Anionic Cu<i>_n</i>I<i>_n</i> Cluster-Based Architectures Induced by In Situ Generated <i>N</i>-Alkylated Cationic Triazolium Salts

Five new copper(I) iodide coordination polymers, (Cu10I10)(Cu6I6)[(Cu(Bta)2]3−·(DMBta)4+·(I−)·x(I2) (x ≈ 1.5) (1), [Cu2I2(MBta)] (2), [Cu2I2(MTa)] (3), (Cu5I5)[Cu(Ta)2]−·(DETa)+ (4), and [Cu3I(Bta)2] (5) (Bta = benzotriazole, DMBta = 1,3-N-dimethylbenzotriazolium, MBta = 1-N-methylbenzotriazole, MTa = 1-N-methyltriazole, Ta = 1,2,3-triazole, DETa = 1,3-N-diethyltriazolium), have been prepared by the solvo(hydro)thermal reactions of CuI, KI, and benzotriazole (or 1,2,3-triazole) in methanol (or ethanol or water) and structurally characterized. Complex 1 shows a highly unusual two-dimensional (2D) → three-dimensional (3D) interpenetrated anionic network containing two new discrete neutral Cu10I10/Cu6I6 cluster units, and complex 4 consists of 2D anionic layers with Cu5I5 cluster units, both of which involve in situ di-N-alkylated cationic triazolium to induce the anionic frameworks. Complexes 2 and 3 both contain neutral in situ mono-N-alkylated ligands and exhibit similar one-dimensional (1D) double-stranded stairlike ribbon structures. Complex 5 exhibits a 2D simple sheet structure containing nonalkylated Bta− ligands. A mechanism of the solvo(hydro)thermal reaction is proposed. As evidenced by means of electrospray ionization mass spectrometry measurements, a simultaneous redox, N-alkylated and self-assembly reaction occurs.