A mixed-valence conducting cation radical salt of the unsymmetrically substituted o-Me2TTF donor molecule (TTF is tetrathiafulvalene) was obtained upon electrocrystallization in the presence of the non-centrosymmetric NO3- anion. It crystallizes at room temperature in the monoclinic P21/c space group, with the anion disordered on an inversion centre. The donor molecules are stacked along the a axis. A 90° rotation of the longest molecular axis of o-Me2TTF generates a chessboard-like structure, preventing lateral S⋯S contacts between stacks and providing a strongly one-dimensional electronic system, as confirmed by overlap interaction energies and band structure calculations. A strong dimerization within the stacks explains the semi-conducting behaviour of the salt, with σroom temp = 3-5 S cm-1 and Eactivated = 0.12-0.14 eV. An X-ray diffuse scattering survey of reciprocal space, combined with full structure resolutions at low temperatures (250, 85 and 20 K), evidenced the succession of two structural transitions: a ferroelastic one with an anion-ordering (AO) process and the establishment of a (0, ½, ½) superstructure below 124 (±3) K, also visible via resistivity thermal dependence, followed by a stack tetramerization with the establishment of a (½, ½, ½) superstructure below 90 (±5) K. The latter ground state is driven by a spin-Peierls (SP) instability, as demonstrated by the temperature dependence of the magnetic susceptibility. Surprisingly, these two kinds of instability appear to be fully decoupled here, at variance with other tetra-methyl-tetra-thia-fulvalene (TMTTF) or tetramethyl-tetra-selena-fulvalene (TMTSF) salts with such non-centrosymmetric counter-ions.
Keywords: anion-ordering transition; molecular crystals; organic conductors; phase transitions; spin-Peierls transition.