Largest discrete supertetrahedral clusters synthesized in ionic liquids

Four discrete T5 cluster compounds with Cu-M-S constituents (M = In for compound 1, Ga for 2-4) have been synthesized in an ionic liquid (IL) [Bmmim]Cl (Bmmim = 1-butyl-2,3-dimethyl-imidazolium), which represent the largest molecular clusters in a Tn series. The in situ decomposition of the IL generates the Bim ligand (Bim 1-butyl-2-methyl-imidazole) that directly coordinates to some of the corner Ga3+ ions of the T5 clusters in 3-4, leading to the formation of the first inorganic-organic hybrid T5 clusters. 2-4 show significantly broad photoluminescent emission bands ranging from 500 to 800 nm with a full width at half maximum (fwhm) at about 180 nm. This research provides a new method for synthesizing molecular metal chalcogenides that uses ILs as a reactive solvent and stabilizer.