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Electrocrystallization of tetramethyl-bis(ethylenedithio)-tetrathiafulvalene (TM-BEDT-TTF) (1) as pure (S,S,S,S) and (R,R,R,R) enantiomers in the presence of (n-Bu4N)2(Mo6O19) and chloroform or bromoform afforded a series of four isostructural enantiopure radical cation salts [(S/R)-1]9(Mo6O19)5·(CHX3)2 (X = Cl, Br) crystallizing in the trigonal non-centrosymmetric space group R32. In the formula unit there are six donors of type A and three donors of type B showing, respectively, (ax, ax, eq, eq) and all-ax conformations (ax = axial, eq = equatorial) of the methyl substituents. The donors form a hexagonal network in the ab plane with a helical twist between them leading to lateral orbital overlap interactions. Electrocrystallization of the racemic donor provided the compound [(rac)-1]2(Mo6O19) which crystallized in the monoclinic system P21/n. Single crystal resistivity measurements show semiconducting behaviour of the enantiopure materials with a relatively high room temperature conductivity of 0.8–1.2 S cm−1, but rather insensitive to applied pressures of up to 2.3 GPa. Analysis of the electronic structure of the conducting solids through extended Hückel tight-binding band structure calculations indicates a Mott insulator behaviour explaining the semiconducting character and suggests that these compounds are valuable candidates for Dirac cone materials. Further insight into the conducting properties is provided by preliminary field effect transistor measurements.

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 tetramethyltetrathiafulvalene (TMTTF) and tetramethyl-tetraselenafulvalene (TMTSF). Here we show that the use of the oxo-bis[pentafluorotantalate(V)] dianion [Ta2F10O]2 affords upon electrocrystallization of TMTTF, TMTSF, bis(ethylenedithio)-tetrathiafulvalene (BEDT-TTF), racemic dimethyl-ethylenedithio-tetrathiafulvalene ((rac)- DM-EDT-TTF), and enantiopure (S,S)-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 b-type. The anion arranges either parallel or perpendicular to the stack direction and establishes numerous intermolecular CH/F hydrogen bonds. Thus, the [Ta2F10O]2 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 Huckel band structure calculations. The room temperature conductivity ¨ values are relatively high, i.e. 0.25–1.1 S cm 1 , 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, i.e. 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 [Ta2F11

An asymmetric mechanism for correlated motion occurring in noninteracting pairs of adjacent orthogonal 1,4-bis(carboxyethynyl)bicyclo[1.1.1]pentane (BCP) rotators 1 in the solid state is unraveled and shown to play an important role in understanding the dynamics in the crystalline rotor, Bu4N+[1–]·H2O. Single crystal X-ray diffraction and calculation of rotor–rotor interaction energies combined with variable-temperature, variable-field 1H spin–lattice relaxation experiments led to the identification and microscopic rationalization of two distinct relaxation processes.