Syntheses, Crystal Structures, and Optical and Photocatalytic Properties of Four Small-Amine-Molecule-Directed M–Sn–Q (M = Zn, Ag; Q = S, Se) Compounds

• Published in: Crystal growth & design 2017-03, Vol.17 (3), p.1235-1244
• Main Authors: Zhang, Bo, Feng, Mei-Ling, Li, Jun, Hu, Qian-Qian, Qi, Xing-Hui, Huang, Xiao-Ying
• Format: Article
• Language: English
• ISSN: 1528-7483; 1528-7505
• DOI: 10.1021/acs.cgd.6b01619

By utilizing different small amine molecules as structure-affecting agents (SAAs) and charge-balancing agents (CBAs), four new M–Sn–Q (M = Zn, Ag; Q = S, Se) compounds with the anionic architectures ranging from a one-dimensional (1D) chain to a three-dimensional (3D) network have been solvothermally synthesized. Compound [(Me)2NH2]2­ZnSn3Se8 (1) features an anionic (4,4) layer of [ZnSn3Se8] n 2n– and represents a rare [ZnSn3Se10] T2 cluster-based two-dimensional Zn–Sn–Se compound directed by organic amine. Compound [NH4]3AgSn3Se8 (2) contains infinite linear anionic chains of [AgSn3Se8] n 3n–. Compound [CH3NH3]2­[H3O]­Ag5Sn4Se12­·C2H5OH (3) exhibits a 3D open-framework structure of [Ag5Sn4Se12] n 3n– with intersecting 3D channels. Compound [CH3NH3]6­Ag12Sn6S21 (4) features a 3D framework structure with 1D channels filled by [CH3NH3]+ cations. The most fascinating structural feature of compound 4 is that a complex 3D [Ag12S17] n 22n– anionic network exists based on the combination of three types of basic building blocks of [AgS2] dumbbells, [AgS3] triangles, and [AgS4] tetrahedra. The thermal stabilities, optical properties of the title compounds 1–4, as well as the theoretical band structure and density of states of compound 4 have been studied. Moreover, compound 3 displayed visible-light-driven photocatalytic activity for the degradation of crystal violet.