Band Filling Control by Chemical Approach in Molecular Conductors, (TTM-TTP)M<i><sub>x</sub></i> Cl<sub>4</sub> [M, M‘ = Fe, Ga, Co, and Mn]

  • Mao Katsuhara
    Department of Organic and Polymeric Materials, Graduate School of Science and Engineering, Tokyo Institute of Technology, Meguro-ku, Tokyo 152-8552, Japan, and Department of Molecular Engineering, Graduate School of Engineering, Kyoto University, Yoshida, Kyoto 606-8501, Japan
  • Shinya Kimura
    Department of Organic and Polymeric Materials, Graduate School of Science and Engineering, Tokyo Institute of Technology, Meguro-ku, Tokyo 152-8552, Japan, and Department of Molecular Engineering, Graduate School of Engineering, Kyoto University, Yoshida, Kyoto 606-8501, Japan
  • Takehiko Mori
    Department of Organic and Polymeric Materials, Graduate School of Science and Engineering, Tokyo Institute of Technology, Meguro-ku, Tokyo 152-8552, Japan, and Department of Molecular Engineering, Graduate School of Engineering, Kyoto University, Yoshida, Kyoto 606-8501, Japan
  • Yohji Misaki
    Department of Organic and Polymeric Materials, Graduate School of Science and Engineering, Tokyo Institute of Technology, Meguro-ku, Tokyo 152-8552, Japan, and Department of Molecular Engineering, Graduate School of Engineering, Kyoto University, Yoshida, Kyoto 606-8501, Japan
  • Kazuyoshi Tanaka
    Department of Organic and Polymeric Materials, Graduate School of Science and Engineering, Tokyo Institute of Technology, Meguro-ku, Tokyo 152-8552, Japan, and Department of Molecular Engineering, Graduate School of Engineering, Kyoto University, Yoshida, Kyoto 606-8501, Japan

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説明

TTM-TTP-based 1:1-composition organic conductors with counteranions containing alloyed metals, [TTM-TTP = 2,5-bis[4,5-bis(methylthio)-1,3-dithiol-2-ylidene]-1,3,4,6-tetrathiapentalene; M, M‘ = Fe, Ga, Co, and Mn], have been prepared. The degrees of oxidization of TTM-TTP molecules change with the ratio of monovalent (FeCl4- and GaCl4-) and divalent anions (CoCl42- and MnCl42-). Accordingly, the band filling of the donor HOMO is chemically changed. These salts have the same crystal structure, consisting of one-dimensional uniform donor stacks, and are highly conductive. The conductivity is essentially flat down to 100−200 K, but the room-temperature resistivity and the thermoelectric power systematically increase as the band filling decreases from half filling to empty.

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