Journal
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
Volume 62, Issue 10, Pages -Publisher
WILEY-V C H VERLAG GMBH
DOI: 10.1002/anie.202211850
Keywords
Chemical Sensing; Dithiolene Complexes; Metal-Organic Framework; Mixed-Linker; Tetrathiafulvalene
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In this study, a mixed-linker conductive MOF system was developed by incorporating tetrathiafulvalene and Ni-bis(dithiolene) moieties, allowing precise control over electronic structures and semiconductor characteristics by adjusting their molar ratio. The semiconducting behavior of the MOF system can be switched from n-type to p-type by increasing the ratio of tetrathiafulvalene to Ni-bis(dithiolene), resulting in a three orders of magnitude increase in electrical conductivity. Additionally, the mixed-linker MOFs showed synergistic and nonlinear modulation effects on the chemiresistive detection of VOCs, with sensing performance modulated by the linker ratios.
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 2.88x10(-7) S m(-1) to 9.26x10(-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.
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