Highly Conducting Organic–Inorganic Hybrid Copper Sulfides CuxC6S6 (x=4 or 5.5): Ligand‐Based Oxidation‐Induced Chemical and Electronic Structure Modulation. (12th October 2020)

• Record Type: Journal Article
• Authors: Huang, Xing; Qiu, Yi; Wang, Yishan; Liu, Liyao; Wu, Xiaoyu; Liang, Yingying; Cui, Yutao; Sun, Yimeng; Zou, Ye; Zhu, Jia; Fang, Weihai; Sun, Junliang; Xu, Wei; Zhu, Daoben
• Is Part Of: Angewandte Chemie. Volume 132:Number 50(2020)
• Page Start: 22791
• Page End: 22798
• Publication Date: 2020-10-12
• Subjects: degenerate semiconductor -- metal–organic frameworks -- organic–inorganic hybrids -- thermoelectric materials; Chemistry -- Periodicals; 540
• DOI: 10.1002/ange.202009613
• Languages: English
• ISSNs: 0044-8249

Abstract

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 Cu5.5 C6 S6 act as degenerate semiconductors. Moreover, Cu5.5 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. Abstract : A family of electrically conductive coordination polymers (Cu x C6 S6 ; x =3, 4 or 5.5) are reported. The hybrid structures of the polymers offer charge‐transport paths and enable a shift of the Fermi level by modulating the oxidation level of the non‐innocent redox‐active ligand. As a result, their band structures range from metal to degenerate semiconductors in which Cu5.5 C6 S6 demonstrates appreciable thermoelectric performance.