Synthesis and Structures of Highly Conducting Charge-Transfer Salts of Selenium Containing TTM-TTP Derivatives

  • Minoru Ashizawa
    Department of Organic and Polymeric Materials, Graduate School of Science and Engineering, Tokyo Institute of Technology
  • Akane Akutsu
    Department of Organic and Polymeric Materials, Graduate School of Science and Engineering, Tokyo Institute of Technology
  • Bunpei Noda
    Department of Organic and Polymeric Materials, Graduate School of Science and Engineering, Tokyo Institute of Technology
  • Hirofumi Nii
    Department of Organic and Polymeric Materials, Graduate School of Science and Engineering, Tokyo Institute of Technology
  • Tadashi Kawamoto
    Department of Organic and Polymeric Materials, Graduate School of Science and Engineering, Tokyo Institute of Technology
  • Takehiko Mori
    Department of Organic and Polymeric Materials, Graduate School of Science and Engineering, Tokyo Institute of Technology
  • Takashi Nakayashiki
    Department of Molecular Engineering, Graduate School of Engineering, Kyoto University
  • Yohji Misaki
    Department of Molecular Engineering, Graduate School of Engineering, Kyoto University
  • Kazuyoshi Tanaka
    Department of Molecular Engineering, Graduate School of Engineering, Kyoto University
  • Kazuo Takimiya
    Department of Applied Chemistry, Graduate School of Engineering, Hiroshima University
  • Tetsuo Otsubo
    Department of Applied Chemistry, Graduate School of Engineering, Hiroshima University

説明

<jats:title>Abstract</jats:title> <jats:p>Selenium-substituted TTM-TTP (2,5-bis[4,5-bis(methylthio)-1,3-dithiol-2-ylidene]-1,3,4,6-tetrathiapentalene) derivatives (1a–1d), in which several 1,3-dithiole rings of the bis-fused TTF framework are replaced by 1,3-diselenole rings, have been prepared. In particular, we have accomplished the first selenium substitution of the inner TTP part (1a). The 1:1 composition iodine salt, (1a)I3, is an insulator constructed of the donor trimers. The 1:1 GaCl4 salt, (1a)GaCl4, has a uniform column isostructural to the sulfur analog, (TTM-TTP)FeBr1.8Cl2.2; it exhibits metallic conduction down to about 60 K, the lowest metal–insulator (M–I) transition temperature in 1:1 salts. The donors 1c and 1d give the iodine salts isostructural to the sulfur analog, (TTM-TTP)(I3)5/3. By the selenium substitution, the M–I transition of (1d)(I3)5/3 is entirely suppressed.</jats:p>

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