Synthesis, Structures and Luminescent Properties of 3D Copper(I) 1,2,4-Triazolates Containing Cubic Cu4X4 Clusters (X = Cl, Br)

Reactions of 3,5-disubstituted-1,2,4-triazoles with CuX2 (X = Cl, Br) under hydrothermal condition yield six copper(I) triazolates: [Cu2(3,5- n Bu2tz)Cl]n (1), [Cu2(3,5- i Bu2tz)Cl]n (2), {Cu2(3,5-(C6H11)2tz)Cl}n (3), [Cu2(3,5- s Bu2tz)Br]n (4), {Cu2(3,5-(C6H11)2tz)Br}n (5), {Cu2[3,5-(p-Tol)2tz]Br}n (6), where 3,5- n Bu2tz, 3,5- i Bu2tz, 3,5- s Bu2tz are 3,5-dibutyl-1,2,4-triazolate, 3,5-dii-butyl-1,2,4-triazolate, 3,5-dis-butyl-1,2,4-triazolate; 3,5-(C6H11)2tz is 3,5-dicyclohexyl-1,2,4-triazolate; 3,5-(p-Tol)2tz is 3,5-di-p-tolyl-1,2,4-triazolate. X-ray analysis demonstrates that all of these complexes are isostructural and exhibit a 3D structure carrying cubic Cu4Cl4 or Cu4Br4 clusters. While 4 and 5 luminesce with maxima at 571 and 619 nm, others are silent under UV irradiation at room temperature.