Conservation of structural arrangements and 3 : 1 stoichiometry in a series of crystalline conductors of TMTTF, TMTSF, BEDT-TTF, and chiral DM-EDT-TTF with the oxo-bis[pentafluorotantalate(v)] dianion.

The occurrence of isostructural conducting radical cation salts of diversely substituted tetrathiafulvalene (TTF) precursors with the same anion is most often limited to very similar derivatives such as tetramethyl-tetrathiafulvalene (TMTTF) and tetramethyl-tetraselenafulvalene (TMTSF). Here we show that the use of the oxo-bis[pentafluorotantalate(v)] dianion [TaFO] affords upon electrocrystallization of TMTTF, TMTSF, bis(ethylenedithio)-tetrathiafulvalene (BEDT-TTF), racemic dimethyl-ethylenedithio-tetrathiafulvalene (()-DM-EDT-TTF), and enantiopure (,)-DM-EDT-TTF a series of mixed valence crystalline radical cation salts with the same 3 : 1 stoichiometry. The donor layers show similar features in the five materials, such as alternation of trimeric units within stacks which arrange in parallel columns of β-type. The anion arranges either parallel or perpendicular to the stack direction and establishes numerous intermolecular CH⋯F hydrogen bonds. Thus, the [TaFO] dianion, most likely because of its shape and propensity to engage in hydrogen bonding, is the first one to be able to induce the same type of structural arrangement for a broad series of different donors, a result which is important in the crystal engineering of molecular conductors. All the compounds are band gap semiconductors, according to single crystal resistivity measurements and extended Hückel band structure calculations. The room temperature conductivity values are relatively high, 0.25-1.1 S cm, except for the TMTTF salt, whose conductivity value is two orders of magnitude smaller than its isostructural TMTSF counterpart, in agreement with the band gap energy value. As a general feature of these materials, variations in the inter- and intra-trimer interactions modulate their band structure, energy dispersion and band gaps. The preparation of this series of radical cation salts with a sturdy 3 : 1 stoichiometry might question previous assignments of the anion as [TaF] in radical cation salts of TMTSF and BEDT-TTF.