Highly Conducting Organic-Inorganic Hybrid Copper Sulfides Cuxc6s6(X=4 Or 5.5): Ligand-Based Oxidation-Induced Chemical And Electronic Structure Modulation

Conductive coordination polymers (CPs) have potential in a wide range of applications because of their inherent structural and functional diversity. Three electrically conductive CPs (CuxC6S6,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 pi-pi 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 CuxC6S6(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.