Control of the Hydroquinone/Benzoquinone Redox State in High-Mobility Semiconducting Conjugated Coordination Polymers
© 2024 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH..
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 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.
| Medienart: |
E-Artikel |
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| Erscheinungsjahr: |
2024 |
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| Erschienen: |
2024 |
| Enthalten in: |
Zur Gesamtaufnahme - year:2024 |
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| Enthalten in: |
Angewandte Chemie (International ed. in English) - (2024) vom: 15. März, Seite e202320091 |
| Sprache: |
Englisch |
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| Beteiligte Personen: |
Huang, Xing [VerfasserIn] |
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| Links: |
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| Themen: |
Benzoquinone |
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| Anmerkungen: |
Date Revised 09.04.2024 published: Print-Electronic Citation Status Publisher |
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| doi: |
10.1002/anie.202320091 |
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| PPN (Katalog-ID): |
NLM369785428 |
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| 245 | 1 | 0 | |a Control of the Hydroquinone/Benzoquinone Redox State in High-Mobility Semiconducting Conjugated Coordination Polymers |
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| 520 | |a © 2024 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH. | ||
| 520 | |a 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 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 | ||
| 650 | 4 | |a Journal Article | |
| 650 | 4 | |a Benzoquinone | |
| 650 | 4 | |a Conjugated coordination polymers | |
| 650 | 4 | |a Metal–organic frameworks | |
| 650 | 4 | |a Opto-electronics | |
| 650 | 4 | |a Semiconductors | |
| 700 | 1 | |a Li, Yang |e verfasserin |4 aut | |
| 700 | 1 | |a Fu, Shuai |e verfasserin |4 aut | |
| 700 | 1 | |a Ma, Chao |e verfasserin |4 aut | |
| 700 | 1 | |a Lu, Yang |e verfasserin |4 aut | |
| 700 | 1 | |a Wang, Mingchao |e verfasserin |4 aut | |
| 700 | 1 | |a Zhang, Peng |e verfasserin |4 aut | |
| 700 | 1 | |a Li, Ze |e verfasserin |4 aut | |
| 700 | 1 | |a He, Feng |e verfasserin |4 aut | |
| 700 | 1 | |a Huang, Chuanhui |e verfasserin |4 aut | |
| 700 | 1 | |a Liao, Zhongquan |e verfasserin |4 aut | |
| 700 | 1 | |a Zou, Ye |e verfasserin |4 aut | |
| 700 | 1 | |a Zhou, Shengqiang |e verfasserin |4 aut | |
| 700 | 1 | |a Helm, Manfred |e verfasserin |4 aut | |
| 700 | 1 | |a Petkov, Petko St |e verfasserin |4 aut | |
| 700 | 1 | |a Wang, Hai I |e verfasserin |4 aut | |
| 700 | 1 | |a Bonn, Mischa |e verfasserin |4 aut | |
| 700 | 1 | |a Li, Jian |e verfasserin |4 aut | |
| 700 | 1 | |a Xu, Wei |e verfasserin |4 aut | |
| 700 | 1 | |a Dong, Renhao |e verfasserin |4 aut | |
| 700 | 1 | |a Feng, Xinliang |e verfasserin |4 aut | |
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