Dihedral-angle dependence of intermolecular transfer integrals in bedt-bdt-based radical-cation salts with θ-type molecular arrangements

Tomofumi Kadoya, Shiori Sugiura, Toshiki Higashino, Keishiro Tahara, Kazuya Kubo, Takahiko Sasaki, Kazuo Takimiya, Jun Ichi Yamada

Research output: Contribution to journalArticlepeer-review

1 Citation (Scopus)


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.

Original languageEnglish
Article number868
Issue number8
Publication statusPublished - 2021 Aug


  • Molecular orbitals
  • Organic conductors
  • Organic semiconductors

ASJC Scopus subject areas

  • Chemical Engineering(all)
  • Materials Science(all)
  • Condensed Matter Physics
  • Inorganic Chemistry


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