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Development of organic superconductors and multifunctional supramolecules based on new π-elecfron systems

Research Project

Project/Area Number 15550127
Research Category

Grant-in-Aid for Scientific Research (C)

Allocation TypeSingle-year Grants
Section一般
Research Field Functional materials chemistry
Research InstitutionUniversity of Tsukuba (2004)
Tokyo Metropolitan University (2003)

Principal Investigator

NISHIKAWA Hiroyuki  University of Tsukuba, Graduate school of Pure and Applied Sciences, Associate Professor, 大学院・数理物質科学研究科, 助教授 (40264585)

Project Period (FY) 2003 – 2004
Project Status Completed (Fiscal Year 2004)
Budget Amount *help
¥3,500,000 (Direct Cost: ¥3,500,000)
Fiscal Year 2004: ¥800,000 (Direct Cost: ¥800,000)
Fiscal Year 2003: ¥2,700,000 (Direct Cost: ¥2,700,000)
KeywordsOrganic Conductor / Superconductor / Charge Order / Phase Diagram / Supramolecule / Intramolecular charge transfer / Organic Thin Film / Organic Solar Cell / π電子系 / 電子供与体 / ドナー-アクセプター系
Research Abstract

In this research project, development of new organic conductors and superconductors based on new molecular design that is destabilization of stable molecular metals as seen in TTP(tetrathiafulvalen) and TTP(tetrathiapentalene) conductors has been conducted. For this purpose, new π-electron donors whose π-electron systems are reduce compared with those of the previous TTF and TTP donors have been designed and synthesized. Structures and physical properties of the conducting radical salts prepared from such π-reduced electron donors have been investigated and a new superconductor, (DODHT)_2BF_4・H_2O, was discovered. By investigating the insulating phase at ambient pressure of the pressure-induced superconductor, (DODHT)_2PF_6, by X-ray diffraction and magnetic susceptibility measurements, the insulator phase was a charge ordering state with stripe type charge pattern. Furthermore, measurement of the transport properties of this material under pressure more precisely, particularly around … More the boundary between superconducting and insulator phases, leads to the pressure-temperature phase diagram ; In the phase diagram, the superconducting and normal resistive states coexists above the pressure of 13 kbar, and the insulator phase exists immediately above the superconducting phase between 13.2 and 15.1 kbar. Because the clear insulator transition was observed in the transport measurement up to 8 kbar, the charge ordering insulator might spread over high pressure region at least 8 kbar. These results suggested that the charge fluctuation might be crucial to the superconductivity in this material and the present material will seive as a simple tool for the investigation of the universality of the interplay between superconductivity and charge fluctuation.
With studying the molecular conductors, development of multifunctional supuramolecular materials and their application to the organic devices have been carried out. For such materials, donor-acceptor linked molecules, such as C_<60>-TTF dyads, were newly prepared and an obvious intramolecular charge transfer interaction was observed unlike the previously reported C_<60>-TTF systems. The life time of the photo-induced charge separated state of the C_<60>-TTF dyad was revealed to be extremely short by the photo-physical study of the excited states, which is disadvantageous for the organic devices such as an organic solar cell. In order to overcome this situation, C_<60>-TTF dendrimers were prepared and the solar cell property was observed in spite of the low efficiency. Less

Report

(3 results)
  • 2004 Annual Research Report   Final Research Report Summary
  • 2003 Annual Research Report
  • Research Products

    (32 results)

All 2004 2003 Other

All Journal Article (24 results) Book (2 results) Publications (6 results)

  • [Journal Article] Photophysical study of new methanofullerene-TTF dyads : an obvious intramolecular charge transfer in the ground stat2004

    • Author(s)
      H.Nishikawa et al.
    • Journal Title

      The Journal of Physical Chemistry A 108

      Pages: 1881-1890

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2004 Annual Research Report 2004 Final Research Report Summary
  • [Journal Article] Magnetic properties of superconducting salts, (DODHT)_2X (X = AsF_6,PF_6 and BF_4)2004

    • Author(s)
      H.Nishikawa et al.
    • Journal Title

      Journal de Physique IV 114

      Pages: 565-567

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2004 Final Research Report Summary
  • [Journal Article] Photophysical study of new methanofullerene-TTF dyads : an obvious intramolecular charge transfer in the ground states2004

    • Author(s)
      H.Nishikawa, S.Kojima, T.Kodama, I.Ikemoto, S.Suzuki, K.Kikuchi, M.Fujitsuka, H.Luo, Y.Araki, O.Ito
    • Journal Title

      J.Phys.Chem.A 108

      Pages: 1881-1890

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2004 Final Research Report Summary
  • [Journal Article] Magnetic properties of superconducting salts, (DODHT)_2X(X=AsF_6,PF_6 and BF_4)2004

    • Author(s)
      H.Nishikawa, Y.Sato, T.Kodama, K.Kikuchi, I.Ikemoto, J.Yamada
    • Journal Title

      J.Phys.IV France 114

      Pages: 565-567

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2004 Final Research Report Summary
  • [Journal Article] New Trends in the Synthesis of π-Electron Donors for Molecular Conductors and Superconductors2004

    • Author(s)
      J.Yamada, H.Akutsu, H.Nishikawa, K.Kikuchi
    • Journal Title

      Chem.Rev. 104

      Pages: 5057-5084

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2004 Final Research Report Summary
  • [Journal Article] Magnetic properties of superconducting salts, (DODHT)_2X (X = AsF_6, PF_6 and BF_4)2004

    • Author(s)
      H.Nishikawa et al.
    • Journal Title

      Journal de Physique IV 114

      Pages: 565-567

    • Related Report
      2004 Annual Research Report
  • [Journal Article] New organic conductor (DMET)_2CuCl_2 : Synthesis, structure and physical properties2004

    • Author(s)
      M.Umemiya et al.
    • Journal Title

      Journal de Physique IV 114

      Pages: 589-590

    • Related Report
      2004 Annual Research Report
  • [Journal Article] New trends in the synthesis of π-electron donors for molecular conductors and superconductors2004

    • Author(s)
      J.Yamada et al.
    • Journal Title

      Chemical Reviews 104

      Pages: 5057-5083

    • Related Report
      2004 Annual Research Report
  • [Journal Article] Isolation and characterization of a new isomer of Ca@C_<72>2004

    • Author(s)
      T.Kodama et al.
    • Journal Title

      Chemistry Letters 33

      Pages: 1008-1009

    • Related Report
      2004 Annual Research Report
  • [Journal Article] A new organic superconductor, (DODHT)_2BF_4・H_2O2003

    • Author(s)
      H.Nishikawa et al.
    • Journal Title

      Chemical Communication 4

      Pages: 494-495

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2004 Final Research Report Summary
  • [Journal Article] New organic superconductors from a donor with reduced π-system2003

    • Author(s)
      H.Nishikawa et al.
    • Journal Title

      Synthetic Metals 133-134

      Pages: 193-195

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2004 Final Research Report Summary
  • [Journal Article] Structure and properties of radical salts of DODHT derivatives2003

    • Author(s)
      H.Nishikawa et al.
    • Journal Title

      Synthetic Metals 137

      Pages: 1253-1254

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2004 Final Research Report Summary
  • [Journal Article] A new organic superconductor, (DODHT)_2BF_4・H_2O2003

    • Author(s)
      H.Nishikawa, A.Machida, T.Morimoto, K.Kikuchi, T.Kodama, I.Ikemoto, J.Yamada, H.Yoshino, K.Murata
    • Journal Title

      Chem.Commun.

      Pages: 494-495

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2004 Final Research Report Summary
  • [Journal Article] New organic superconductors from a donor with reduced π-system2003

    • Author(s)
      H.Nishikawa, T.Morimoto, T.Kodama, I.Ikemoto, K.Kikuchi, J.Yamada, H.Yoshino, K.Murata
    • Journal Title

      Synth.Met. 133-134

      Pages: 193-195

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2004 Final Research Report Summary
  • [Journal Article] Crystal structures and physical properties of new Ni complexes with dihydro-TTF dithiolate2003

    • Author(s)
      K.Yokoyama, H.Nishikawa, K.Kikuchi, T.Kodama, I.Ikemoto, J.Yamada
    • Journal Title

      Synth.Met. 135-136

      Pages: 659-660

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2004 Final Research Report Summary
  • [Journal Article] Structural studies of DODHT superconductor and related salts2003

    • Author(s)
      K.Kikuchi, H.Nishikawa, T.Morimoto, T.Kodama, I.Ikemoto, J.Yamada
    • Journal Title

      Synth.Met. 137

      Pages: 1199-1200

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2004 Final Research Report Summary
  • [Journal Article] Synthesis and physical properites of new C_<60> derivatives linked with TTF2003

    • Author(s)
      S.Kojima, H.Nishikawa, T.Kodama, I.Ikemoto, K.Kikuchi
    • Journal Title

      Synth.Met. 135-136

      Pages: 775-776

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2004 Final Research Report Summary
  • [Journal Article] Structures and properties of radical salts of DODHT derivatives2003

    • Author(s)
      H.Nishikawa, T.Morimoto, A.Machida, T.Kodama, I.Ikemoto, K.Kikuchi, J.Yamada, H.Yoshino, K.Murata
    • Journal Title

      Synth.Met. 137

      Pages: 1253-1254

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2004 Final Research Report Summary
  • [Journal Article] A new organic superconductor, β(BDA-TTP)_2GaCl_4 [BDA-TTP=2,5-(1,3-dithian-2-ylidene)-1,3,4,6-tetrathiapentalene]2003

    • Author(s)
      J.Yamada, T.Toita, H.Akutsu, S.Nakatsuji, H.Nishikawa, I.Ikemoto, K.Kikuchi, E.S.Choi, D.Graf, J.S.Brooks
    • Journal Title

      Chem.Commun.

      Pages: 2230-2231

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2004 Final Research Report Summary
  • [Journal Article] Chemical pressure effect on bandwidth and dimensionality of quasi-one-dimensional organic conductors : (DMET)_2X[X=Au(CN)_2,Au_2,AuCl_2,IBr_2,I_3,AuBr_2,and SCN]2003

    • Author(s)
      H.Yoshino, K.Murata, K.Saito, H.Nishikawa, K.Kikuchi, I.Ikemoto
    • Journal Title

      Phys.Rev. 67

      Pages: 35111-35111

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2004 Final Research Report Summary
  • [Journal Article] Crystal structure and physical properite of (DODHT)_2FeCl_4

    • Author(s)
      H.Nishikawa et al.
    • Journal Title

      Polyhedron (in press)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2004 Final Research Report Summary
  • [Journal Article] Physical properties and crystal structures of MeDA-TTP salts

    • Author(s)
      H.Nishikawa, H.Sekiya, D.Watanabe, T.Kodama, K.Kikuchi, I.Ikemoto, J.Yamada
    • Journal Title

      Synth.Met. (in press)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2004 Final Research Report Summary
  • [Journal Article] Crystal structure and physical properties of (DODHT)_2FeCl_4

    • Author(s)
      H.Nishikawa, Y.Yasuda, T.Kodama, K.Kikuchi, I.Ikemoto, J.Yamada, H.Oshio
    • Journal Title

      Polyhedron (in press)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2004 Final Research Report Summary
  • [Journal Article] Crystal structure and physical properite of (DODHT)_2FeCl_4

    • Author(s)
      H.Nishikawa et al.
    • Journal Title

      Polyhedron (In press)

    • Related Report
      2004 Annual Research Report
  • [Book] Dihydro-TTFs and bis-fused 1,3-dithiol-2-ylidene donors, TTF chemistry-Fundamentals and applications of tetrathiafulvalene, Chapter 112004

    • Author(s)
      J.Yamada et al.
    • Total Pages
      23
    • Publisher
      Kodansya and Springer
    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2004 Final Research Report Summary
  • [Book] Dihydro-TTFs and bis-fused 1,3-dithiol-2-ylidene donors, TTF chemistry - Fundamentals and applications of tetrathiafulvalene, Chapter 112004

    • Author(s)
      J.Yamada et al.
    • Total Pages
      23
    • Publisher
      Kodansya and Springer
    • Related Report
      2004 Annual Research Report
  • [Publications] H.Nishikawa et al.: "A new organic superconductor, (DODHT)_2BF_4-H_2O"Chemical Communication. 4. 494-495 (2003)

    • Related Report
      2003 Annual Research Report
  • [Publications] H.Nishikawa et al.: "New organic superconductors from a donor with reduced π-system"Synthetic Metals. 133-134. 193-195 (2003)

    • Related Report
      2003 Annual Research Report
  • [Publications] H.Nishikawa et al.: "Structure and properties of radical salts of DODHT derivatives"Synthetic Metals. 137. 1253-1254 (2003)

    • Related Report
      2003 Annual Research Report
  • [Publications] K.Yokoyama et al.: "Crystal structures and physical properties of new Ni complexes with dihydro-TTF dithiolato"Synthetic Metals. 137. 659-660 (2003)

    • Related Report
      2003 Annual Research Report
  • [Publications] S.Kojima et al.: "Synthesis and physical properites of new C60 derivatives linked with TTF"Synthetic Metals. 137. 775-776 (2003)

    • Related Report
      2003 Annual Research Report
  • [Publications] H.Nishikawa et al.: "Photophysical study of new methanofullerene-TTF dyads : an obvious intramolecular charge transfer in the ground stat"The Journal of Physical Chemistry A. 108. 1881-1890 (2004)

    • Related Report
      2003 Annual Research Report

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Published: 2003-04-01   Modified: 2016-04-21  

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