Convenient synthesis of copper(i) halide quasi-one-dimensional coordination polymers: their structures and solid-state luminescent properties

The heterogeneous reaction between copper(i) halide and pyridine derivative ligand in a suspension conveniently afforded luminescent copper(i) complexes. The progress of the reaction was confirmed by powder X-ray diffraction (PXRD) and thermogravimetric (TG) measurements. The structure of the obtained complexes was clarified by comparison with the X-ray analysis of a single crystal obtained by the homogeneous reaction in a solution. The reaction was affected by the type of solvent and substituents on the pyridine ligand. The reaction proceeded quantitatively, not depending on copper(i) halide, when ethyl acetate and 3-bromopyridine were used as the solvent and ligand, respectively. X-ray analysis of the single-crystals obtained by the corresponding reaction in solution revealed that the reaction in suspension afforded the same stair-shaped quasi-one-dimensional structure. The obtained copper(i) complex powders displayed luminescence, which was attributed to the halide/metal-to-ligand charge transfer (XMLCT), as elucidated by crystal orbital distribution and principal component of excitation based on density functional theory (DFT) calculations.

Automated summary

In this study, the heterogenous reaction between copper(I) halide and pyridine derivative ligand produced luminescent copper(I) complexes. The progress of the reaction was monitored using PXRD and TG measurements, and the structure was elucidated by comparing it to single crystal X-ray analysis. The reaction proceeded quantitatively, regardless of the type of copper(I) halide used, when specific solvents and ligands were employed.