Old Donors for New Molecular Conductors: Combining TMTSF and BEDT-TTF with Anionic (TaF6)1−x/(PF6)x Alloys

Tetramethyl-tetraselenafulvalene (TMTSF) and bis(ethylenedithio)-tetrathiafulvalene (BEDT-TTF) are flagship precursors in the field of molecular (super)conductors. The electrocrystallization of these donors in the presence of (n-Bu4N)TaF6 or mixtures of (n-Bu4N)TaF6 and (n-Bu4N)PF6 provided Bechgaard salts formulated as (TMTSF)2(TaF6)0.84(PF6)0.16, (TMTSF)2(TaF6)0.56(PF6)0.44, (TMTSF)2(TaF6)0.44(PF6)0.56 and (TMTSF)2(TaF6)0.12(PF6)0.88, together with the monoclinic and orthorhombic phases δm-(BEDT-TTF)2(TaF6)0.94(PF6)0.06 and δo-(BEDT-TTF)2(TaF6)0.43(PF6)0.57, respectively. The use of BEDT-TTF and a mixture of (n-Bu4N)TaF6/TaF5 afforded the 1:1 phase (BEDT-TTF)2(TaF6)2·CH2Cl2. The precise Ta/P ratio in the alloys has been determined by an accurate single crystal X-ray data analysis and was corroborated with solution 19F NMR measurements. In the previously unknown crystalline phase (BEDT-TTF)2(TaF6)2·CH2Cl2 the donors organize in dimers interacting laterally yet no organic-inorganic segregation is observed. Single crystal resistivity measurements on the TMTSF based materials show typical behavior of the Bechgaard phases with room temperature conductivity σ ≈ 100 S/cm and localization below 12 K indicative of a spin density wave transition. The orthorhombic phase δo-(BEDT-TTF)2(TaF6)0.43(PF6)0.57 is semiconducting with the room temperature conductivity estimated to be σ ≈ 0.16–0.5 S/cm while the compound (BEDT-TTF)2(TaF6)2·CH2Cl2 is also a semiconductor, yet with a much lower room temperature conductivity value of 0.001 to 0.0025 S/cm, in agreement with the +1 oxidation state and strong dimerization of the donors.

One-Dimensional Alternating Extended Hubbard Model at Quarter-Filling and Its Applications to Structural Instabilities of Organic Conductors

The one-dimensional extended Hubbard model with lattice dimerization and alternated site potentials is analyzed using the renormalization group method. The coupling of electrons to structural degrees of freedom such as the anion lattice and acoustic phonons is investigated to obtain the possible instabilities against the formation of lattice superstructures. Applications of the theory to anionic and spin-Peierls instabilities in the Fabre and Bechgaard salts series of organic conductors and ordered alloys are presented and discussed.

Application of superhalogens in the design of organic superconductors

This study shows that the acceptors of super-electrons in organic superconductors belong to the class of superhalogens and proposes that a new series of salts, (TMTSF)2X, can be realized where X is a superhalogen, which possess similar properties to those of the existing Bechgaard salts. Thus, the concept of superhalogens can be useful in designing potential candidates for organic superconductors.

Electrodynamics of Bechgaard Salts: Optical Properties of One-Dimensional Metals

The electrodynamic properties of the quasi-one-dimensional organic conductors (TMTSF)2X are discussed, with particular emphasis on important deviations from the simple Drude model, the transition from a Luttinger-liquid to a Fermi-liquid behavior at the dimensional crossover when pressure is applied or temperature reduced, indications of a pseudogap as well as a low-frequency collective mode. Superconductivity and spin-density-wave ground states breaking the symmetry and gaps should occur in the excitation spectra. The previous literature is summarized and the current status of our understanding presented. Novel THz experiments on (TMTSF)2PF6 and (TMTSF)2ClO4 not only shine light into some of the open questions, but also pose new ones.