A Unique Mixed-Valence CuII/CuI Organic–Inorganic Hybrid Supramolecular Cluster: Syntheses, Crystal Structure, Luminescence and 2,4,6-Trinitrophenol Sensing Properties

A unique mixed-valence CuII/CuI organic–inorganic hybrid supramolecular cluster {[Cu(DMSO)5][Cu4I6(DMSO)]}n (1) has been achieved in the presence of CuI under the acid condition, and characterized by X-ray single and powder crystal diffractions, elemental analysis, IR, UV–vis, thermogravimetric analysis. 1 has an unusual five DMSO coordinated bivalent copper cation [Cu(DMSO)5]2+; while the anionic architecture of 1 exhibits a 1-D wavelike CuI iodide hybrid cluster chain, constructed by [Cu4I6(DMSO)]2− repeated cluster units linking each other through shared μ2-I and μ3-I atoms. The solvent-coordinated cations interact with the 1-D anionic cluster chains to form a 3-D supramolecular framework through hydrogen bonds. Moreover, the luminescence and 2,4,6-trinitrophenol (TNP) sensing properties of 1 were explored in 2-propanol suspension, which revealed that 1 exhibits highly sensitive for TNP detection through energy transfer process.