In situ solvothermal syntheses of a heteronuclear copper(I)-alkaline metallic tetrazole-based coordination polymer

Three novel heteronuclear coordination complexes, namely, [Cu2K(Mtta)I-2] (1), [Cu3K(Mtta)(3)I] (2) and [Cu2Na(Mtta)(2)(CH3CN)I] (3) (HMtta = 5-methyl-1H-tetrazole) have been solvothermal synthesized by CuI, MCl [M = K (1) and (2); M = Na (3)], sodium azide and acetonitrile generated via a [3 + 2] cycloaddition reaction of acetonitrile and sodium azide. Single crystal X-ray diffraction reveals that all complexes are three-dimensional (3D) frameworks, where complex 1 is constructed by connecting rare mu(5)-N bridging Mtta ligands to Cu-I-K layers, complex 2 is built up by connecting inorganic cationic [Cu6I2](4+) clusters with numerous Mtta ligands, while complex 3 is constructed from open Cu(Mtta) subnets and Na+ centers. Furthermore, the luminescence properties of all complexes have been investigated. This work further supplements the mechanism of the Demko-Sharpless reaction in heteronuclear tetrazole-based coordination polymers.