| Project/Area Number |
16350100
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| Research Category |
Grant-in-Aid for Scientific Research (B)
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| Allocation Type | Single-year Grants |
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| Section | 一般 |
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| Research Field |
Functional materials/Devices
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| Research Institution | Kyoto University |
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Principal Investigator |
TANAKA Kazuyoshi KYOTO UNIVERSITY, MOLECULAR ENGINEERING, PROFESSOR, 工学研究科, 教授 (90155119)
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| Co-Investigator(Kenkyū-buntansha) |
ITO Akihiro KYOTO UNIVERSITY, MOLECULAR ENGINEERING, ASSOCIATE PROFESSOR, 工学研究科, 助教授 (90293901)
FUENO Hiroyuki KYOTO UNIVERSITY, MOLECULAR ENGINEERING, RESEARCH ASSOCIATE, 工学研究科, 助手 (30212179)
MISAKI Yohji EHIME UNIVERSITY, MATERIALS SCIENCE AND BIOTECHNOLOGY, PROFESSOR, 理工学研究科, 教授 (90202340)
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| Project Period (FY) |
2004 – 2006
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| Project Status |
Completed (Fiscal Year 2006)
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| Budget Amount *help |
¥14,800,000 (Direct Cost: ¥14,800,000)
Fiscal Year 2006: ¥1,700,000 (Direct Cost: ¥1,700,000)
Fiscal Year 2005: ¥1,700,000 (Direct Cost: ¥1,700,000)
Fiscal Year 2004: ¥11,400,000 (Direct Cost: ¥11,400,000)
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| Keywords | tetrathiapentalene / molecular conductors / cyclic votammetry / X-ray structure analysis / band calculation / electrical conductivity / テトラセレナフルバレン / 酸化還元電位 / ドナー / 有機伝導体 / 磁化率 |
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| Research Abstract |
(1)X-Ray structure analysis of (CHTM-TTP)_2GaCl_4(PhCl)_x and (CHSM-TTP)_2MCl_4(PhCl)_x (M = Ga, Fe) have been carried out. These three salts are isostructural with each other. The donors form a face-to-face stacked column along the a axis. The two neighboring columns along the c direction are divided by the insulating MCl_4- anions and the solvents used for crystallization. The donors are a little dimerized in the column, and the interstack interactions are approximately 20-25% as large as that of the larger intrastack overlap integral. These three salts exhibited relatively high conductivity of σrt. = 2-11 S cm^1 on a single crystal. They showed metallic temperature dependence down to 160-250 K, below which the resisitivity gradually increased.
(2) Single crystals of radical cations with octahedral anions based on BTM-TTP have been prepared. X-Ray structure analysis revealed that needle-like crystals of (BTM-TTP)_2X (X = PF_6, TaF_6) have the so-called 13-type array of the donors. On the other hand, the plate-like crystal of (BTM-TTP)_2SbF_6 possesses the 0-type array of the donors. Electrical conductivity measurement revealed that β-(BTM-TTP)_2X (X = PF_6, TaF_6), exhibited metallic temperature dependence of resistivity down to 5 K. In contrast, θ-(BTM-TTP)_2SbF_6 showed semiconductive temperature dependence of 0.13 eV.
(3) Selenium analogues of TTP derivatives involving TSF moiety have been synthesized. Cylic voltamograms revealed that the positive charge formed by the first oxidation mainly distributes over the TTF moiety. The vinylogous TTF analogues forms highly conducting I_<3-> salt of σ_<rt> = 8-36 S cm^<-1> on a compressed pellet. Because this salt has exhibited semiconductive behavior with very low activation energy of 0.02-0.05 eV, it is expected to show metallic conductivity on a single crystal.
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