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, [Me(4)N][Cu(3)(CN)(2)Br(2)] (1) with a 1-D ribbon motif and [Me(4)N](2)[Cu(4)(CN)(5)Cl] (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 [Cu(4)Br(4)] 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 [Me(4)N](+) cations. Results of optical and luminescent studies indicate that both two complexes are potential materials for semiconductors and long-lived highly luminescent materials.