Experimental and ab Initio Study of Catena(bis(μ2‑iodo)-6-methylquinoline-copper(I)) under Pressure: Synthesis, Crystal Structure, Electronic, and Luminescence Properties

Copper­(I) iodine compounds can exhibit interesting mechanochromic and thermochromic luminescent properties with important technological applications. We report the synthesis and structure determination by X-ray diffraction of a new polymeric staircase copper­(I) iodine compound catena­(bis­(μ2-iodo)-6-methylquinoline-copper­(I), [C10H9CuIN]. The structure is composed of isolated polymeric staircase chains of copper–iodine coordinated to organic ligands through Cu–N bonds. High pressure X-ray diffraction to 6.45 GPa shows that the material is soft, with a bulk modulus K 0 = 10.2(2)­GPa and a first derivative K′0 = 8.1(3), typical for organometallic compounds. The unit-cell compression is very anisotropic with the stiffest direction [302] arising from a combination of the stiff CuI ladders and the shear of the planar quinolone ligands over one another. Full structure refinements at elevated pressures show that pressures reduce the Cu···Cu distances in the compound. This effect is detected in luminescence spectra with the appearance of four sub-bands at 515, 600, 647, and 712 nm above 3.5 GPa. Red-shifts are observed, and they are tentatively associated with interactions between copper­(I) ions due to the shortening of the Cu···Cu distances induced by pressure, below twice the van der Waals limit (2.8 Å). Additionally, ab initio simulations were performed, and they confirmed the structure and the results obtained experimentally for the equation of state. The simulation allowed the band structure and the electronic density of states of this copper­(I) iodine complex to be determined. In particular, the band gap decreases slowly with pressure in a quadratic way with dE g /dP = −0.011 eV/GPa and d2 E g /dP 2 = 0.001 eV/GPa2.