Luminescent Thermochromism of 2D Coordination Polymers Based on Copper(I) Halides with 4‐Hydroxythiophenol

Abstract Solvothermal reactions between copper(I) halides and 4‐mercaptophenol give rise to the formation of three coordination polymers with general formula [Cu 3 X(HT) 2 ] n (X=Cl, 1 ; Br, 2 ; and I, 3 ). The structures of these coordination polymers have been determined by X‐ray diffraction at both room‐ and low temperature (110 K), showing a general shortening in Cu−S, Cu−X and Cu−Cu bond lengths at low temperatures. 1 and 2 are isostructural, consisting of layers in which the halogen ligands act as μ 3 ‐bridges joining two Cu1 and one Cu2 atoms whereas in 3 the iodine ligands is as μ 4 ‐mode but the layers are quasi‐isostructural with 1 or 2 . These compounds show a reversible thermochromic luminescence, with strong orange emission for 1 and 2 , but weaker for 3 at room temperature, whereas upon cooling at 77 K 1 and 2 show stronger yellow emission, and 3 displays stronger green emission. DFT calculations have been used to rationalize these observations. These results suggest a high potential for this novel and promising stimuli‐responsive materials.