Discrete Supertetrahedral T3 InQ Clusters (Q = S, S/Se, Se, Se/Te): Ionothermal Syntheses and Tunable Optical and Photodegradation Properties

Abstract

Presented are the ionothermal syntheses, characterizations and photodegradation properties of four isostructural chalcogenidometalate compounds, namely [Bmmim]5[In10Q16Cl3(Bim)] (Q = S (IL-InS-1), S7.12Se8.88 (IL-InSSe-2), Se (IL-InSe-3), Se13.80Te2.20 (IL-InSeTe-4); Bmmim = 1-butyl-2,3-dimethylimidazolium, Bim = 1-butyl-2-methylimidazole). According to the single-crystal X-ray diffraction analysis, the title compounds belong to the C2/c space group and feature isolated supertetrahedral T3 anionic units of [In10Q16Cl3(Bim)]5– stabilized by [Bmmim]+ cations. The ionic liquid not only provided the [Bmmim]+ as the counter ions but also acted as the reactive solvent releasing [Bim] ligands that are covalently bonded to In atoms. Unlike the widely-reported extended frameworks that contain T3 InS/Se as building units, IL-InSe-3 represents the first example of discrete T3 InSe clusters, and InTe-based discrete T3 cluster (IL-InSeTe-4) was characterized for the first time. The optical absorption edges of the titl...