Redox‐Active Mixed‐Linker Metal–Organic Frameworks with Switchable Semiconductive Characteristics for Tailorable Chemiresistive Sensing
Xiao‐Cheng Zhou, Cheng Liu, Jian Su, Yi‐Fan Liu, Zhangyan Mu, Yamei Sun, Zhimei Yang, Shuai Yuan, Mengning Ding, Jing‐Lin Zuo
Abstract
Abstract Metal–organic frameworks (MOFs), with diverse metal nodes and designable organic linkers, offer unique opportunities for the rational engineering of semiconducting properties. In this work, we report a mixed‐linker conductive MOF system with both tetrathiafulvalene and Ni‐bis(dithiolene) moieties, which allows the fine‐tuning of electronic structures and semiconductive characteristics. By continuously increasing the molar ratio between tetrathiafulvalene and Ni‐bis(dithiolene), the switching of the semiconducting behaviors from n‐type to p‐type was observed along with an increase in electrical conductivity by 3 orders of magnitude (from 2.88×10 −7 S m −1 to 9.26×10 −5 S m −1 ). Furthermore, mixed‐linker MOFs were applied for the chemiresistive detection of volatile organic compounds (VOCs), where the sensing performance was modulated by the corresponding linker ratios, showing synergistic and nonlinear modulation effects.