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 (BEDTBDT)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.