Structural and Luminescence Properties of Cu(I)X-Quinoxaline under High Pressure (X = Br, I)

Abstract

A study of high-pressure single-crystal X-ray diffraction and luminescence experiments together with ab initio simulations based on the density functional theory has been performed for two isomorphous copper(I) halide compounds with the empirical formula [C8H6Cu2X2N2] (X = Br, I) up to 4.62(4) and 7.00(4) GPa for X-ray diffraction and 6.3(4) and 11.6(4) GPa for luminescence, respectively. An exhaustive study of compressibility has been completed by means of determination of the isothermal equations of state and structural changes with pressure at room temperature, giving bulk moduli of K0 = 14.4(5) GPa and K′0 = 7.7(6) for the bromide compound and K0 = 13.0(2) GPa and K′0 = 7.4(2) for the iodide compound. Both cases exhibited a phase transition of second order around 3.3 GPa that was also detected in luminescence experiments under the same high-pressure conditions, wherein redshifts of the emission bands with increasing pressure were observed due to shortening of the Cu–Cu distances. Additionally, ab initio studies were carried out which confirmed the results obtained experimentally, although unfortunately, the phase transition was not predicted.