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 chalcogenide 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) 2 Cu 3 I 3 } 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 coordination 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 NO 2 /N 2 O 4. 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 NO 2 /N 2 O 4 molecules. [Display omitted] • The first 3D copper-halide-sulfur semiconductive framework was prepared via a well-designed synthesis strategy. • Functional organic pyridines hanging on the inorganic semiconductive skeleton affords fascinating electrical detections. • Detecting both UV and visible light with high switching on/off ratios and excellent photocurrent reproducibility. • Detecting hazardous NO 2 with good sensitivity, short response time and high selectivity. • Experimental and theoretical technologies were employed to disclose the difunctional detection mechanism. [ABSTRACT FROM AUTHOR]