Control of the Hydroquinone/Benzoquinone Redox State in High-Mobility Semiconducting Conjugated Coordination Polymers
Huang, Xing; Li, Yang; Fu, Shuai; Ma, Chao; Lu, Yang; Wang, Mingchao; Zhang, Peng; Li, Ze; He, Feng; Huang, Chuanhui; Liao, Zhongquan; Zou, Ye; Zhou, Shengqiang; Helm, Manfred; Petkov, Petko St; Wang, Hai I.; Bonn, Mischa; Li, Jian; Xu, Wei; Dong, Renhao; Feng, Xinliang
(2024) Angewandte Chemie - International Edition, volume 63, issue 20
(Article)
Abstract
Conjugated coordination polymers (c-CPs) are unique organic–inorganic hybrid semiconductors with intrinsically high electrical conductivity and excellent charge carrier mobility. However, it remains a challenge in tailoring electronic structures, due to the lack of clear guidelines. Here, we develop a strategy wherein controlling the redox state of hydroquinone/benzoquinone (HQ/BQ) ligands allows
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for the modulation of the electronic structure of c-CPs while maintaining the structural topology. The redox-state control is achieved by reacting the ligand TTHQ (TTHQ=1,2,4,5-tetrathiolhydroquinone) with silver acetate and silver nitrate, yielding Ag4TTHQ and Ag4TTBQ (TTBQ=1,2,4,5-tetrathiolbenzoquinone), respectively. In spite of sharing the same topology consisting of a two-dimensional Ag−S network and HQ/BQ layer, they exhibit different band gaps (1.5 eV for Ag4TTHQ and 0.5 eV for Ag4TTBQ) and conductivities (0.4 S/cm for Ag4TTHQ and 10 S/cm for Ag4TTBQ). DFT calculations reveal that these differences arise from the ligand oxidation state inhibiting energy band formation near the Fermi level in Ag4TTHQ. Consequently, Ag4TTHQ displays a high Seebeck coefficient of 330 μV/K and a power factor of 10 μW/m ⋅ K2, surpassing Ag4TTBQ and the other reported silver-based c-CPs. Furthermore, terahertz spectroscopy demonstrates high charge mobilities exceeding 130 cm2/V ⋅ s in both Ag4TTHQ and Ag4TTBQ.
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Keywords: Benzoquinone, Conjugated coordination polymers, Metal–organic frameworks, Opto-electronics, Semiconductors, Catalysis, General Chemistry
ISSN: 1433-7851
Publisher: John Wiley and Sons Ltd
Note: Publisher Copyright: © 2024 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH.
(Peer reviewed)
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