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

Angew Chem Int Ed Engl. 2024 May 13;63(20):e202320091. doi: 10.1002/anie.202320091. Epub 2024 Apr 9.

Authors

Xing Huang^{1

2}, Yang Li³, Shuai Fu^{1

4}, Chao Ma⁵, Yang Lu¹, Mingchao Wang¹, Peng Zhang¹, Ze Li³, Feng He³, Chuanhui Huang¹, Zhongquan Liao⁶, Ye Zou³, Shengqiang Zhou⁷, Manfred Helm⁷, Petko St Petkov⁸, Hai I Wang^{4

9}, Mischa Bonn⁴, Jian Li⁵, Wei Xu³, Renhao Dong¹⁰, Xinliang Feng^{1

2}

Affiliations

¹ Center for Advancing Electronics Dresden (cfaed), Faculty of Chemistry and Food Chemistry, Technische Universität Dresden, Dresden, 01062, Germany.
² Max Planck Institute of Microstructure Physics, Halle (Saale), 06120, Germany.
³ Laboratory of Organic Solids, Institute of Chemistry Chinese Academy of Science, Beijing, 100190, China.
⁴ Max Planck Institute for Polymer Research, Mainz, 55128, Germany.
⁵ State Key Laboratory of Coordination Chemistry, School of Chemistry and Chemical Engineering, Nanjing University, Nanjing, Jiangsu 210023, China.
⁶ Fraunhofer Institute for Ceramic Technologies and Systems (IKTS), Dresden, 01109, Germany.
⁷ Institute of Ion Beam Physics and Materials Research, Helmholtz-Zentrum Dresden-Rossendorf, Dresden, 01328, Germany.
⁸ Faculty of Chemistry and Pharmacy, University of Sofia, Sofia, 1164, Bulgaria.
⁹ Nanophotonics, Debye Institute for Nanomaterials Science, Utrecht University, 3584, CC Utrecht, The Netherlands.
¹⁰ Key Laboratory of Colloid and Interface Chemistry of the Ministry of Education, School of Chemistry and Chemical Engineering, Shandong University, Jinan, 250100, China.

PMID: 38488855
DOI: 10.1002/anie.202320091

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.

Abstract

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