Powder Structure Determination of a series of homoleptic copper(I)-arylthiolate conducting polymers

Abstract

Homoleptic copper(I) arylthiolates [Cu(p-SC6H4-X)]n (X = CH3 1, H 2, CH3O 3, tBu 4, CF3 5, NO2 6, COOH 7 and n = infinity) were insoluble crystalline solids.[1] Structure determination using powder diffraction revealed that 1-3 and 6 formed 1-D polymers with Cu atoms bridged by arylthiolate ligands. Weak intra-chain pi-pi stacking interactions are present in 1-3. In 6, the intra-chain pi-pi interactions are insignificant and the chain polymers are associated via non-covalent C-H...O hydrogen bonding interactions. As revealed by TEM, the solid samples of 1-5 and [Cu(SCH3)]n contained homogenously dispersed crystalline nano-rods whereas smaller plate nano-crystals were found for 6 and 7. SAED further confirmed that the chain polymers of 1-3 and [Cu(SCH3)]n similarly grow along the long axes of their nano-rods. The nano-rods of 1-5 and [Cu(SCH3)]n exhibited p-type field-effect transistor behavior with charge mobility of 10E-2 to 10E-5 cm2V-1s-1. Their charge mobility is correlated to their unique chain-like copper-sulfur networks, and the para-substitutent of arylthiolate ligand alter the ultimate particle morphology and charge transport properties. [1] Chem. Eur. J. 2008, 14, 2965.