Journal of the Electrochemical Society, Vol.141, No.7, 1713-1720, 1994
Heterogeneous and Homogeneous Electron-Transfer Reactions of Tetrathiafulvalene in Ambient-Temperature Chloraluminate Molten-Salts
The electrochemistry of tetrathiafulvalene (TTF) in an ambient temperature chloroaluminate molten salt composed of 1-ethyl-3-methylimidazolium chloride mixed with AlCl3 has been examined. In both basic and acidic melts TTF is oxidized in two consecutive, one-electron steps to TTF+ and then to TTF2+. In basic melts, neutral TTF is stable and its oxidations are well-behaved on the voltammetric time scale. TTF2+ is adsorbed at a glassy carbon working electrode in basic melts. Constant current electrolysis of TTF to TTF+ at a Pt electrode in basic melt produces purple crystals which appear to be electronically conductive. In acidic melts HCl, present as an impurity, oxidizes TTF to TTF+. Diffusion coefficient measurements by pulse voltammetry suggest that TTF forms a slowly diffusing AlCl3 adduct in acidic melts.