Control of the Hydroquinone/Benzoquinone Redox State in High-Mobility Semiconducting Conjugated Coordination Polymers

Xing Huang; Yang Li; Shuai Fu; Chao Ma; Yang Lu; Mingchao Wang; Peng Zhang; Ze Li; Feng He; Chuanhui Huang; Zhongquan Liao; Ye Zou; Shengqiang Zhou; Manfred Helm; Petko St Petkov; Hai I. Wang; Mischa Bonn; Jian Li; Wei Xu; Renhao Dong; Xinliang Feng

doi:10.1002/anie.202320091

Control of the Hydroquinone/Benzoquinone Redox State in High-Mobility Semiconducting Conjugated Coordination Polymers

Xing Huang, Yang Li, Shuai Fu, Chao Ma, Yang Lu, Mingchao Wang, Peng Zhang, Ze Li, Feng He, Chuanhui Huang, Zhongquan Liao, Ye Zou, Shengqiang Zhou, Manfred Helm, Petko St Petkov, Hai I. Wang, Mischa Bonn, Jian Li^*, Wei Xu^*, Renhao Dong^*Xinliang Feng^*

^*Corresponding author for this work

Research output: Contribution to journal › Article › Academic › peer-review

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 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.

Original language	English
Article number	e202320091
Journal	Angewandte Chemie - International Edition
Volume	63
Issue number	20
Early online date	15 Mar 2024
DOIs	https://doi.org/10.1002/anie.202320091
Publication status	Published - May 2024

Bibliographical note

Publisher Copyright:
© 2024 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH.

Funding

This work is financially supported by ERC starting grant (FC2DMOF, No. 852909), National Natural Science Foundation of China (22272092), ERC Consolidator Grant (T2DCP, No. 819698) and DFG projects (CRC\u20101415, No. 417590517; RTG 2861, No. 491865171). The authors acknowledge cfaed and the Dresden Center for Nano\u2010analysis (DCN) at TUD. R.D. thanks the Taishan Scholars Program of Shandong Province (tsqn201909047) and Natural Science Foundation of Shandong Province (ZR2023JQ005). W.X. acknowledges the financial support from the National Natural Science Foundation of China (Grant 22071256 and 22379150). J.L. acknowledges the financial support from the National Natural Science Foundation of China (grant numbers: 22371121), the Fundamental Research Funds for the Central Universities of China (020514380306) and the Natural Science Foundation of Jiangsu Province (BK20230772) The authors also appreciate the crew of the BL14B1 beamline at the Shanghai Synchrotron Radiation Facility (SSRF) for their assistance in synchrotron PXRD data collection. The authors acknowledge Dr. Bo Guan and Dr. Xiang Hao from the Institute of Chemistry, Chinese Academy of Sciences for the measurements of rotation electron diffraction. P.\u2005St. P. is grateful to the European Union\u2010NextGenerationEU, through the National Recovery and Resilience Plan of the Republic of Bulgaria, project No BG\u2010RRP\u20102.004\u20130008 for the financial support and Discoverer PetaSC and EuroHPC JU for awarding access to Discoverer supercomputer resources.

Funders	Funder number
European Union‐NextGenerationEU
Natural Science Foundation of Jiangsu Province	BK20230772
Natural Science Foundation of Jiangsu Province
National Natural Science Foundation of China	819698, 22272092
National Natural Science Foundation of China
Fundamental Research Funds for the Central Universities	020514380306
Fundamental Research Funds for the Central Universities
European Research Council	852909, FC2DMOF
European Research Council
Natural Science Foundation of Shandong Province	22071256, 22371121, 22379150, ZR2023JQ005
Natural Science Foundation of Shandong Province
Taishan Scholar Project of Shandong Province	tsqn201909047
Taishan Scholar Project of Shandong Province
National Recovery and Resilience Plan of the Republic of Bulgaria	BG‐RRP‐2.004–0008
Deutsche Forschungsgemeinschaft	RTG 2861, CRC‐1415, 417590517, 491865171
Deutsche Forschungsgemeinschaft

Keywords

Benzoquinone
Conjugated coordination polymers
Metal–organic frameworks
Opto-electronics
Semiconductors

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10.1002/anie.202320091Licence: CC BY-NC

Angew Chem Int Ed - 2024 - Huang - Control of the Hydroquinone Benzoquinone Redox State in High‐Mobility SemiconductingFinal published version, 2.76 MBLicence: CC BY-NC

Cite this

Huang, X., Li, Y., Fu, S., Ma, C., Lu, Y., Wang, M., Zhang, P., Li, Z., He, F., Huang, C., Liao, Z., Zou, Y., Zhou, S., Helm, M., Petkov, P. S., Wang, H. I., Bonn, M., Li, J., Xu, W., ... Feng, X. (2024). Control of the Hydroquinone/Benzoquinone Redox State in High-Mobility Semiconducting Conjugated Coordination Polymers. Angewandte Chemie - International Edition, 63(20), Article e202320091. https://doi.org/10.1002/anie.202320091

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title = "Control of the Hydroquinone/Benzoquinone Redox State in High-Mobility Semiconducting Conjugated Coordination Polymers",

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 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.",

keywords = "Benzoquinone, Conjugated coordination polymers, Metal–organic frameworks, Opto-electronics, Semiconductors",

author = "Xing Huang and Yang Li and Shuai Fu and Chao Ma and Yang Lu and Mingchao Wang and Peng Zhang and Ze Li and Feng He and Chuanhui Huang and Zhongquan Liao and Ye Zou and Shengqiang Zhou and Manfred Helm and Petkov, \{Petko St\} and Wang, \{Hai I.\} and Mischa Bonn and Jian Li and Wei Xu and Renhao Dong and Xinliang Feng",

note = "Publisher Copyright: {\textcopyright} 2024 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH.",

year = "2024",

month = may,

doi = "10.1002/anie.202320091",

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Huang, X, Li, Y, Fu, S, Ma, C, Lu, Y, Wang, M, Zhang, P, Li, Z, He, F, Huang, C, Liao, Z, Zou, Y, Zhou, S, Helm, M, Petkov, PS, Wang, HI, Bonn, M, Li, J, Xu, W, Dong, R & Feng, X 2024, 'Control of the Hydroquinone/Benzoquinone Redox State in High-Mobility Semiconducting Conjugated Coordination Polymers', Angewandte Chemie - International Edition, vol. 63, no. 20, e202320091. https://doi.org/10.1002/anie.202320091

TY - JOUR

T1 - Control of the Hydroquinone/Benzoquinone Redox State in High-Mobility Semiconducting Conjugated Coordination Polymers

AU - Huang, Xing

AU - Li, Yang

AU - Fu, Shuai

AU - Ma, Chao

AU - Lu, Yang

AU - Wang, Mingchao

AU - Zhang, Peng

AU - Li, Ze

AU - He, Feng

AU - Huang, Chuanhui

AU - Liao, Zhongquan

AU - Zou, Ye

AU - Zhou, Shengqiang

AU - Helm, Manfred

AU - Petkov, Petko St

AU - Wang, Hai I.

AU - Bonn, Mischa

AU - Li, Jian

AU - Xu, Wei

AU - Dong, Renhao

AU - Feng, Xinliang

PY - 2024/5

Y1 - 2024/5

N2 - 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.

AB - 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.

KW - Benzoquinone

KW - Conjugated coordination polymers

KW - Metal–organic frameworks

KW - Opto-electronics

KW - Semiconductors

UR - https://www.scopus.com/pages/publications/85189802382

U2 - 10.1002/anie.202320091

DO - 10.1002/anie.202320091

M3 - Article

AN - SCOPUS:85189802382

SN - 1433-7851

VL - 63

JO - Angewandte Chemie - International Edition

JF - Angewandte Chemie - International Edition

IS - 20

M1 - e202320091

ER -

Control of the Hydroquinone/Benzoquinone Redox State in High-Mobility Semiconducting Conjugated Coordination Polymers

Abstract

Bibliographical note

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Keywords

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