Fan Xin-Xin, Yang Mei, Yao Wen-Dong, Zhou Wenfeng, Jiang Tengfei, Liu Wenlong, Guo Sheng-Ping
School of Chemistry and Chemical Engineering, Yangzhou University, Yangzhou 225002, P. R. China.
Inorg Chem. 2024 Apr 29;63(17):7549-7554. doi: 10.1021/acs.inorgchem.3c04336. Epub 2024 Apr 12.
Oxychalcogenides are increasingly attracting wide attention because they contain multiple anions that may combine the advantages of oxides and chalcogenides. In this work, two new pentanary oxythiogermanates, BaMGeOS [M = Ca (), Zn ()], were synthesized by a high-temperature solid-state reaction. They crystallize in the orthorhombic space group , and their structures contain isolated [GeOS] units constructed by one [GeOS] and two [GeOS] tetrahedra that link with M ions to build the {[MGeOS]} chain, representing a new type of oxythiogermanate. Notably, a [ZnS] square pyramid exists in . Their structural chemistry and relationship with relevant structures are analyzed. and exhibit wide band gaps of 3.93 and 2.63 eV, birefringences of 0.100 and 0.089 at 2100 nm, respectively, and also obvious photocurrent responses. This work may be extended to a family of AEMMOQ (AE = alkali-earth metal; M = Ca, Zn, Cd, Hg; M = Si, Ge, Sn; Q = S, Se), and further systematic survey on them can be performed to enrich the study of multifunctional oxychalcogenides.
氧硫族化合物因其包含多种阴离子而越来越受到广泛关注，这些阴离子可能兼具氧化物和硫族化合物的优点。在本工作中，通过高温固态反应合成了两种新型五元氧硫代锗酸盐BaMGeOS [M = Ca (), Zn ()]。它们结晶于正交空间群，其结构包含由一个[GeOS]和两个[GeOS]四面体构建的孤立[GeOS]单元，这些单元与M离子相连形成{[MGeOS]}链，代表了一种新型的氧硫代锗酸盐。值得注意的是， 中存在一个[ZnS]四方锥。分析了它们的结构化学及其与相关结构的关系。 和 在2100 nm处分别表现出3.93和2.63 eV的宽带隙、0.100和0.089的双折射，并且还具有明显的光电流响应。这项工作可能扩展到AEMMOQ族（AE = 碱土金属；M = Ca、Zn、Cd、Hg；M = Si、Ge、Sn；Q = S、Se），并且可以对它们进行进一步的系统研究以丰富多功能氧硫族化合物的研究。
