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2013 Fiscal Year Annual Research Report

複合スピン機能と柔軟な有機機能を併せ持つ超分子的磁性体の合成開発とその評価

Research Project

Project/Area Number 22350059
Research InstitutionThe University of Electro-Communications

Principal Investigator

石田 尚行  電気通信大学, 情報理工学(系)研究科, 教授 (00232306)

Project Period (FY) 2010-04-01 – 2014-03-31
Keywords分子性磁性体 / 集積型金属錯体 / 超分子科学 / 単分子磁石 / 高スピン分子 / 相転移
Research Abstract

分子を基調とする新規磁性体の中から、メモリー、表示材料、磁気抵抗などの複合機能性材料への応用を示すことは今後のエレクトロニクスのために重要である。一方で分子性材料が無機物質では考えられなかったような特性も有することから、「分子性物質ならでは」という性質の導入も必要である。本課題ではこのような複合スピン系に、柔軟性、加工性、反応性、光吸収などの有機由来・分子由来の機能を導入し具体化しつつある。
1.サーモクロミック有機磁性体:基底三重項ビラジカルの一連化合物群が、逐次構造相転移を示し、反磁性からS = 1/2常磁性、続いてS = 1常磁性となることを明らかにしている。反磁性相は薄いオレンジ色、常磁性相は濃赤色である。この一つの誘導体で、ビラジカルであるにも関わらず幅広い温度領域でS = 1/2常磁性を示すものも見いだした。
2.有機ラジカルと希土類からなる磁性材料:4f-2p系のヘテロスピン間交換相互作用で、これまでの最大の大きさを有するものを開発した。いくつかの錯体分子は単分子磁石または単イオン磁石として振る舞った。また、2p-4f-2pのヘテロ3スピン系で、従来の予想を越える強い2p-2p超交換相互作用を見いだした。
3.有機ラジカルと遷移金属イオンからなる磁性材料:わずかな構造変化により、基底高スピン状態と基底低スピン状態をスイッチする物質群を見いだした。広義の3中心スピンクロスオーバー現象であると理解することができた。
4.分子包接誘起磁性体、磁気検出型イオンセンサー:ラジカル置換のホスト・配位子分子を合成開発した。金属イオンの有無に従って、開いた構造から閉じた構造に変化する。ポリエーテル鎖の長さに依存して、カルシウムイオンやバリウムイオンを選択的に取り込むことを電子スピン共鳴法から明らかにした。これは将来イオン検出試薬の開発に繋がる可能性がある。

Current Status of Research Progress
Reason

25年度が最終年度であるため、記入しない。

Strategy for Future Research Activity

25年度が最終年度であるため、記入しない。

  • Research Products

    (22 results)

All 2014 2013 Other

All Journal Article (14 results) (of which Peer Reviewed: 14 results) Presentation (5 results) (of which Invited: 2 results) Book (1 results) Remarks (2 results)

  • [Journal Article] Multifunctional π-Expanded Macrocyclic Oligothiophene 6-Mers and Related Macrocyclic Oligomers2014

    • Author(s)
      M. Iyoda, K. Tanaka, H. Shimizu, M. Hasegawa, T. Nishiuchi, S. Sugibayashi, T. Nishinaga, Y. Kunugi, T. Ishida, H. Otani, H. Sato, K. Inukai, K. Tahara, and Y. Tobe
    • Journal Title

      J. Am. Chem. Soc.

      Volume: 136 Pages: 2389-2396

    • DOI

      10.1021/ja4101744

    • Peer Reviewed
  • [Journal Article] Doubly TEMPO-Coordinated Gadolinium(III), Lanthanum(III), and Yttrium(III) Complexes. Strong Superexchange Coupling across Rare Earth Ions2014

    • Author(s)
      R. Murakami, T. Nakamura, and T. Ishida
    • Journal Title

      Dalton Trans.

      Volume: 43 Pages: 5893-5898

    • DOI

      10.1039/c3dt53586j

    • Peer Reviewed
  • [Journal Article] Preparation and Characterization of [Gd(hfac)3(DTBN)(H2O)] (DTBN = Di-t-butyl Nitroxide). Ferromagnetic Gd3+-Gd3+ Super-superexchange2014

    • Author(s)
      T. Kanetomo and T. Ishida
    • Journal Title

      Chemical Communications

      Volume: 50 Pages: 2529-2531

    • DOI

      10.1039/c3cc48326f

    • Peer Reviewed
  • [Journal Article] Linker Stoichiometry Controlled Stepwise Supramolecular Growth of a Flexible Cu2Tb Single Molecule Magnet from Monomer to Dimer to 1D Chain2014

    • Author(s)
      S. Ghosh, Y. Ida, T. Ishida, and A. Ghosh
    • Journal Title

      Crystal Growth & Design

      Volume: 14 Pages: 2588-2598

    • DOI

      10.1021/cg500290m

    • Peer Reviewed
  • [Journal Article] A New Family of Trinuclear Nickel(II) Complexes as Single-Molecule Magnets2013

    • Author(s)
      R. Biswas, Y. Ida, M. L. Baker, S. Biswas, P. Kar, H. Nojiri, T. Ishida, and A. Ghosh
    • Journal Title

      Chem. Eur. J.

      Volume: 19 Pages: 3943-3953

    • DOI

      10.1002/chem.201202795

    • Peer Reviewed
  • [Journal Article] Ground Triplet Pyrimidine-4,6-diyl Bis(tert-butyl Nitroxide) as a Paramagnetic Building Block for Metal-Organic Frameworks2013

    • Author(s)
      Y. Homma, A. Okazawa, and T. Ishida
    • Journal Title

      Tetrahedron Lett.

      Volume: 54 Pages: 3120-3123

    • DOI

      10.1016/j.tetlet.2013.04.008

    • Peer Reviewed
  • [Journal Article] Formation of Two Drastically Different MOFs Based on Mn(II)-Benzoate and Pyrazine with a Change in Seasonal Temperature: Structural Analysis and Magnetic Study2013

    • Author(s)
      P. Kar, Y. Ida, T. Ishida, and A. Ghosh
    • Journal Title

      CrystEngComm

      Volume: 15 Pages: 400-410

    • DOI

      10.1039/c2ce26258d

    • Peer Reviewed
  • [Journal Article] Syntheses, Structures, and Magnetic Properties of Acetato- and Diphenolato-Bridged 3d-4f Binuclear Complexes [M(3-MeOsaltn)(MOH)x(ac)Ln(hfac)2] (M = Zn,Cu,Ni,Co; Ln = La,Gd,Tb,Dy; 3-MeOsaltn = N,N′-Bis(3-methoxy-2-oxybenzylidene)-1,3-propanediaminato; ...2013

    • Author(s)
      M. Towatari, K. Nishi, T. Fujinami, N. Matsumoto, Y. Sunatsuki, M. Kojima, N. Mochida, T. Ishida, N. Re, and J. Mrozinski
    • Journal Title

      Inorganic Chemistry

      Volume: 52 Pages: 6160-6178

    • DOI

      10.1021/ic400594u

    • Peer Reviewed
  • [Journal Article] A Supramolecular Switch between Ground High- and Low-Spin States Using 2,2’:6’,2”-Terpyridine-6,6”-diyl Bis(tert-butyl Nitroxide)2013

    • Author(s)
      T. Konno, K. Koide, and T. Ishida
    • Journal Title

      Chemical Communications

      Volume: 49 Pages: 5156-5158

    • DOI

      10.1039/c3cc41894d

    • Peer Reviewed
  • [Journal Article] Carbonate-Bridged NiII2LnIII2 (LnIII = GdIII, TbIII, DyIII) Complexes Generated by Atmospheric CO2 Fixation and Their Single-Molecule-Magnet Behavior: [(μ-CO3)2{NiII(3-MeOsaltn)(MeOH or H2O)LnIII(NO3)}2].solvent...2013

    • Author(s)
      S. Sakamoto, T. Fujinami, K. Nishi, N. Matsumoto, N. Mochida, T. Ishida, Y. Sunatsuki, and N. Re
    • Journal Title

      Inorganic Chemistry

      Volume: 52 Pages: 7218-7229

    • DOI

      10.1021/ic4008312

    • Peer Reviewed
  • [Journal Article] Single-Molecule Magnet [Tb(hfac)3(2pyNO)] (2pyNO = t-Butyl 2-Pyridyl Nitroxide) with a Relatively High Barrier of Magnetization Reversal2013

    • Author(s)
      R. Murakami, T. Ishida, S. Yoshii, and H. Nojiri
    • Journal Title

      Dalton Transactions

      Volume: 42 Pages: 13968-13973

    • DOI

      10.1039/c3dt51784e

    • Peer Reviewed
  • [Journal Article] Exchange Couplings and Its Chemical Trend Studied by High-Frequency EPR on Heterometallic [Ln2Ni] Complexes2013

    • Author(s)
      A. Okazawa, T. Shimada, N. Kojima, S. Yoshii, H. Nojiri, and T. Ishida
    • Journal Title

      Inorganic Chemistry

      Volume: 52 Pages: 13351-13355

    • DOI

      10.1021/ic402417h

    • Peer Reviewed
  • [Journal Article] Determination of Crystal-Field Energy Levels and Temperature Dependence of Magnetic Susceptibility for Dy3+ in [Dy2Pd] Heterometallic Complex2013

    • Author(s)
      M. Karbowiak, C. Rudowicz, and T. Ishida
    • Journal Title

      Inorganic Chemistry

      Volume: 52 Pages: 13199-13206

    • DOI

      10.1021/ic4021542

    • Peer Reviewed
  • [Journal Article] Synthesis, Structure, Luminescent and Magnetic Properties of Carbonato-Bridged ZnII2LnIII2 Complexes [(μ4-CO3)2{ZnIILnLnIII(NO3)}2] (LnIII = GdIII, TbIII, DyIII; ...2013

    • Author(s)
      K. Ehama, Y. Ohmichi, S. Sakamoto, T. Fujinami, N. Matsumoto, N. Mochida, T. Ishida, Y. Sunatsuki, M. Tsuchimoto, and N. Re
    • Journal Title

      Inorganic Chemistry

      Volume: 52 Pages: 12828-12841

    • DOI

      10.1021/ic4022273

    • Peer Reviewed
  • [Presentation] Preparation and characterization of [Gd(hfac)3(DTBN)(H2O)] (DTBN = di-t-butyl nitroxide). Ferromagnetic Gd3+-Gd3+ super-superexchange2013

    • Author(s)
      T. Kanetomo and T. Ishida
    • Organizer
      The 7th Japanese-Russian Workshop on Open Shell Compounds and Molecular Spin Devices
    • Place of Presentation
      Awaji, Hyogo
    • Year and Date
      20131117-20131120
    • Invited
  • [Presentation] Exchange Coupling of Rare-earth-Radical Hetero-Spin Magnetic Clusters-ESR and Neutron Scattering Study2013

    • Author(s)
      T. Tanaka, M. Baker, H. Nojiri and T. Ishida
    • Organizer
      The 12th Asia Pacific Physics Conference, APPC12
    • Place of Presentation
      Makuhari, Chiba
    • Year and Date
      20130714-20130719
  • [Presentation] Relatively Strong Exchange Coupling in Lanthanoid-Nitroxide Heterospin Compounds2013

    • Author(s)
      T. Kanetomo, R. Murakami, and T. Ishida
    • Organizer
      The 1st Awaji International Workshop on Electron Spin Science & Technology: Biological and Materials Science Oriented Applications, 1st AWEST
    • Place of Presentation
      Awaji, Hyogo
    • Year and Date
      20130616-20130618
  • [Presentation] Entropy-Driven Three-Centered Spin-Crossover-Like Behavior in a Nickel(II) Bis(nitroxide) Complex2013

    • Author(s)
      Y. Homma and T. Ishida
    • Organizer
      The 1st Awaji International Workshop on Electron Spin Science & Technology: Biological and Materials Science Oriented Applications, 1st AWEST
    • Place of Presentation
      Awaji, Hyogo
    • Year and Date
      20130616-20130618
    • Invited
  • [Presentation] Determination of Crystal-Field Energy Levels and Temperature Dependence of Magnetic Susceptibility for Dy3+ in [Dy2Pd] Heterometallic Complex2013

    • Author(s)
      M. Karbowiak, C. Rudowicz, and T. Ishida
    • Organizer
      International Conference on Rare Earth Materials, REMAT2013
    • Place of Presentation
      Wroclaw, Poland
    • Year and Date
      20130426-20130428
  • [Book] 分子磁性の最前線-第19章 f-d系およびf-p系単分子磁石2014

    • Author(s)
      石田尚行
    • Total Pages
      6
    • Publisher
      化学同人
  • [Remarks] 論文リスト

    • URL

      http://kjk.office.uec.ac.jp/Profiles/4/0000392/theses1.html

  • [Remarks] Ishida, Takayuki のホームページ

    • URL

      http://ttf.pc.uec.ac.jp/www.page/Ishida.html

URL: 

Published: 2015-05-28  

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