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安定有機ラジカルを用いた分子性有機磁性金属・超伝導体の開発

Research Project

Project/Area Number 14740389
Research Category

Grant-in-Aid for Young Scientists (B)

Allocation TypeSingle-year Grants
Research Field 機能・物性・材料
Research InstitutionOsaka Prefecture University (2003-2004)
Okazaki National Research Institutes (2002)

Principal Investigator

藤原 秀紀  大阪府立大学, 先端科学研究所, 助手 (70290898)

Project Period (FY) 2002 – 2004
Project Status Completed (Fiscal Year 2004)
Budget Amount *help
¥3,900,000 (Direct Cost: ¥3,900,000)
Fiscal Year 2004: ¥1,200,000 (Direct Cost: ¥1,200,000)
Fiscal Year 2003: ¥1,300,000 (Direct Cost: ¥1,300,000)
Fiscal Year 2002: ¥1,400,000 (Direct Cost: ¥1,400,000)
Keywords有機伝導体 / 電子供与体 / 磁性体 / カチオンラジカル塩 / 構造有機化学 / 結晶構造 / 安定有機ラジカル
Research Abstract

伝導性と磁性の複合機能を有する物質の開発に注目が集まっている。今回、部分構造として2,2,5,5-tetramethylpyrrolin-1-yloxylを有する新たなタイプの各種π拡張型ドナーを合成し、そのカチオンラジカル塩の作製を行ったので、それらの構造と物性について調べた。エチレンジチオ基を有するドナーについて単結晶構造解析を行った。TTF部分はほぼ平面構造で、ラジカル部位はTTF平面に対して約45°の角度で折れ曲がって存在していた。電気化学的性質を調べる目的で合成したドナーについてCVの測定を行った結果、3つの1,3-ジチオール環と1つのラジカル部位が存在することに対応して、いずれも4つの可逆的酸化還元波を示した。また、その酸化電位から第三酸化還元波はNOラジカル部位に起因するものと考えられる。得られたドナーについて磁化率の測定を行った。磁化率は室温からCurie-Weiss的な温度依存性を示し、Weiss温度は-1から-2K程度で弱い反強磁性的相互作用を示した。Curie定数はS=1/2から予想される値とほぼ一致する。また、ドナーの室温ESR測定では、NOラジカルに由来する3本のシグナルが観測され、g=2.0059、a_N=14.3-14.4Gであった。さらにエチレンジチオ基を有するドナーは、対応する支持電解質を含む10%EtOH/PhCl中、電解酸化することによりReO_4^-塩とPF_6^-塩を与え、これらの塩はそれぞれE_a=0.075,0.103eVで、σ_<rt>=10^<-1>S・cm^<-1>のオーダーの半導体であった。

Report

(3 results)
  • 2004 Annual Research Report
  • 2003 Annual Research Report
  • 2002 Annual Research Report
  • Research Products

    (18 results)

All 2005 2004 Other

All Journal Article (6 results) Publications (12 results)

  • [Journal Article] Ferromagnetic Ordering of Fe(III) d Spins of FeBr_4^- Ions in (Ethlenedithio-tetrathiafulvalenothioquinone-ethylenedithio-1,3-dithiolemethide)・FeBr_42005

    • Author(s)
      M.-X.Wang et al.
    • Journal Title

      Inorg.Chem. 44

      Pages: 1184-1184

    • Related Report
      2004 Annual Research Report
  • [Journal Article] Crystal structures and physical properties of single-component molecular conductors consisting of nickel and gold complexes with bis(trifluoromethyl)tetrathiafulvalenedithiolate ligands2005

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

      J.Mater.Chem. 15

      Pages: 155-155

    • Related Report
      2004 Annual Research Report
  • [Journal Article] Synthesis, Structures and Physical Properties of a New Organic Conductor Based on a π-Extended Donor Containing a Stable PROXYL Radical2004

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

      Adv.Mater. 16

      Pages: 1765-1765

    • Related Report
      2004 Annual Research Report
  • [Journal Article] Novel π-Extended Donors Containing a 2,2,5,5-Tetramethylpyrrolin-1-yloxyl Radical Designed for Magnetic Molecular Conductors2004

    • Author(s)
      E.Fujiwara et al.
    • Journal Title

      Chem.Lett., 33

      Pages: 964-964

    • NAID

      10013447372

    • Related Report
      2004 Annual Research Report
  • [Journal Article] The pressure effect on the antiferromagnetic and superconducting transitions of κ-(BEST)_2FeBr_42004

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

      J.Mater.Chem. 14

      Pages: 1682-1682

    • Related Report
      2004 Annual Research Report
  • [Journal Article] Magnetic-field-induced superconductivity in the antiferromagnetic organic superconductor2004

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

      Phys.Rev. B70

      Pages: 94514-94514

    • Related Report
      2004 Annual Research Report
  • [Publications] A.Kobayashi et al.: "Infrared Electronic Absorption in a Single-Component Molecular Metal"J.Am.Chem.Soc.. 126. 426-427 (2004)

    • Related Report
      2003 Annual Research Report
  • [Publications] H.Fujiwara et al.: "A Novel TTP Donor Containing a PROXYL Radical for Magnetic Molecular Conductors"Chem.Lett.. 32. 482-483 (2003)

    • Related Report
      2003 Annual Research Report
  • [Publications] Z.-M.Wang et al.: "Mn_3(HCOO)_6 :a 3D porous magnet of diamond framework with nodes of Mn-centered MnMn_4 tetrahedron and guest-modulated ordering temperature"Chem.Commun.. 416-417 (2004)

    • Related Report
      2003 Annual Research Report
  • [Publications] E.Fujiwara et al.: "Syntheses, Structures, and Physical Properties of Nickel Bis(dithiolene) Complexes Containing Tetrathiafulvalene (TTF) Units"Inorg.Chem.. 43. 1122-1129 (2004)

    • Related Report
      2003 Annual Research Report
  • [Publications] H.Fujiwara et al.: "Synthesis, structures and physical properties of donors containing a PROXYL radical"Synth.Met.. 135-136. 533-534 (2003)

    • Related Report
      2003 Annual Research Report
  • [Publications] H.Fujiwara et al.: "Synthesis, structures and properties of new organic donors connecting to a TEMPO radical through a pyrrolidine ring"Synth.Met.. 133-134. 359-360 (2003)

    • Related Report
      2003 Annual Research Report
  • [Publications] H.Fujiwara et al.: "An indication of magnetic-field-induced superconductivity in a bifunctional layered organic conductor, κ-(BETS)_2FeBr_4"J. Am. Chem. Soc.. 124. 6816-6817 (2002)

    • Related Report
      2002 Annual Research Report
  • [Publications] H.Fujiwara et al.: "Novel π-Electron Donors for Magnetic Conductors Containing a PROXYL Radical"Chem. Lett.. 1048-1049 (2002)

    • Related Report
      2002 Annual Research Report
  • [Publications] B.Zhang et al.: "Dual-Action Molecular Superconductors with Magnetic Anions"J. Am. Chem. Soc.. 124. 9982-9983 (2002)

    • Related Report
      2002 Annual Research Report
  • [Publications] W.Suzuki et al.: "Highly Conducting Crystals Based on Single-Component Gold Complexes with Extended-TTF Dithiolate Ligands"J. Am. Chem. Soc.. 125. 1486-1487 (2003)

    • Related Report
      2002 Annual Research Report
  • [Publications] E.Fujiwara et al.: "Magnetic molecular conductors based on BETS molecules and divalent magnetic anions [BETS=bis(ethylenedithio)tetraselenafulvalene]"Inorg. Chem.. 41. 3230-3238 (2002)

    • Related Report
      2002 Annual Research Report
  • [Publications] E.Fujiwara et al.: "A Series of Organic Conductors κ-(BETS)_2EeBr_xCl_<4-x>(0【less than or equal】x【less than or equal】4) Exhibiting Successive Anti-ferromagnetic and Superconducting Transitions"Adv. Marer.. 14. 1376-1379 (2002)

    • Related Report
      2002 Annual Research Report

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Published: 2002-04-01   Modified: 2016-04-21  

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