Diversity of Architecture of Copper(I) Coordination Polymers Constructed of Copper(I) Halides and 4-Methyl-1,2,4-Triazole-3-Thiol (Hmptrz) Ligand: Syntheses, Structures, and Luminescent Properties

Abstract

Solvo(hydro)thermal reactions of CuX (X = Cl, Br, I) with 4-methyl-1,2,4-triazole-3-thiol (Hmptrz) ligand afforded four new copper(I) coordination polymers, namely, [Cu(μ4-mptrz)]n (1), [Cu(μ2-Hmptrz)(μ2-I)]n (2), [Cu12(μ4-mptrz)4(μ4-I)3(μ3-I)4(μ2-I)]n (3), and [Cu(μ2-Hmptrz)(μ2-DmptrzSS)I]n (4) (DmptrzSS = 4,4′-dimethyl-3,3′-dithiodi-1,2,4-triazole), respectively. Single-crystal X-ray diffraction revealed that compound 1 has a two-dimensional (2D) layered structure with (44·62) topology and contains meso-helical (CuS)n chains. Compound 2 features a one-dimensional (1D) chain structure constructed from an unusual inorganic [Cu(μ2-S)2Cu(μ2-I)2Cu]n chain formed from two types of four-membered Cu2(μ2-S)2 and Cu2(μ2-I)2 rings. Compound 3 is a two-dimensional (2D) structure constructed from rugby-shaped Cu6I5 and planar Cu4I3 cluster units, and two types of Cu(mptrz)2 units. The I− ion in structure 3 displays its coordination versatility with μ4-, μ3-, and μ2- bridging coordination modes. Compound 4 has a doub...