An unprecedented three-dimensional copper-halide-sulfur semiconductive framework for effective light and nitrogen dioxide electrical detections

The coordination of copper(I) halide moiety and sulfur-donor ligand to construct copper-halide-sulfur complex is proposed to combine the prominent optical and electronic functions from both copper halide and copper chal-cogenide moieties. However, currently reported copper-halide-sulfur complexes mostly possess low dimensional structure or lack continuous electron transportation, thereby being unfavorable for electrical-based application. Herein, we report an unprecedented copper (I) complex {(pt)2Cu3I3}n (denoted as UJN-Cu6, pt = pyridin-1-ium-4-thiolate), which contains the first reported three-dimensional (3D) copper-halide-sulfur semiconductive framework. UJN-Cu6 was constructed by a deliberately synthesis strategy, where the copper iodine species were monodentate bridged by the sulfur-donor ligand, which is different from the most reported multidentate coor-dination mode. The thin film device of UJN-Cu6 can detect both UV and visible light with high switching on/off ratios and excellent photocurrent reproducibility. Further, the thin film device exhibits good sensitivity, short response time and high selectivity toward detecting hazardous NO2/N2O4. Mechanism studies indicate that the semiconductive copper-halide-sulfur skeleton contributes a lot to the electrical-based detection applications. The functional -N-H groups hanging on the surface of channel bring about highly selective recognition of NO2/N2O4 molecules.