構造制御に基づく新規機能性導電体の開拓

2007 Fiscal Year Final Research Report Summary

• Project/Area Number: 15073215
• Research Category: Grant-in-Aid for Scientific Research on Priority Areas
• Allocation Type: Single-year Grants
• Review Section: Science and Engineering
• Research Institution: Kyoto University
• Principal Investigator: 矢持 秀起 Kyoto University, 低温物質科学研究センター, 教授 (20182660)
• Co-Investigator(Kenkyū-buntansha): 前里 光彦 京都大学, 大学院・理学研究科, 助教 (60324604) ; 大塚 晃弘 京都大学, 低温物質科学研究センター, 助教 (90233171)
• Project Period (FY): 2003 – 2007
• Keywords: 有機導体 / 分子性固体 / 光誘起相転移 / 電荷整列 / 合成化学 / 電子-格子相互作用

Research Abstract

透明かつ金属的挙動を示すBEDO-TTF錯体を組込んだ導電性高分子膜(RDP膜)について、可逆的な結晶水の出入りと、これに伴う導電性の変化を観測した。
擬1次元的な電子状態を持ち、際立った分子変形を伴う金属-絶縁体転移を起こす(EDO-TTF)_2PF_6の低温相への光照射に伴う超高速・高効率な応答が、熱的転移現象ではなく光誘起相転移であることが確定された。また、この系が電子-格子相互作用の強い系である事も確認された。更に、一軸歪により熱的相転移温度が劇的に変化したり、部分重水素化によって転移温度が変化する等、僅かな外的・内的変化に敏感に応答する物質であることが見出された。また、同形錯体との比較を行い、室温相でのドナー分子の2量化の強さと転移温度の相関を検討した。
EDO-TTFにメチル基を導入することにより、2次元的な電子状態を持ち低温まで金属状態を保つ錯体を得る事が出来た。また、室温直上で相転移を起こす電荷秩序物質も開拓できた。
κ-(ET)_2Cu_2(CN)_3の基底状態がスピン液体であることを確定し、1軸歪を加えることにより超伝導状態に転移させる事も見出した。β"-(ET)_2SF_5CH_2CF_2SO_3の1軸歪下での超伝導転移温度を検討した。κ-(ET)_4M(CN)_6[Et_4N]・2H_2O(M=Co, Fe)が冷却に伴い徐々に電荷秩序状態へと転移することが判った。ヨウ素を含むドナーDIETSeと鉄を含む陰イオンとの錯体について、前者のπ電子と後者のd電子が相互作用することにより磁気秩序が形成される事を見出した。また、磁気抵抗にメモリー効果がある事が判った。
C_<60>, C_<70>の陰イオンラジカルを含む錯体を作成し温度変化に伴う可逆的な2量体形成・解離を観測した。これらの中には、低温相においてC_60同士が単結合で結ばれたものと2重結合で結ばれたものが共存する物質も見出された。

Research Products

• [Journal Article] Formation of Two-dimensional Metals by Weak Intermolecular Interactions Based on the Asymmetric EDO-TTF Derivatives (2008)
  • Author(s): X. F. Shao, Y. Nakano, H. Yamochi, A. D. Dubrovskiy, A. Otsuka, T. Murata, Y. Yoshida, G. Saito, S. Koshihara
  • Journal Title: Journal of Materials Chemistry 18 Pages: 2131-2140
  • Peer Reviewed
• [Journal Article] Dimerization of C_<60>^<□_> in Multi-component Ionic Complexes with Bis(ethylenedithio) tetrathiafulvalene: (cation^+)_2□ET□(C_<60>^<□_>)_2 (2007)
  • Author(s): D. V. Konarev, S. S. Khasanov, G. Saito, A. Otsuka, R. N. Lyubovskaya
  • Journal Title: Journal of Materials Chemistry 17 Pages: 4171-4177
  • Peer Reviewed
• [Journal Article] Phase transition from Mott insulating phase into charge ordering phase with molecular deformation in the charge transfer saltsκ-(BEDT-TTF)_4 [M (CN)_6][N(C_2H_5)_4]・2H_2O (M = Co^<III> and Fe^<III>) (2007)
  • Author(s): A. Ota, L. Ouahab, S. Golhen, Y. Yoshida, M. Maesato, G. Saito, R. Swietlik
  • Journal Title: Chemistry of Materials 19 Pages: 2455-2462
  • Peer Reviewed
• [Journal Article] Crystal structures and physical properties of (EDO-TTF)_5(BF_4)_3 and(EDO-TTF)_4(Sb_2F_<11>)_<0.85>(H_2O)_4 (2007)
  • Author(s): A. Ota, H. Yamochi, G. Saito
  • Journal Title: "Multifunctional Conducting Molecular Materials", eds. G. Saito, F. Wudl, R. C. Haddon, K. Tanigaki, T. Enoki, H. E. Katz, M. Maesato, RSC Publishing, Cambridge, UK. Pages: 115-118
  • Peer Reviewed
• [Journal Article] Recent progress of (EDO-TTF)_2PF_6 and related complexes (2007)
  • Author(s): H. Yamochi, G. Saito
  • Journal Title: "Multifunctional Conducting Molecular Materials", eds. G. Saito, F. Wudl, R. C. Haddon, K. Tanigaki, T. Enoki, H. E. Katz, M. Maesato, RSC Publishing, Cambridge, UK. Pages: 107-114
  • Peer Reviewed
• [Journal Article] Charge disproportionation with metallic conductivity in new ET salt, (ET)_3 (AuBr_2)_2 (AuBr_4)_2 (solv)_x, having a peculiar crystal structure (2007)
  • Author(s): M. Sakata, M. Maesato, G. Saito, T. Yamamoto, K. Yakushi, S. S. Khasanov, N. G. Spitsina, A. D. Dubrovskii, E. B. Yagubskii, p. Deplano, M. L. Mercuri
  • Journal Title: "Multifunctional Conducting Molecular Materials", eds. G. Saito, F. Wudl, R. C. Haddon, K. Tanigaki, T. Enoki, H. E. Katz, M. Maesato, RSC Publishing, Cambridge, UK. Pages: 91-96
  • Peer Reviewed
• [Journal Article] Coexistence of quasi-one- and -two-dimensional electronic structures in(EDO-TTF)_2X (X = GaCl_4, ReO_4) (2006)
  • Author(s): A. Ota, H. Yamochi, G. Saito
  • Journal Title: J. Low Temp. Phys. 142 Pages: 425-428
  • Peer Reviewed
• [Journal Article] Negatively charged π-(C_<60^->)_2 dimer with biradical state at room temperature (2006)
  • Author(s): D. V. Konarev, S. S. Khasanov, A. Otsuka, G. Saito, R. N. Lyubovskaya
  • Journal Title: J. Am. Chem. Soc. 128 Pages: 9292-9293
  • Peer Reviewed
• [Journal Article] New organic conductors based on dibromo- and diiodo-TSeFs with magnetic and non-magnetic MX_4 counter anions (M = Fe, Ga ; X = C1, Br) (2006)
  • Author(s): T. Shirahata, M. Kibune, M. Maesato, T. Kawashima, G. Saito, T. Imakubo
  • Journal Title: J. Mater. Chem. 16 Pages: 3381-3390
  • Peer Reviewed
• [Journal Article] Emergence of inhomogeneous moments from spin liquid in the triangular-lattice Mott insulator κ-(ET)_2Cu_2(CN)_3 (2006)
  • Author(s): Y. Shimizu, K. Miyagawa, K. Kanoda, M. Maesato, G. Saito
  • Journal Title: Phys. Rev., B 73 Pages: 140407/1-4
  • Peer Reviewed
• [Journal Article] Anomalous magnetoresistance in the π-d system (DIETSe)_2FeCl_4. (2006)
  • Author(s): M. Maesato, T. Kawashima, G. Saito, M. Kibune, T. Shirahata, T. Imakubo
  • Journal Title: Mol. Cryst. Liq. Cryst. 455 Pages: 123-127
  • Peer Reviewed
• [Journal Article] Uniaxial Strain Investigation on the Metal-Insulator Transition of (EDO-TTF)_2PF_6 (2005)
  • Author(s): M. Sakata, M. Maesato, A. Ota, H. Yamochi, G. Saito
  • Journal Title: Synthetic Metals 153 Pages: 393-396
  • Peer Reviewed
• [Journal Article] NMR study of Spin-Liquid State and Mott Transition in the Spin-Frustrated Organic System, κ-(ET)_2Cu_2(CN)_3 (2005)
  • Author(s): Y. Shimizu, Y. Kurosaki, K. Miyagawa, K. Kanoda, M. Maesato, G. Saito
  • Journal Title: Synthetic Metals 152 Pages: 393-396
  • Peer Reviewed
• [Journal Article] Crystal Structure and Magnetic Properties of an Ionic Multi-Component Complex of Fullerene (OMTTF・I_3)・C_<60> Comparison with OMTTF・I_3 Salts (2005)
  • Author(s): D. V. Konarev, S. S. Khasanov, A. Otsuka, G. Saito, R. N. Lyubovskaya
  • Journal Title: Synthetic Metals 151 Pages: 231-238
  • Peer Reviewed
• [Journal Article] Neutral and Ionic Complexes of C_<60> with Metal Dibenzyldithiocarbamates. Reversible Dimerization of C_<60>^・-in Ionic Multicomponet Complex [Cr^I(C_6H_6)_2^<・+>]・(C_<60>^・-)・0.5[Pd(dbctc)_2] (2005)
  • Author(s): D. V. Konarev, A. Y. Kovalevsky, A. Otsuka, G. Saito, R. N. Lybovskaya
  • Journal Title: Inorg. Chem. 44 Pages: 9547-9553
  • Peer Reviewed
• [Journal Article] Entropic Evidence for Cooperation of Multiple Instabilities upon a Metal-Insulator Transition in (EDO-TTF)_2PF_6 (2005)
  • Author(s): K. Saito, S. Ikeuchi, A. Ota, H. Yamochi, G. Saito
  • Journal Title: Chem. Phys. Lett. 401 Pages: 76-79
  • Peer Reviewed
• [Journal Article] Gigantic Photoresponse in 1/4-Filled-Band Organic Salt, (EDO-TTF)_2PF_6 (2005)
  • Author(s): M. Chollet, L Guerin, N. Uchida, S. Fukaya, H. Shimoda, T. Ishikawa, K. Matsuda, T. Hasegawa, A. Ota, H. Yamochi, G. Saito, R. Tazaki, S. Adachi, S. Koshihara
  • Journal Title: Science 307 Pages: 86-89
  • Peer Reviewed
• [Journal Article] Humidity Sensitive Conductivity of (BEDO-TTF)_2Br(H_2O)_3 as a Bulk Property (2004)
  • Author(s): H. Yamochi, T. Haneda, A. Tracz, J. Ulanski, O. Drozdova, K. Yakushi, G. Saito
  • Journal Title: J. Phys. IV France 114 Pages: 591-593
  • Peer Reviewed
• [Journal Article] Direct Observation of Bonding and Charge Ordering in (EDO-TTF)_2PF_6 (2004)
  • Author(s): S. Aoyagi, K. Kato, A. Ota, H. Yamochi, G. Saito, H. Suematsu, M. Sakata, M. Takata
  • Journal Title: Angew. Chem. Int. Ed. 43 Pages: 3670-3673
  • Peer Reviewed
• [Journal Article] Formation of Single-Bonded (C_<60^->)_2 and (C_<70^->)_2 Dimers in Crystalline Ionic Complexes of Fullenes (2003)
  • Author(s): D. V. Konarev, S. S. Khasanov, G. Saito, A. Otsuka, Y. Yoshida, R. N. Lyubovskaya
  • Journal Title: J. Am Chem. Soc. 125 Pages: 10074-10083
  • Peer Reviewed
• [Journal Article] Anisotropy in the superconducting transition temperature ofκ-(BEDT-TTF)_2X (2003)
  • Author(s): M. Maesato, Y. Shimizu, T. Ishikawa, G. Saito
  • Journal Title: Synthetic Metals 137 Pages: 1243-1244
  • Peer Reviewed
• [Journal Article] A Novel Metal-Insulator Transition in (EDO-TTF)_2X (X = PF_6, AsF_6) (2003)
  • Author(s): A. Ota, H. Yamochi, G. Saito
  • Journal Title: Synthetic Metals 133 Pages: 463-465
  • Peer Reviewed
• [Journal Article] Spectroscopic Sutudy of the [0110] Ordering in (EDO-TTF)_2PF_6 (2003)
  • Author(s): O. Drozdova, K. Yakushi, A. Ota, H. Yamochi, G. Saito
  • Journal Title: Synthetic Metals 133 Pages: 277-279
  • Peer Reviewed
• [Presentation] Novel Complexes of Ethylenedioxy-1, 3-Dithiole Derivatives (2007)
  • Author(s): Hideki Yamochi, Gunzi Saito
  • Organizer: The 9th China-Japan Joint Symposium on Conduction and Photoconduction in Organic Solids and Related Phenomena
  • Place of Presentation: Friendship Hotel, Beijing, China
  • Year and Date: 20071027-20071029
• [Presentation] Structures and Physical Properties of the Mono-methyl Substituted EDO-TTF (2007)
  • Author(s): X. F. Shao, H. Yamochi, Y. Nakano, Y. Yoshida, M. Sakata, M. Maesato, T. Murata, A. Otsuka, G. Saito, S. Koshihara
  • Organizer: The 9th China-Japan Joint Symposium on Conduction and Photoconduction in Organic Solids and Related Phenomena
  • Place of Presentation: Friendship Hotel, Beijing, China
  • Year and Date: 20071027-20071029
• [Presentation] Isotope Effect on Metal-Insulator Transition: (EDO-TTF)_2X (X =PF_6, AsF_6)Cation Radical Salts (2007)
  • Author(s): Yoshiaki Nakano, Hideki Yamochi, Gunzi Saito, Mikio Uruichi, Kyuya Yakushi
  • Organizer: The 9th China-Japan Joint Symposium on Conduction and Photoconduction in Organic Solids and Related Phenomena
  • Place of Presentation: Friendship Hotel, Beijing, China
  • Year and Date: 20071027-20071029
• [Presentation] Effects of a Methyl Group Introduced in Ethylenedioxy-TTF (2007)
  • Author(s): Hideki Yamochi, Xiangfeng Shao, Yoshiaki Nakanko, Gunzi Saito
  • Organizer: 7th International Symposium on Crystalline Organic Metals, Superconductors and Ferromagnets
  • Place of Presentation: Peniscola, Spain
  • Year and Date: 20070924-20070929
• [Presentation] Isotope Effect on Metal-Insulator Transition: (EDO-TTF)_2XF_6 (X =P, As) with Multi-instability of Metallic State (2007)
  • Author(s): Yoshiaki Nakano, Hideki Yamochi, Gunzi Saito, Mikio Uruichi, Kyuya Yakushi
  • Organizer: 7th International Symposium on Crystalline Organic Metals, Superconductors and Ferromagnets
  • Place of Presentation: Peniscola, Spain
  • Year and Date: 20070924-20070929
• [Presentation] Annihilation of Magnetism due to Faint Molecular Displacements in (TP-EDOT)_3(Sb)_2F_<11>) (benzene) (2006)
  • Author(s): H. Yamochi, J. Hagiwara, M. Soeda, G. Saito
  • Organizer: The International Conference on Science and Technology of Synthetic Metals (ICSM 2006)
  • Place of Presentation: Trinity College, Dublin, Ireland
  • Year and Date: 20060702-20060707
• [Presentation] Recent progress of (EDO-TTF)_2PF_6 and related complexes (2005)
  • Author(s): H. Yamochi, G. Saito
  • Organizer: PACIFICHEM2005 Symposium #115; Science and Engineering of the Future with Multifunctional Conducting Molecular Materials
  • Place of Presentation: Honolulu, HI, USA
  • Year and Date: 20051215-20051217
• [Presentation] Mesomeric fused betainic radicals as single component organic conductors (2005)
  • Author(s): G. Saito, K. Balodis, Y. Yoshida, M. Maesato, H. Yamochi, S. Khasanov
  • Organizer: PACIFICHEM2005 Symposium #115: Science and Engineering of the Future with Multifunctional Conducting Molecular Materials
  • Place of Presentation: Honolulu, HI, USA
  • Year and Date: 20051215-20051217
• [Presentation] Intriguing electrical transport property of C7TET-TTF(TCNQ) (2005)
  • Author(s): A. Otsuka, G. Saito, O. Kina, Y. Yoshida, H. Yamochi
  • Organizer: PACIFICHEM2005 Symposium #115; Science and Engineering of the Feature with Multifunctional Conducting Molecular Materials
  • Place of Presentation: Honolulu, HI, USA
  • Year and Date: 20051215-20051217
• [Presentation] Crystal structure and physical properties of (BO)_2(Mo_6Br_<14>)_2(PhCN) (2005)
  • Author(s): H. Hosoda, K. Nishimura, H. Yamochi, G. Saito, K. Kirakci, S. Cordier, C. Perrin
  • Organizer: PACIFICHEM2005 Symposium #115; Science and Engineering of the Future with Multifunctional Conducting Molecular Materials
  • Place of Presentation: Honolulu, HI, USA
  • Year and Date: 20051215-20051217
• [Presentation] Crystal structures and physical properties of (EDO-TTF)_5(BF_4)_3 and (EDO-TTF)_4(Sb_2F_<11>)_<0.85>(H_2O) (2005)
  • Author(s): A. Ota, H. Yamochi, G. Saito
  • Organizer: PACIFICHEM2005 Symposium #115: Science and Engineering of the Future with Multifunctional Conducting Molecular Materials
  • Place of Presentation: Honolulu, HI, USA
  • Year and Date: 20051215-20051217
• [Presentation] (TP-EDOT)_2PF_6 - Two Dimensional Spin Array in a Three Dimensional Lattice (2005)
  • Author(s): Hideki Yamochi
  • Organizer: Sixth International Symposium on Crystalline Organic Metals, Superconductors, and Ferromagnets
  • Place of Presentation: Key West, Florida, Wyndham Casa Marina Resort
  • Year and Date: 20050911-20050916
• [Presentation] Ultra-fast and Highly Efficient Photo Induced Phase Transition in(EDO-TTF)_2PF_6 (2005)
  • Author(s): H. Yamochi, G. Saito, s. Koshihara
  • Organizer: 54th Fujihara Seminar "Organic Semiconductors and Conductors: Half Century and Future Prospects"
  • Place of Presentation: Ground Hotel New Oji, Tomakomai, Hokkaido, Japan
  • Year and Date: 20050831-20050904
• [Presentation] (EDO-TTF)_2PF_6 - the status quo (2005)
  • Author(s): Hideki Yamochi
  • Organizer: International Symposium on Molecular Conductors (ISMC)
  • Place of Presentation: Hayama, JAPAN
  • Year and Date: 20050717-20050721
• [Presentation] The novel electronic structure of the PF_6 complex of a new donormolecule, TP-EDOT (2004)
  • Author(s): H. Yamochi, J. Hagiwara, M. Soeda, G. Saito
  • Organizer: The International Conference on Science and Technology of Synthetic Metals (ICSM 2004)
  • Place of Presentation: The University of Wollongong, New South Wales, Australia
  • Year and Date: 20040628-20040702
• [Presentation] Recent Progresses in (EDO-TTF)_2PF_6 (2004)
  • Author(s): Hideki Yamochi
  • Organizer: 特定領域研究「新しい環境下における分子性導体の特異な機能の探索」第1回シンポジウム
  • Place of Presentation: 東京工業大学大岡山西9号館デジタル多目的ホール
  • Year and Date: 20040119-20040120
• [Book] "Design of Organic (Super)conductors and Study of their Physical Properties" in NATO SCIENCE Series : II: Mathematics, Physics And Chemistry : Volume139, Organic Conductors, Superconductors and Magnets : From Synthesis to Molecular Electronics, eds. L. Ouahab, E. Yagubskii (2004)
  • Author(s): G. Saito, H. Yamochi, M. Maesato, Y. Yoshida, A. Ota, Y. Shimizu
  • Total Pages: 26
  • Publisher: Kluwer Academic Press, Netherland
• [Book] "Chapter 4. Oxygen Analogues of TTFs" in TTF Chemistry, eds. J. Yamada, T. Sugimoto (2004)
  • Author(s): H. Yamochi
  • Total Pages: 36
  • Publisher: Kodansha & Springer, Tokyo