Arylamine-solvated copper(I)/iodide coordination polymers cooperatively formed by the amination of aryl iodides and the assembly of [Cu2I2] species with 1,2-bis(4-pyridyl)ethane

Solvothermal reactions of Cu2(OH)2CO3 with 1,2-bis(4-pyridyl)ethane (bpe) and iodobenzene or 4-iodotoluene in acetonitrile and aqueous ammonia afforded two arylamine-solvated [Cu2I2]-based coordination polymers {[Cu2I2(bpe)2]∙Am}n (1: Am = aniline; 2: Am = p-toluidine). Compounds 1 and 2 were characterized by elemental analysis, IR spectra, and powder X-ray diffraction (PXRD). Compounds 1 and 2 have a two-dimensional (4,4) topological network in which every rhombic [Cu2I2] dimer acts as a planar four-connected node to link other four equivalent ones by four bpe bridges. Each layer is further stacked via π–π interactions to form a 3D structure with 1D rhombic channels occupied by the guest aniline or p-toluidine molecules. These guest molecules were in situ generated through Ullmann coupling reactions of iodobenzene or 4-iodotoluene with ammonia. The thermal and photoluminescent properties of 1 and 2 were also investigated.