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

Abstract

Reactions of 3,5-disubstituted-1,2,4-triazoles with CuX 2 (X = Cl, Br) under hydrothermal condition yield six copper(I) triazolates: [Cu 2 (3,5-n Bu 2 tz)Cl] n (1), [Cu 2 (3,5-i Bu 2 tz)Cl] n (2), {Cu 2 (3,5-(C 6 H 11 ) 2 tz)Cl} n (3), [Cu 2 (3,5-s Bu 2 tz)Br] n (4), {Cu 2 (3,5-(C 6 H 11 ) 2 tz)Br} n (5), {Cu 2 [3,5-(p-Tol) 2 tz]Br} n (6), where 3,5-n Bu 2 tz, 3,5-i Bu 2 tz, 3,5-s Bu 2 tz 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-(C 6 H 11 ) 2 tz is 3,5-dicyclohexyl-1,2,4-triazolate; 3,5-(p-Tol) 2 tz 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 Cu 4 Cl 4 or Cu 4 Br 4 clusters. While 4 and 5 luminesce with maxima at 571 and 619 nm, others are silent under UV irradiation at room temperature.Keywords Copper(I) Á Triazole Á Structure Á Cu 4 Cl 4 cluster Á Cu 4 Br 4 cluster Electronic supplementary material The online version of this article (

Investigation of Luminescent Triplet States in Tetranuclear CuI Complexes: Thermochromism and Structural Characterization

“…[13] At the same time, analogous tetranuclearc lusters have been reported,w hich are formally built up by combining two Cu 2 I 2 subunits. [10,[14][15][16][17][18][19][20][21][22][23][24][25][26][27][28] At this point, it is important to mention that the very first OLED based on Cu I contained the tetranuclear complexC u 4 (CCph) 4 L 2 (L = 1,8-bis(diphenylphosphino)-3,6-dioxaoctane). [29] Lu et al reported on ah ighly luminescent tetranuclear system with aC u 4 Cl 4 core and 2-(bis(2-methyl-phenyl)phosphino)-6-methylpyridine as bridging ligand,s howinga combination of TADF and fast phosphorescence at room temperature.…”

Synthesis, X‐Ray Structures, and Fluxional Properties of Symmetrical, Asymmetrical Binuclear and Cubane Type Copper(I) Complexes Bearing the Pyrrole‐Based P, N‐Hetero Donor Ligand

“…The majority of complexes are binuclear with a rhomboidal shape, which acts as a building block for higher nuclearity molecular and for polymeric complexes . Conversely, for complexes containing four copper nuclei, several distorted cubane type, stair step and planar parallelogram structures with varying Cu ⋅⋅⋅ Cu interactions have been reported, as the topological arrangement of four atoms in space changes with the nature of ancillary ligand and halide ion. This structural diversity of copper(I) complexes continues to grow, as new tailor‐made ligands with unique steric and electronic factors are invented in conjunction with different sizes of halide atoms and reaction conditions…”