Highly Conducting Organic-Inorganic Hybrid Copper Sulfides Cux C6 S6 (x=4 or 5.5): Ligand-Based Oxidation-Induced Chemical and Electronic Structure Modulation

Xing Huang; Yi Qiu; Yishan Wang; Liyao Liu; Xiaoyu Wu; Yingying Liang; Yutao Cui; Yimeng Sun; Ye Zou; Jia Zhu; Weihai Fang; Junliang Sun; Wei Xu; Daoben Zhu

doi:10.1002/anie.202009613

Highly Conducting Organic-Inorganic Hybrid Copper Sulfides Cu_x C₆ S₆ (x=4 or 5.5): Ligand-Based Oxidation-Induced Chemical and Electronic Structure Modulation

Angew Chem Int Ed Engl. 2020 Dec 7;59(50):22602-22609. doi: 10.1002/anie.202009613. Epub 2020 Oct 12.

Authors

Xing Huang^{1

2}, Yi Qiu³, Yishan Wang⁴, Liyao Liu^{1

2}, Xiaoyu Wu^{1

2}, Yingying Liang^{1

2}, Yutao Cui^{1

2}, Yimeng Sun¹, Ye Zou¹, Jia Zhu⁴, Weihai Fang⁴, Junliang Sun³, Wei Xu^{1

2}, Daoben Zhu^{1

2}

Affiliations

¹ Beijing National Laboratory for Molecular Sciences, CAS Key Laboratory of Organic Solids, Insititute of Chemistry, Chinese Academy of sciences, Beijing, 100190, China.
² University of Chinese Academy of Sciences, Beijing, 100049, China.
³ College of Chemistry and Molecular Engineering, Peking University, Beijing, 100871, China.
⁴ Key Laboratory of Theoretical and Computational Photochemistry, Ministry of Education, College of Chemistry, Beijing Normal University, Beijing, 100875, China.

PMID: 32893955
DOI: 10.1002/anie.202009613

Abstract

Conductive coordination polymers (CPs) have potential in a wide range of applications because of their inherent structural and functional diversity. Three electrically conductive CPs (Cu_x C₆ S₆ , x=3, 4 or 5.5) derived from the same organic linker (benzenehexathiol) and metal node (copper(I)) were synthesized and studied. Cu_x C₆ S₆ materials are organic-inorganic hybrid copper sulfides comprising a π-π stacking structure and cooper sulfur networks. Charge-transport pathways within the network facilitate conductivity and offer control of the Fermi level through modulation of the oxidation level of the non-innocent redox-active ligand. Two Cu_x C₆ S₆ (x=4 or 5.5) CPs display high electrical conductivity and they feature a tunable structural topology and electronic structure. Cu₄ C₆ S₆ and Cu_5.5 C₆ S₆ act as degenerate semiconductors. Moreover, Cu_5.5 C₆ S₆ is a p-type thermoelectric material with a ZT value of 0.12 at 390 K, which is a record-breaking performance for p-type CPs.

Keywords: degenerate semiconductor; metal-organic frameworks; organic-inorganic hybrids; thermoelectric materials.

Abstract

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