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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.
Huang et al. (Mon,) studied this question.