Solvent-Free Synthesis of Luminescent Copper(I) Coordination Polymers with Thiourea Derivatives

Abstract

This communication reports the solvent-free synthesis of a series of copper(I) cyanide (CuCN) -based coordination polymers showing interesting luminescence properties and specific three-dimensional structures. The new compounds have been achieved by directly grinding CuCN together with thiourea (tu), N-methylthiourea (mtu), N-phenylthiourea (ptu), N,N′-diphenylthiourea (dptu), and 2,4-difluorophenylthiourea (fptu). The resulting compounds are [(CuCN)2(tu)]n, [(CuCN)5(mtu)3]n, [(CuCN)3(mtu)2]n, [CuCN(ptu)]n, [CuCN(dptu)]n, and [(CuCN)3(fptu)2]n. “Seeding” crystallization was successful for [(CuCN)2(tu)]n, [CuCN(ptu)]n, [CuCN(dptu)]n, and [(CuCN)3(fptu)2]n, and their structures have been resolved using X-ray single crystal diffraction. Owing to the microcrystalline powdered nature of compounds [(CuCN)5(mtu)3]n and [(CuCN)3(mtu)2]n, their characterization was mainly based on solid-state NMR, via 13C cross polarization magic angle spinning for ligand coordination and 1H magic angle spinning for the weak inter...