New Radical-Cation Salts Based on the TMTTF and TMTSF Donors with Iron and Chromium Bis(Dicarbollide) Complexes: Synthesis, Structure, Properties

New radical-cation salts based on tetramethyltetrathiafulvalene (TMTTF) and tetramethyltetraselenefulvalene (TMsTSF) with metallacarborane anions (TMTTF)[3,3′-Cr(1,2-C2B9H11)2], (TMTTF)[3,3′-Fe(1,2-C2B9H11)2], and (TMTSF)2[3,3′-Cr(1,2-C2B9H11)2] were synthesized by electrocrystallization. Their crystal structures were determined by single crystal X-ray diffraction, and their electrophysical properties in a wide temperature range were studied. The first two salts are dielectrics, while the third one is a narrow-gap semiconductor: σRT = 5 × 10−3 Ohm−1cm−1; Ea ≈ 0.04 eV (aprox. 320 cm−1).

Dihedral-Angle Dependence of Intermolecular Transfer Integrals in BEDT-BDT-Based Radical-Cation Salts with θ-Type Molecular Arrangements

We report the structural and physical properties of a new organic Mott insulator (BEDT-BDT)AsF6 (BEDT-BDT: benzo[1,2-g:4,5-g′]bis(thieno[2,3-b][1,4dithiin). This AsF6 salt has the same structure as the PF6 salt. Although the anions are disordered, the donor molecules form a θ-type arrangement. The temperature dependence of the resistivity exhibits semiconducting behavior. The static magnetic susceptibility follows Curie–Weiss law over a wide temperature range; however, below 25 K, the magnetic susceptibility is in agreement with a one-dimensional chain model with the exchange coupling J = 7.4 K. No structural phase transition was observed down to 93 K. At 270 K, the Fermi surface calculated by the tight-binding approximation is a two-dimensional cylinder; however, it is significantly distorted at 93 K. This is because the dihedral angles between the BEDT-BDT molecules become larger due to lattice shrinkage at low temperatures, which results in a smaller transfer integral (t1) along the stack direction. This slight change in the dihedral angle gives rise to a significant change in the electronic structure of the AsF6 salt. Radical-cation salts using BEDT-BDT, in which the highest occupied molecular orbital does not have a dominant sign throughout the molecule, are sensitive to slight differences in the overlap between the molecules, and their electronic structures are more variable than those of conventional θ-type conductors.

First Molecular Superconductor with the Tris(Oxalato)Aluminate Anion, β″-(BEDT-TTF)4(H3O)Al(C2O4)3·C6H5Br, and Isostructural Tris(Oxalato)Cobaltate and Tris(Oxalato)Ruthenate Radical Cation Salts

Peter Day’s research group reported the first molecular superconductor containing paramagnetic metal ions in 1995, β″-(BEDT-TTF)4(H3O)Fe(C2O4)3·C6H5CN. Subsequent research has produced a multitude of BEDT-TTF-tris(oxalato)metallate salts with a variety of structures and properties, including 32 superconductors to date. We present here the synthesis, crystal structure, and conducting properties of the newest additions to the Day series including the first superconductor incorporating the diamagnetic tris(oxalato)aluminate anion, β″-(BEDT-TTF)4(H3O)Al(C2O4)3·C6H5Br, which has a superconducting Tc of ~2.5 K. β″-(BEDT-TTF)4(H3O)Co(C2O4)3·C6H5Br represents the first example of a β″ phase for the tris(oxalato)cobaltate anion, but this salt does not show superconductivity.

Chiral Radical Cation Salts of Me-EDT-TTF and DM-EDT-TTF with Octahedral, Linear and Tetrahedral Monoanions

Methyl-ethylenedithio-tetrathiafulvalene (Me-EDT-TTF (1) and dimethyl-ethylenedithio-tetrathiafulvalene (DM-EDT-TTF (2) are valuable precursors for chiral molecular conductors, which are generally obtained by electrocrystallization in the presence of various counter-ions. The number of the stereogenic centers, their relative location on the molecule, the nature of the counter-ion and the electrocrystallization conditions play a paramount role in the crystal structures and conducting properties of the resulting materials. Here, we report the preparation and detailed structural characterization of the following series of radical cation salts: (i) mixed valence (1)2AsF6 as racemic, and (S) and (R) enantiomers; (ii) [(S)-1]AsF6·C4H8O and [(R)-1]AsF6·C4H8O where a strong dimerization of the donors is observed; (iii) (1)I3 and (2)I3 as racemic and enantiopure forms and (iv) [(meso)-2]PF6 and [(meso)-2]XO4 (X = Cl, Re), based on the new donor (meso)-2. In the latter, the two methyl substituents necessarily adopt axial and equatorial conformations, thus leading to a completely different packing of the donors when compared to the chiral form (S,S)/(R,R) of 2 in its radical cation salts. Single crystal resistivity measurements, complemented by thermoelectric power measurements in the case of (1)2AsF6, suggest quasi-metallic conductivity for the latter in the high temperature regime, with σRT ≈ 1–10 S cm–1, while semiconducting behavior is observed for the (meso)-2 based salts.

New Radical Cation Salts Based on BDH-TTP Donor: Two Stable Molecular Metals with a Magnetic [ReF6]2− Anion and a Semiconductor with a [ReO4]− Anion

Three radical cation salts of BDH-TTP with the paramagnetic [ReF6]2− and diamagnetic [ReO4]− anions have been synthesized: κ-(BDH-TTP)4ReF6 (1), κ-(BDH-TTP)4ReF6·4.8H2O (2) and pseudo-κ″-(BDH-TTP)3(ReO4)2 (3). The crystal and band structures, as well as the conducting properties of the salts, have been studied. The structures of the three salts are layered and characterized by alternating κ-(1, 2) and κ″-(3) type organic radical cation layers with inorganic anion sheets. Similar to other κ-salts, the conducting layers in the crystals of 1 and 2 are formed by BDH-TTP dimers. The partial population of positions of Re atoms and disorder in the anionic layers of 1–3 are their distinctive features. Compounds 1 and 2 show the metallic character of conductivity down to low temperatures, while 3 is a semiconductor. The ac susceptibility of crystals 1 was investigated in order to test the possible slow relaxation of magnetization associated with the [ReF6]2− anion.

Unusual stoichiometry, band structure and band filling in conducting enantiopure radical cation salts of TM-BEDT-TTF showing helical packing of the donors

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...