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2008 Fiscal Year Annual Research Report

π空間に閉じこめられた物質系の創製と機能

Planned Research

Project AreaEmergence of highly elaborated pai-space and its function
Project/Area Number 20108002
Research InstitutionUniversity of Tsukuba

Principal Investigator

赤阪 健  University of Tsukuba, 大学院・数理物質科学研究科, 教授 (60089810)

Keywords金属内包フラーレン / 化学修飾 / π電子 / π曲面 / π空間
Research Abstract

本研究では、湾曲した拡張π電子系を有するフラーレン内部の高次π空間に常磁性金属原子を取り込んだ金属内包フラーレンを鍵物質とし、その高効率で高選択的な化学修飾法の開発を行うと共に機能性金属内包フラーレンを合成することを目的とする。得られた機能性金属内包フラーレンを超分子的に配列し、磁性-伝導ハイブリッド素子へと展開する。電子的、磁気的特性に優れた金属内包フラーレンを自在に配列し、集積化することができれば、次世代のスピンナノデバイスへの応用の可能性が飛躍的に高まると考えられる。この集積化の手段として、申請者は化学修飾による機能化が有効であると考える。
常磁性内包フラーレンを大量合成し、合成した内包フラーレンを用いて化学反応性の解明と共に化学修飾による誘導体の合成を行った。具体的にはスピンの形式の異なる以下3種類の常磁性内包フラーレンを合成した。(1) 炭素ケージ上にスピンを有する内包フラーレンLa@C_<82>、(2) 内包原子上にスピンを有する内包フラーレン[Sc_3N@C_<80>]^<*->や[La_2@C_<80>]^<*->、そして(3) ケージと内包原子の両方にスピンを有する内包フラーレンCe@C_<82>やGd@C_<82>。これらを大量に合成し、我々が開発した簡便分離法を用いて効率的に精製を行った。次にこれらの内包フラーレンに対し光ケイ素化反応、カルベン付加、1, 3-双極子付加反応、Diels-Alder反応等を用いた化学修飾を行い、金属内包フラーレン誘導体の合成を行った。さらに、合成した誘導体について各種スペクトルおよび電気化学等の測定から、金属内包フラーレン誘導体の電子的特性や酸化還元特性などを明らかにした。

  • Research Products

    (31 results)

All 2009 2008 Other

All Journal Article (21 results) (of which Peer Reviewed: 20 results) Presentation (9 results) Remarks (1 results)

  • [Journal Article] Radical Coupling Reaction of Paramagnetic Endohedral Metallofullerene La@C_<82>2008

    • Author(s)
      Y. Takano, et.al.
    • Journal Title

      J. Am. Chem. Soc. 130

      Pages: 16224-16230

    • Peer Reviewed
  • [Journal Article] Does Gd@C_<82> Have an Anomalous Endohedral Structure? Synthesis and Single Crystal X-ray Structure of the Carbene Adduct2008

    • Author(s)
      T. Akasaka, et.al.
    • Journal Title

      J. Am. Chem. Soc. 130

      Pages: 12840-12841

    • Peer Reviewed
  • [Journal Article] Chemical Understanding of a Non-IPR Metallofullerene : Stabilization of Encaged Metals on Fused-pentagon Bonds in La_2@C_<72>2008

    • Author(s)
      X. Lu, et.al
    • Journal Title

      J. Am. Chem. Soc. 130

      Pages: 9129-9136

    • Peer Reviewed
  • [Journal Article] Metal Atoms Collinear with the Spiro Carbon of 6, 6-Open Adducts, M_2@C_<80>(Ad) (M = La and Ce, Ad = Adamantylidene)2008

    • Author(s)
      M. Yamada, et.al.
    • Journal Title

      J. Am. Chem. Soc. 130

      Pages: 1171-1176

    • Peer Reviewed
  • [Journal Article] Addition of Adamantylidene to La_2@C_<78> : Isolation and Single-Crystal X-ray Structural Determination of the Monoadducts2008

    • Author(s)
      B. Cao, et.al.
    • Journal Title

      J. Am. Chem. Soc. 130

      Pages: 983-989

    • Peer Reviewed
  • [Journal Article] Nanorods of Endohedral Metallofullerene Derivative2008

    • Author(s)
      T. Tsuchiya, et.al.
    • Journal Title

      J. Am. Chem. Soc. 130

      Pages: 450-451

    • Peer Reviewed
  • [Journal Article] Bis-carbene Adducts of Non-IPR La2@C72 : Localization of High Reactivi ty around Fused-pentagons and Toward Controllable Tuning of Electroc hemical Properties of Metallofullerenes2008

    • Author(s)
      X. Lu, et.al.
    • Journal Title

      Angew. Chem. Int. Ed. 47

      Pages: 8642-8645

    • Peer Reviewed
  • [Journal Article] Observation of ^<13>C NMR Chemical Shifts of Metal Carbides Encapsulate d in Fullerenes : Sc_2C_2@C_<82>, Sc_2C_2@C_<84>, and Sc_3C_2@C_<80>2008

    • Author(s)
      Y. Yamazaki, et.al.
    • Journal Title

      Angew. Chem. Int. Ed. 47

      Pages: 7905-7908

    • Peer Reviewed
  • [Journal Article] [2+1]-Cycloaddition of Nitrene onto C_<60> Revisited : Interconversion between Aziridinofullerene and Azafulleroid2008

    • Author(s)
      T. Nakahodo, et.al.
    • Journal Title

      Angew. Chem. Int. Ed. 47

      Pages: 1298-1300

    • Peer Reviewed
  • [Journal Article] Excited-State and Photoelectrochemical Behavior of Pyrene-Linked Phen yleneethynylene Oligomer2008

    • Author(s)
      Y. Matsunaga, et.al.
    • Journal Title

      J. Phys. Chem. B 112

      Pages: 14539-14547

    • Peer Reviewed
  • [Journal Article] Spectroscopic and Theoretical Study of Endohedral Dimetallofullerene Having a Non-IPR Fullerene Cage : Cc_2@C_<72>2008

    • Author(s)
      NI. Yamada, et.al.
    • Journal Title

      J. Phys. Chem. A 112

      Pages: 7627-7631

    • Peer Reviewed
  • [Journal Article] Isolation and Characterization of Carbene Derivatives of La@C_<82>(Cs)2008

    • Author(s)
      T. Akasaka, et.al.
    • Journal Title

      J. Phys. Chem. A 112

      Pages: 1294-1297

    • Peer Reviewed
  • [Journal Article] Simple Purification and Selective Enrichment of Metallic SWCNTs Produced Using the Arc-discharge Method2008

    • Author(s)
      Y. Maeda, et.al.
    • Journal Title

      Carbon 46

      Pages: 1563-1569

    • Peer Reviewed
  • [Journal Article] Preparation of Transparent and Conductive Thin Films of Metallic Single-walled Carbon Nanotubes2008

    • Author(s)
      Y. Maeda, et.al.
    • Journal Title

      J. Mater. Chem. 18

      Pages: 4189-4192

    • Peer Reviewed
  • [Journal Article] Synthesis of Selenylfullerene with Seleniumcontaining Dibenzo[b, g]cyclooctane Moiety2008

    • Author(s)
      T. Nakahodo, et.al.
    • Journal Title

      Tetrahedron Lett 49

      Pages: 2302-2305

    • Peer Reviewed
  • [Journal Article] Location of the Metal Atoms in Ce_2@C_<78> and its Bis-silylated Derivative2008

    • Author(s)
      M. Yamada, et.al.
    • Journal Title

      Chem. Commun. 2008

      Pages: 558-560

    • Peer Reviewed
  • [Journal Article] Generation of Nitrene by the Photolysis of N-substituted Iminodibenzothiophene2008

    • Author(s)
      H. Morita, et.al.
    • Journal Title

      J. Org. Chem. 73

      Pages: 7159-7163

    • Peer Reviewed
  • [Journal Article] Selective Adsorption of Cations on Single-walled Carbon Nanotubes : A Density Functional Theory Study2008

    • Author(s)
      D. Wang, et.al.
    • Journal Title

      Computational Materials Science 43

      Pages: 886-891

    • Peer Reviewed
  • [Journal Article] Synthesis and Characterization of Co(II), Ni(II), and Cu(II) Complexes Containing an Eightmembered Disulfanenitrile Chelating Ring2008

    • Author(s)
      T. Fujii, et.al.
    • Journal Title

      Inorganica Chimica Acta 361

      Pages: 2540-2546

    • Peer Reviewed
  • [Journal Article] C_<60>(OH)_n Assisted dispersion of single-walled carbon nanotubes2008

    • Author(s)
      Y. Maeda, et.al.
    • Journal Title

      Nano 3

      Pages: 455-459

    • Peer Reviewed
  • [Journal Article] 金属性単層カーボンナノチューブの分離法の開拓2008

    • Author(s)
      前田優、長谷川正、赤阪健、永瀬茂
    • Journal Title

      ケミカルエンジニアリング 53

      Pages: 363-369

  • [Presentation] 高次π空間の創発2009

    • Author(s)
      T. Akasaka
    • Organizer
      日本化学会第89回春季年会
    • Place of Presentation
      船橋市
    • Year and Date
      20090327-30
  • [Presentation] Emergence of Highly Elaborated pi-Space : Endohedral Metallofullerenes2009

    • Author(s)
      T. Akasaka
    • Organizer
      College of Chemistry and Molecular Engineering, Peking University
    • Place of Presentation
      Beijing, China
    • Year and Date
      2009-03-23
  • [Presentation] New Progress in Nanocarbon Science : Endohedral Metallofullerene2008

    • Author(s)
      T. Akasaka
    • Organizer
      The Yong Hae Kim Lectureship, Korean Institute of Science and Technology
    • Place of Presentation
      Daejeon, Korea
    • Year and Date
      2008-12-03
  • [Presentation] New Fullerene World Opened by Functionalization with Main Group Element Compounds2008

    • Author(s)
      T. Akasaka
    • Organizer
      Polish Academy of Sciences
    • Place of Presentation
      Lodz, Poland
    • Year and Date
      2008-11-27
  • [Presentation] ナノカーボンの新展開 : 金属内包フラーレン2008

    • Author(s)
      T. Akasaka
    • Organizer
      有機金属部会平成20年度第3回例会
    • Place of Presentation
      仙台市
    • Year and Date
      2008-10-30
  • [Presentation] New Progress in Nanocarbon Science : Endohedral Metallofullerene2008

    • Author(s)
      T. Akasaka
    • Organizer
      Plenary Lecture at Faculty of Chemical Engineering, Nanjing University of Science and Technology
    • Place of Presentation
      Nanjing, China
    • Year and Date
      2008-09-08
  • [Presentation] A New Approach for Nano-Device Applications -More is Different in Metallofullerenes2008

    • Author(s)
      T. Akasaka
    • Organizer
      NIMS Week 2008
    • Place of Presentation
      Tsukuba, Japan
    • Year and Date
      2008-07-15
  • [Presentation] A New Approach for Nano-Device Applications -More is Different in Metallofullerenes2008

    • Author(s)
      T. Akasaka
    • Organizer
      University of California at Davis
    • Place of Presentation
      Davis, USA
    • Year and Date
      2008-07-01
  • [Presentation] New Progress in Chemistry of Nanocarbons : Endohedral Metallofullerpnes2008

    • Author(s)
      T. Akasaka
    • Organizer
      Department of Chemistry, University of Compultense at Madrid
    • Place of Presentation
      Madrid, Spain
    • Year and Date
      2008-06-09
  • [Remarks]

    • URL

      http://www.tara.tsukuba.ac.jp/~akasaka-lab/

URL: 

Published: 2010-06-11   Modified: 2016-04-21  

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