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A new highly stable copper(I)-based metal-organic framework (MOF), namely, [Cu(SiWO)(L)]·6HO·2DMF (1), was synthesized by incorporating Keggin-type polyoxometalate (POM) anions and a functionalized wheel-like resorcin[4]arene-based ligand (L) under sovothermal condition. 1 exhibits a charming 3D supramolecular architecture sandwiched by the POM anions. Noticeably, 1 has exceptional chemical stability, especially in organic solvents or aqueous solutions with a wide range of pH values. Considering the catalytically active Cu(I) sites in 1, the azide-alkyne cycloaddition (AAC) reaction was studied by employing 1 as the heterogeneous catalyst. Most strikingly, 1 exhibits excellent catalytic activity as well as recyclability for the AAC reaction.

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