Highly Conducting Organic–Inorganic Hybrid Copper Sulfides Cu<sub><i>x</i></sub>C<sub>6</sub>S<sub>6</sub> (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, Wei‐Hai Fang, Junliang Sun, Wei Xu, Daoben Zhu
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 C 6 S 6 , x =3, 4 or 5.5) derived from the same organic linker (benzenehexathiol) and metal node (copper(I)) were synthesized and studied. Cu x C 6 S 6 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 C 6 S 6 ( x =4 or 5.5) CPs display high electrical conductivity and they feature a tunable structural topology and electronic structure. Cu 4 C 6 S 6 and Cu 5.5 C 6 S 6 act as degenerate semiconductors. Moreover, Cu 5.5 C 6 S 6 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.