Synthesis and Properties of 2-Alkylidene-1,3-dithiolo[4,5-d]-4,5-ethylenediselenotetrathiafulvalene Derivatives and Crystal Structures of Their Cation Radical Salts

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  • Keisuke Furuta
    Department of Applied Chemistry, Graduate School of Science and Engineering, Ehime University, 3 Bunkyo-cho, Matsuyama 790-8577, Japan
  • Shuhei Kohno
    Department of Applied Chemistry, Graduate School of Science and Engineering, Ehime University, 3 Bunkyo-cho, Matsuyama 790-8577, Japan
  • Takashi Shirahata
    Department of Applied Chemistry, Graduate School of Science and Engineering, Ehime University, 3 Bunkyo-cho, Matsuyama 790-8577, Japan
  • Koya Yamasaki
    Department of Applied Chemistry, Graduate School of Science and Engineering, Ehime University, 3 Bunkyo-cho, Matsuyama 790-8577, Japan
  • Shojun Hino
    Department of Applied Chemistry, Graduate School of Science and Engineering, Ehime University, 3 Bunkyo-cho, Matsuyama 790-8577, Japan
  • Yohji Misaki
    Department of Applied Chemistry, Graduate School of Science and Engineering, Ehime University, 3 Bunkyo-cho, Matsuyama 790-8577, Japan

説明

<jats:p>Tetrathiafulvalene derivatives condensed with 2-alkylidene-1,3-dithiole moiety, MeDTES (2-isopropylidene-1,3-dithiolo[4,5-d]-4,5-ethylenediselenotetrathiafulvalene), EtDTES (2-(pentan-3-ylidene)-1,3-dithiolo[4,5-d]-4,5-ethylenediselenotetrathiafulvalene), and CPDTES (2-cyclopentanylidene-1,3-dithiolo[4,5-d]-4,5-ethylenediselenotetrathiafulvalene) have been synthesized. Crystal structure analysis of MeDTES salts with Au(CN)4−, ReO4−, and I3− and a CPDTES salt with I3− reveals that the donor−anion ratios of all salts are 1:1. Band calculation of (MeDTES)[Au(CN)4] suggests a quasi-one-dimensional Fermi surface that could be the result of the uniform stack of donor molecules. In spite of this stacking, the salt is a Mott insulator because of a large on-site Coulomb interaction U. (MeDTES)(ReO4)(H2O)0.5 possesses Fermi points and exhibits semiconducting behavior with small activation energy (Ea = 0.058 eV). I3− ions form disordered infinite chain in (MeDTES)(I3)(DCE)0.25, but those in (CPDTES)(I3) exist as discrete ions. They show low conductivity (10−4−10−2 S cm−1) at room temperature and the band calculation suggests that they are band insulator.</jats:p>

収録刊行物

  • Crystals

    Crystals 2 (2), 393-412, 2012-05-09

    MDPI AG

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