Two Halogeno(cyano)cuprates with Long-Lived and Strong Luminescence

Solvothermal reactions of copper(I) cyanide with tetramethylammonium salts in anhydrous tetrahydrofuran (THF) lead to two novel halogeno(cyano)cuprates, namely, [Me4N][Cu3(CN)2Br2] (1) with a 1-D ribbon motif and [Me4N]2[Cu4(CN)5Cl] (2) with a 3-D nanoporous framework. In 1, four Cu(I) ions are connected via two (mu)-Br and two (mu)3-Br atoms into a neutral [Cu4Br4] cluster, and such clusters are further double bridged by [Cu(CN)2]2- linkers to form a 1-D ribbonlike chain. While in 2, Cu(I) ions are connected via (mu)-CN and (mu)3-CN ligands and (mu)-Cl atoms into a 2-D fluctuant sheet along the a-c plane, and these sheets are further linked by another kind of (mu)-CN ligand to form a 3-D nanoporous framework in whose channels reside [Me4N]+ cations. Results of optical and luminescent studies indicate that both two complexes are potential materials for semiconductors and long-lived highly luminescent materials.