C1tet-Ttf Salts With Octahedral Anions

A hybrid molecule between BEDT-TTF and TTC1-TTF (tetrakis(methylthio)-TTF); C1TET-TTF (bis(methylthio)ethylenedithio-TTF), gave cation radical salts with PF6, AsF6, and Sb2F11 anions. Two PF6 and two AsF6 salts were electrochemically prepared in methanol or ethanol, and all of the four showed metallic temperature dependence of d.c. resistivity at around room temperature. These four salts are isomorphic, however, there are slight differences in the anion arrangement which is dependent on the solvent used. The salts from ethanol gave narrower EPR line widths than those from methanol at r.t.. The temperature dependence of EPR intensity for the four salts showed a similar fashion to one another, though the four-probe resistivity measurements exhibited a variety of temperature dependences. Unexpectedly, the Sb2F11 salt was obtained by the electrolysis with TBA.SbF6 in methanol, and showed semiconducting behavior. The composition was (C1TET-TTF)4Sb2F11 with a binuclear anion of two Sb centered octahedra sharing a F atom.