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分子磁性体における新規な光磁性現象と磁気光学効果

Research Project

Project/Area Number 15685004
Research Category

Grant-in-Aid for Young Scientists (A)

Allocation TypeSingle-year Grants
Research Field Inorganic chemistry
Research InstitutionThe University of Tokyo

Principal Investigator

大越 慎一  東京大学, 大学院・工学系研究科, 助教授 (10280801)

Project Period (FY) 2003 – 2005
Project Status Completed (Fiscal Year 2005)
Budget Amount *help
¥29,510,000 (Direct Cost: ¥22,700,000、Indirect Cost: ¥6,810,000)
Fiscal Year 2005: ¥9,490,000 (Direct Cost: ¥7,300,000、Indirect Cost: ¥2,190,000)
Fiscal Year 2004: ¥9,620,000 (Direct Cost: ¥7,400,000、Indirect Cost: ¥2,220,000)
Fiscal Year 2003: ¥10,400,000 (Direct Cost: ¥8,000,000、Indirect Cost: ¥2,400,000)
Keywords光誘起相転移 / 電荷移動 / シアノ架橋型金属錯体 / 温度ヒステリシス / 協同効果 / 光磁性 / スピン転移 / 磁気光学効果 / 光誘起強磁性 / 電気化学的合成 / 薄膜 / 分子磁性体
Research Abstract

プルシアンブルー類似体Rb_<0.98>Mn_<1.01>[Fe(CN)_6]-0.2H_2Oは大きな温度ヒステリシス(T_<1/2↓>=220K,T_<1/2↑>=314K)を示す相転移材料であることを見出した。高温相の電子状態はFe(III)(S=1/2)-CN-Mn(II)(S=5/2)であり、低温相の電子状態はFe(II)(S=0)-CN-Mn(III)(S=2)である。また、低温相は10000-20000cm^<-1>にMn(III)からFe(II)への原子価間電荷移動バンドをもつ。温度ヒステリシス内の295K((22℃)で、低温相に532nm光を1ショット照射すると、高温相に転移することが赤外吸収スペクトルより確認された。この光誘起相転移の閾値は6mJ cm^<-2> pulse^<-1>であり、量子効率は24mJ cm^<-2> pulse^<-1>の時にΦ=38と最大であった。これらの結果は、この光誘起相転移には協同効果が存在していることを示唆している。
集積型金属錯体Co_3[W(CN)_8]_2-(pyrimidine)_4-6H_2Oは、シアノ基によりCoとWが交互に架橋された3次元構造をしている。この錯体は、大きな温度ヒステリシス(T_<1/2↓>=208K,T_<1/2↑>=298K)を示す相転移材料であり、相転移に伴い赤色(高温相)から緑色(低温相)へと色相が変化する。高温相の電子状態はW(V)(S=1/2)-CN-Co(II)_<HS>(S=3/2)であり、低温相の電子状態はW(IV)(S=0)-CN-Co(III)_<LS>(3=0)である。常磁性体である低温相に840nm光を照射すると、磁化が増加し強磁性体へと変化した。光誘起強磁性相の強磁性転移温度は40Kであり、保磁力は12000Gであった。これらの値は、光誘起強磁性体の中では最高の値である。光照射により、低温相から高温相へと相転移したために、強磁性が発現したと考えられる。

Report

(3 results)
  • 2005 Annual Research Report
  • 2004 Annual Research Report
  • 2003 Annual Research Report
  • Research Products

    (33 results)

All 2006 2005 2004 Other

All Journal Article (17 results) Book (1 results) Publications (15 results)

  • [Journal Article] Photo-induced magnetization with a high Curie temperature and a large coercive field in a cyano-bridged cobalt-tungstate bimetallic assembly2006

    • Author(s)
      S.Ohkoshi, S.Ikeda, T.Hozumi, T.Kashiwagi, K.Hashimoto
    • Journal Title

      Journal of the American Chemical Society 128(印刷中)

    • Related Report
      2005 Annual Research Report
  • [Journal Article] Noncollinear spin structure in Sm_xTb_<1-x>[Cr(CN)_6]-4H_2O having orthogonal single-ion anisotropies2006

    • Author(s)
      T.Hozumi, K.Hashimoto, S.Ohkoshi
    • Journal Title

      Physical Review B 73・9

      Pages: 92409-92409

    • Related Report
      2005 Annual Research Report
  • [Journal Article] Optical switching between bistable phases in rubidium manganese hexacyanoferrate at room temperature2005

    • Author(s)
      H.Tokoro, T.Matsuda, K.Hashimoto, S.Ohkoshi
    • Journal Title

      Journal of Applied Physics 97・10

    • Related Report
      2005 Annual Research Report
  • [Journal Article] Cyano-bridged gadolinium(III)-tungstate(V) bimetallic assembly with a one-dimensional chain structure2005

    • Author(s)
      S.Ikeda, T.Hozumi, K.Hashimoto, S.Ohkoshi
    • Journal Title

      Dalton Transactions 2005・12

      Pages: 2120-2120

    • Related Report
      2005 Annual Research Report
  • [Journal Article] Synthesis of Ferromagnetic CsCuCr Prussian Blue Analogue with a Tetragonal Structure2005

    • Author(s)
      W.Kosaka, T.Ishihara, H.Yashiro, Y.Taniguchi, K.Hashimoto, S.Ohkoshi
    • Journal Title

      Chemistry Letters 34・9

      Pages: 1278-1278

    • NAID

      130004722725

    • Related Report
      2005 Annual Research Report
  • [Journal Article] Colored magnetic films composed of cyano-bridged metal assemblies and magneto-optical functionalities2005

    • Author(s)
      T.Nuida, T.Hozumi, W.Kosaka, S.Sakurai, S.Ikeda, T.Matsuda, H.Tokoro, K.Hashimoto, S.Ohkosni
    • Journal Title

      Polyhedron 24・16-17

      Pages: 2901-2901

    • Related Report
      2005 Annual Research Report
  • [Journal Article] Temperature- and photo-induced phase transition in rubidium manganese-hexacyanoferrates2005

    • Author(s)
      S.Ohkoshi, H.Tokoro, K.Hashimoto
    • Journal Title

      Coordiantion Chemistry Reviews 249・17-18

      Pages: 1830-1830

    • Related Report
      2005 Annual Research Report
  • [Journal Article] Magnetization-induced second harmonic generation and third harmonic generation in transparent magnetic films2005

    • Author(s)
      S.Ohkoshi, J.Shimura, K.Ikeda, K.Hashimoto
    • Journal Title

      Journal of the Optical Society of America B 22

      Pages: 196-196

    • Related Report
      2005 Annual Research Report
  • [Journal Article] Electric state and local structures of photomagnetic CuMo cyanides studied by x-ray-absorption spectroscopy2005

    • Author(s)
      X.D.Ma, T.Yokoyama, T.Hozumi, K.Hashimoto, S.Ohkoshi
    • Journal Title

      Physical Review B 72・9

      Pages: 94107-94107

    • Related Report
      2005 Annual Research Report
  • [Journal Article] Spectroscopic investigation of the dynamic behavior of the photoinduced phase transition of Na_<0.6>Co_<1.3>[Fe(CN)_6]-4H_2O2005

    • Author(s)
      T.Yamauchi, A.Nakamura, Y.Moritomo, T.Hozumi, K.Hashimoto.S.Ohkoshi
    • Journal Title

      Physical Review B 72・21

      Pages: 214425-214425

    • Related Report
      2005 Annual Research Report
  • [Journal Article] Magnetic and Mossbauer investigation of the photo-magnetic Prussian Blue analogue Na0.37Co[Fe(CN)6]3.4H2O cooperative relaxation of the thermally quenched state2005

    • Author(s)
      S.Gawali-Salunke, F.Varret, I.Maurin, C.Enach_escu, K.Boukheddaden, E.Codjovi, H.Tokoro, S.Ohkoshi, K.Hashimoto
    • Journal Title

      Journal of the Physical Chemistry B 109・16

      Pages: 8251-8251

    • Related Report
      2005 Annual Research Report
  • [Journal Article] A Surprisingly Large Thermal Hysteresis Loop in a Reversible Phase Transition of Rb_xMn[Fe(CN)_6]_<(x+2)/3>・zH_2O2005

    • Author(s)
      S.Ohkoshi, T.Matsuda, H.Tokoro, K.Hashimoto
    • Journal Title

      Chemistry of Materials 17・1

      Pages: 81-81

    • Related Report
      2004 Annual Research Report
  • [Journal Article] Electrochemical synthesis, crystal structure, and photomagnetic properties of a three-dimensional cyano-bridged copper-molybdenum complex2005

    • Author(s)
      T.Hozumi, K.Hashimoto, S.Ohkoshi
    • Journal Title

      Journal of the American Chemical Society 127・11

      Pages: 3864-3864

    • Related Report
      2004 Annual Research Report
  • [Journal Article] Humidity-induced magnetization and magnetic pole inversion in a cyano-bridged metal assembly2004

    • Author(s)
      S.Ohkoshi, K.Arai, Y.Sato, K.Hashimoto
    • Journal Title

      Nature Materials 3・3

      Pages: 857-857

    • Related Report
      2004 Annual Research Report
  • [Journal Article] A Large Thermal Hysteresis Loop Produced by a Charge-Transfer Phase Transition in a Rubidium Manganese Hexacyanoferrate2004

    • Author(s)
      H.Tokoro, S.Ohkoshi, T.Matsuda, K.Hashimoto
    • Journal Title

      Inorganic Chemistry 43・17

      Pages: 5231-5231

    • Related Report
      2004 Annual Research Report
  • [Journal Article] Magnetic specific heat of the low-temperature phase of rubidium manganese hexacyanoferrate2004

    • Author(s)
      H.Tokoro, S.Ohkoshi, T.Matsuda, T.Hozumi, K.Hashimoto
    • Journal Title

      Chemical Physics Letters 388・4-6

      Pages: 379-379

    • Related Report
      2004 Annual Research Report
  • [Journal Article] Manganese(II) Octacyanotungstate(V)-Based Magnet Containing a Noncoordinated Aromatic Molecule2004

    • Author(s)
      T.Kashiwagi, S.Ohkoshi, H.Seino, Y.Mizobe, K.Hashimoto
    • Journal Title

      Journal of the American Chemical Society 126・16

      Pages: 5024-5024

    • Related Report
      2004 Annual Research Report
  • [Book] Magnetism: Molecule to Materials V2005

    • Author(s)
      K.Inoue, S.Ohkoshi, H.Imai
    • Total Pages
      30
    • Publisher
      Wiley-VCH
    • Related Report
      2005 Annual Research Report
  • [Publications] S.Ohkoshi, Y.Arimoto, T.Hozumi, H.Seino, Y.Mizobe, K.Hashimoto: "Two-dimensional metamagnet composed of cyano-bridged Cu^<II>-W^V bimetallic assembly"Chem.Commun.. 2772 (2003)

    • Related Report
      2003 Annual Research Report
  • [Publications] M.Tozawa, S.Ohkoshi, N.Kojima, K.Hashimoto: "Ion-exchange synthesis and magneto-optical spectra of colored magnetic thin films composed of metal(II) hexacyanochromate(III)"Chem.Commun.. 1204 (2003)

    • Related Report
      2003 Annual Research Report
  • [Publications] K.Kato, Y.Moritomo, M.Takata, M.Sakata, M.Umekawa, N.Hamada, S.Ohkoshi, H.Tokoro, K.Hashimoto: "Direct Observation of Charge Transfer in Double-Perovskite-Like RbMn[Fe(CN)_6]"Phys.Rev.Lett.. 91. 255502 (2003)

    • Related Report
      2003 Annual Research Report
  • [Publications] H.Tokoro, S.Ohkoshi, K.Hashimoto: "One-shot-laser-pulse-induced demagnetization in rubidium manganese hexacyanoferrate"Appl.Phys.Lett.. 82. 1245 (2003)

    • Related Report
      2003 Annual Research Report
  • [Publications] K.Ikeda, S.Ohkoshi, K.Hashimoto: "Magnetization-induced second-harmonic generation in electrochemically synthesized magnetic films of ternary metal Prussian blue analogs"J.Appl.Phys.. 93. 1371 (2003)

    • Related Report
      2003 Annual Research Report
  • [Publications] Y.Moritomo, A.Kurik, K.Ohoyama, H.Tokoro, S.Ohkosh, K.Hashimoto, N.Hamada: "Ferromagnetic spin-ordering in photo-active RbMn Fe(CN)_6",J.Phys.Soc.Jpn."J.Phys.Soc.Jpn.. 72. 456 (2003)

    • Related Report
      2003 Annual Research Report
  • [Publications] H.Osawa, T.Iwazumi, H.Tokoro, S.Ohkoshi, K.Hashimoto, H.Shoji, E.Hirai, T.Nakamura, S.Nanao, Y.Isozumi: "Thermal phase transition of RbMnFe(CN)_6 observed by X-ray emission and absorption spectroscopy"Solid State Commun.. 125. 237 (2003)

    • Related Report
      2003 Annual Research Report
  • [Publications] T.Kanai, S.Ohkoshi, K.Hashimoto: "Magnetic, Electric, and Optical Functionalities of (PLZT)_x(BiFeO_3)_<1-x> Ferroelectric-Ferromagnetic Thin Films"J.Phys.Chem.Solids. 64. 391 (2003)

    • Related Report
      2003 Annual Research Report
  • [Publications] Y.song, S.Ohkoshi, Y.Arimoto, H.Seino, Y.Mizobe, K.Hashimoto: "Synthesis, crystal structures, and magnetic properties of two cyano-bridged tungstate(V)-manganese(II) bimetallic magnets"Inorg.Chem.. 42. 1848 (2003)

    • Related Report
      2003 Annual Research Report
  • [Publications] S.Ohkoshi, T.Hozumi, M.Utsunomiya, M.Abe, K.Hashimoto: "The observation of two compensation temperatures in a cobalt-manganese hexacyanochromate"Physica B. 329. 691 (2003)

    • Related Report
      2003 Annual Research Report
  • [Publications] J.Shimura, S.Ohkoshi, K.Hashimoto: "External magnetic field effect on third-harmonic generation in Bi, Al-doped yttrium iron garnet"Appl.Phys.Lett.. 82. 3290 (2003)

    • Related Report
      2003 Annual Research Report
  • [Publications] Y.Sato, S.Ohkoshi, K.Arai, M.tozawa, K.Hashimoto: "Solvatomagnetism-induced faraday effect in a cobalt hexacyanochromate-based magnet"J.Am.Chem.Soc.. 125. 14590 (2003)

    • Related Report
      2003 Annual Research Report
  • [Publications] Y.Moritomo, K.Kato, A.Kuriki, M.Takata, M.Sakata, H.Tokoro, S.Ohkoshi, K.Hashimoto: "Structural transition induced by charge-transfer in RbMn Fe(CN)_6"J.Phys.Soc.Jpn.. 72. 2698 (2003)

    • Related Report
      2003 Annual Research Report
  • [Publications] Y.Moritomo, M.Hanawa, Y.Ohishi, K.Kato, M.Takata, A.Kuriki, E.Nishibori, M.Sakata, S.Ohkoshi, H.Tokoro, K.Hashimoto: "Pressure- and photoinduced transformation into a metastable phase in RbMnFe(CN)_6"Phys.Rev.B. 68. 144106 (2003)

    • Related Report
      2003 Annual Research Report
  • [Publications] T.Hozumi, S.Ohkoshi, Y.Arimoto, H.Seino, Y.Mizobe, K.Hashimoto: "Cooling-rate Dependent Ferromagnetism in a Two-dimensional Cyano-bridged Sm(III)-W(V) Complex"J.Phys.Chem.B. 107. 11571 (2003)

    • Related Report
      2003 Annual Research Report

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

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