卤化物，此类工作将有助于镓配位化学的结构多样性。
