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2012 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  筑波大学, 数理物質科学研究科(系), 教授 (60089810)

Co-Investigator(Kenkyū-buntansha) 山田 道夫  東京学芸大学, 教育学部, 助教 (00583098)
土屋 敬広  筑波大学, 数理物質科学研究科(系), 講師 (10375412)
Project Period (FY) 2008-04-01 – 2013-03-31
Keywords金属内包フラーレン / 化学修飾 / π電子 / π曲面 / π空間
Outline of Annual Research Achievements

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。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。
前年度に引き続き、炭素ケージや内包原子にスピンを有する常磁性内包フラーレン(Sc@C82, Y@C82, La@C82, Ce@C82, Gd@C82, Sc3C2@C80等)の大量合成と精製を行なった。合成した内包フラーレンを用いて化学反応性の解明を行うと共に化学修飾による誘導体の合成を行った。内包フラーレンに対し、アダマンチルカルベン、アゾメチンイリド、シクロペンタジエン等を用いた反応により、高効率および高選択的に化学修飾し常磁性内包フラーレン誘導体の合成を行った。また、一付加誘導体へのさらなる付加反応で、二付加誘導体の合成も行った。
有機ドナーやアクセプターとの複合系を構築すると共にその光誘起電子移動挙動や結晶の電荷輸送特性について検討を行った。

Research Progress Status

24年度が最終年度であるため、記入しない。

Strategy for Future Research Activity

24年度が最終年度であるため、記入しない。

  • Research Products

    (32 results)

All 2013 2012 Other

All Journal Article (21 results) (of which Peer Reviewed: 21 results) Presentation (8 results) (of which Invited: 4 results) Book (2 results) Remarks (1 results)

  • [Journal Article] An Improbable Monometallic Cluster Entrapped in a Popular Fullerene Cage: YCN@Cs(6)-C822013

    • Author(s)
      S. Yang, C. Chen, F. Liu, Y. Xie, F. Li, M. Jiao, M. Suzuki, T. Wei, S. Wang, Z. Chen, X. Lu, T. Akasaka
    • Journal Title

      Scientific Reports

      Volume: 3 Pages: 1487/1-1487/5

    • DOI

      10.1038/srep01487

    • Peer Reviewed
  • [Journal Article] X-Ray Observation of a Helium Atom and Placing a Nitrogen Atom inside He@C60 and He@C702013

    • Author(s)
      Y. Morinaka, S. Sato, A. Wakamiya, H. Nikawa, N. Mizorogi, F. Tanabe, M. Murata, K. Komatsu, K. Furukawa, T. Kato, S. Nagase, T. Akasaka, Y. Murata
    • Journal Title

      Nature Commun.

      Volume: 4 Pages: 1554/1-1554/5

    • DOI

      10.1038/ncomms2574

    • Peer Reviewed
  • [Journal Article] Analysis of Functionalization Degree of Single-Walled Carbon Nanotubes Having Various Substituents2012

    • Author(s)
      Y. Maeda, K.Saito, N. Akanlatsu, Y. Chiba, S. Ohno, Y. Okui, M. Yamada, T. Hasegawa, M. Kako, T. Akasaka
    • Journal Title

      J. Am. Chem. Soc

      Volume: 134 Pages: 18101-18108

    • DOI

      DOI:10.1021/ja308969p

    • Peer Reviewed
  • [Journal Article] An Endohedral Metallofullerene as a Pure Electron Donor: Intramolecular Electron Transfer in Donor-Acceptor Conjugates of La2@C80 and 11,11,12,12- tetracyano-9,10-anthra-p-quinodimethane (TCAQ)2012

    • Author(s)
      Y. Takano, S. Obuchi, N. Mizorogi, R. Garia, M. A. Herranz, M. Rudolf, D. M. Guldi, N. Martin, S. Nagase, T. Akasaka
    • Journal Title

      J. Am. Chem. Soc.

      Volume: 134 Pages: 19401-19408

    • DOI

      10.1021/ja307341g

    • Peer Reviewed
  • [Journal Article] Single Crystal X-ray Diffraction Study of Three Yb@C82 Isomers Cocrystallized with NiII(octaethylporphyrin)2012

    • Author(s)
      M. Suzuki, Z. Slanina, N. Mizorogi, X. Lu, S. Nagase, M. M. Olmstead, A. L. Balch, T. Akasaka
    • Journal Title

      J. Am. Chem. Soc.

      Volume: 134 Pages: 18772-18778

    • DOI

      10.1021/ja308706d

    • Peer Reviewed
  • [Journal Article] Stabilizing Ion and Radical Ion Pair States in a Paramagnetic Endohedral Metallofullerene and a π-Extended Tetrathiafulvalene2012

    • Author(s)
      Y. Takano, S. Obuchi, N. Mizorogi, R. Garcia, M. A. Herranz, M. Rudolf, S. Wolfrum, D. M. Guldi, N. Martin, S. Nagase, T. Akasaka
    • Journal Title

      J. Am. Chem. Soc.

      Volume: 134 Pages: 16103-16106

    • DOI

      10.1021/ja3055386

    • Peer Reviewed
  • [Journal Article] Synthesis of a Silylene-Bridged Endohedral Metallofullerene Lu3N@Ih-C802012

    • Author(s)
      K. Sato, M. Kako, M. Suzuki, N. Mizorogi, T. Tsuchiya, M. Olmstead, A. Balch, T. Akasaka, S. Nagase
    • Journal Title

      J. Am. Chem. Soc.

      Volume: 134 Pages: 16033-16039

    • DOI

      10.1021/ja3073929

    • Peer Reviewed
  • [Journal Article] Exceptional Chemical Properties of Sc@C2v(9)-C82 Probed with Adamantylidine Carbene2012

    • Author(s)
      M. Hachiya, H. Nikawa, N. Mizorogi, T. Tsuchiya, X. Lu, T. Akasaka
    • Journal Title

      J. Am. Chem. Soc.

      Volume: 134 Pages: 15550-15555

    • DOI

      10.1021/ja306890x

    • Peer Reviewed
  • [Journal Article] A Paradigmatic Change ― Linking Fullerenes to Electron Acceptors2012

    • Author(s)
      L. Feng, M. Rudolf, S. Wolfrum, A. Troeger, Z. Slanina, T. Akasaka, S. Nagase, N. Martin, T. Ameri, C. Brabec, D. Guldi
    • Journal Title

      J. Am. Chem. Soc

      Volume: 134 Pages: 12190-12197

    • DOI

      10.1021/ja3039695

    • Peer Reviewed
  • [Journal Article] Tunable Charge-transport Property of Ih-C80 Endohedral Metallofullerenes: Investigation of La2@C80, Sc3N@C80, and Sc3C2@C802012

    • Author(s)
      S. Sato, S. Seki, G. Luo, M. Suzuki, J. Lu, S. Nagase, T. Akasaka
    • Journal Title

      J. Am. Chem. Soc

      Volume: 134 Pages: 11681-11686

    • DOI

      10.1021/ja303660g

    • Peer Reviewed
  • [Journal Article] Unexpected Formation of a Sc3C2@C80 Bisfulleroid Derivative2012

    • Author(s)
      H. Kurihara, Y. Iiduka, Y. Rubin, M. Waelchli, N. Mizorogi, Z. Slanina, T. Tsuchiya, S. Nagase, T. Akasaka
    • Journal Title

      J. Am. Chem. Soc.

      Volume: 134 Pages: 4092-4095

    • DOI

      10.1021/ja300279x

    • Peer Reviewed
  • [Journal Article] Chemical Understanding of Carbide Cluster Metallofullerenes: A Case Study on Sc2C2@C2v(5)-C80 with Complete X-Ray Crystallographic Characterizations2012

    • Author(s)
      H. Kurihara, X. Lu, Y. Iiduka, H. Nikawa, N. Mizorogi, Z. Slanina, T. Tsuchiya, S. Nagase, T. Akasaka
    • Journal Title

      J. Am. Chem. Soc.

      Volume: 134 Pages: 3139-3144

    • DOI

      10.1021/ja210101f

    • Peer Reviewed
  • [Journal Article] The Long-Believed Sc2@C2v(17)-C84 is Actually Sc2C2@C2v(9)-C82. Unambiguous Structure Assignment and Chemical Functionalization2012

    • Author(s)
      X. Lu, K. Nakajima, Y. Iiduka, H. Nikawa, T. Tsuchiya, N. Mizorogi, Z. Slanina, S. Nagase, T. Akasaka
    • Journal Title

      Angew. Chem. Int. Ed.

      Volume: 51 Pages: 5889-5892

    • DOI

      10.1002/anie.201201325

    • Peer Reviewed
  • [Journal Article] A Co-Crystal Composed of the Paramagnetic Endohedral Metallofullerene La@C82 and a Nickel Porphyrin with High Electron Mobility2012

    • Author(s)
      S. Sato, H. Nikawa, S. Seki, L. Wang, G. Luo, J. Lu, M. Haranaka, T. Tsuchiya, S. Nagase, T. Akasaka
    • Journal Title

      Angew. Chem. Int. Ed.

      Volume: 51 Pages: 1589-1591

    • DOI

      10.1002/anie.201106912

    • Peer Reviewed
  • [Journal Article] Sc2@C3v(8)-C82 vs. Sc2C2@C3v(8)-C82: Drastic Effect of C2 Capture on the Redox Properties of Scandium Metallofullerenes2012

    • Author(s)
      H. Kurihara, X. Lu, Y. Iiduka, N. Mizorogi, Z. Slanina, T. Tsuchiya, S. Nagase, T. Akasaka
    • Journal Title

      Chem. Commun.

      Volume: 48 Pages: 1290-1292

    • DOI

      10.1039/c2cc16422a

    • Peer Reviewed
  • [Journal Article] Where Does the Metal Cation Stay in Gd@C2v(9)-C82? A Single-Crystal X-Ray Diffraction Study2012

    • Author(s)
      M. Suzuki, X. Lu, S. Sato, H. Nikawa, N. Mizorogi, Z. Slanina, T. Tsuchiya, S. Nagase, T. Akasaka
    • Journal Title

      Inorg. Chem.

      Volume: 51 Pages: 5270-5273

    • DOI

      10.1021/ic300186y

    • Peer Reviewed
  • [Journal Article] X-Ray Structures of Sc2C2@C2n (n = 40, 41, 42): In-Depth Understanding of the Core-Shell Interplay in Carbide Cluster Metallofullerenes2012

    • Author(s)
      H. Kurihara, X. Lu, Y. Iiduka, H. Nikawa, M. Hachiya, N. Mizorogi, Z. Slanina, T. Tsuchiya, S. Nagase, T. Akasaka
    • Journal Title

      Inorg. Chem.

      Volume: 51 Pages: 746-750

    • DOI

      10.1021/ic202438u

    • Peer Reviewed
  • [Journal Article] Electron Transport through Single Endohedral Ce@C82 Metallofullerenes2012

    • Author(s)
      S. Kaneko, L. Wang, G. Luo, J. Lu, S. Nagase, S. Sato, M. Yamada, Z. Slanina, T. Akasaka, M. Kiguchi
    • Journal Title

      Phys. Rev. B

      Volume: 86 Pages: 155406-1~7

    • DOI

      10.1103/PhysRevB.86.155406

    • Peer Reviewed
  • [Journal Article] Stability Computations for Isomers of La@Cn (n = 72, 74, 76)2012

    • Author(s)
      Z. Slanina, F. Uhlik, S.-L. Lee, L. Adamowicz, T. Akasaka, S. Nagase
    • Journal Title

      Molecules

      Volume: 17 Pages: 13146-13156

    • DOI

      10.3390/molecules171113146

    • Peer Reviewed
  • [Journal Article] Bis-Silylation of Lu3N@Ih-C80: Considerable Variation in the Electronic Structures2012

    • Author(s)
      K. Sato, M. Kako, N. Mizorogi, T. Tsuchiya, T. Akasaka
    • Journal Title

      Org. Lett

      Volume: 15 Pages: 5908-5911

    • DOI

      10.1021/ol302832k

    • Peer Reviewed
  • [Journal Article] Diameter-Selective Purification of Carbon Nanotubes by Microwave-Assisted Acid Processing2012

    • Author(s)
      H. Qiu, Y. Maeda, T. Akasaka, J. Yang
    • Journal Title

      Sep. Purif. Technol.

      Volume: 96 Pages: 182-186

    • DOI

      org/10.1016/j.seppur.2012.06.001

    • Peer Reviewed
  • [Presentation] フラーレンを鍵物質とする高次π空間の創発と機能開拓2013

    • Author(s)
      赤阪 健
    • Organizer
      科研費新学術領域研究「融合マテリアル」第6回公開シンポジウム
    • Place of Presentation
      TKPガーデンシティ仙台、仙台市
    • Year and Date
      2013-01-28
    • Invited
  • [Presentation] New Vistas in Fullerene Chemistry: Oraganosulfur Compounds Expand the Performance of Carbon Nanomaterials2012

    • Author(s)
      Takeshi Akasaka
    • Organizer
      25th International Symposium on the Organic Chemistry of Sulfur
    • Place of Presentation
      Czestochowa, Poland
    • Year and Date
      20120624-29
  • [Presentation] フラーレンを鍵物質とする高次π空間の創発と機能開拓2012

    • Author(s)
      赤阪 健
    • Organizer
      第6回有機π電子系シンポジウム
    • Place of Presentation
      道後温泉 茶波瑠、松山市
    • Year and Date
      2012-12-14
    • Invited
  • [Presentation] New Vistas in Chemistry of Nanocarbons: Organic Nanomaterials Based on Endohedral Metallofullerenes2012

    • Author(s)
      Takeshi Akasaka
    • Organizer
      The Symposium on Material Chemistry in Heilongjiang University
    • Place of Presentation
      Harbin, China
    • Year and Date
      2012-09-14
    • Invited
  • [Presentation] New Vistas in fullerene Endohedrals2012

    • Author(s)
      Takeshi Akasaka
    • Organizer
      XXIst International Symposium on Jahn-Teller Effect
    • Place of Presentation
      Univ. of Tsukuba, Japan
    • Year and Date
      2012-08-26
    • Invited
  • [Presentation] New Vistas in Chemistry of Nanocarbons: Organic Nanomaterials Based on Endohedral Metallofullerenes2012

    • Author(s)
      赤阪健
    • Organizer
      岡山大学異分野研究連携コア講演会
    • Place of Presentation
      岡山大学、岡山
    • Year and Date
      2012-08-07
  • [Presentation] New Vistas in Chemistry of Synthetic Carbon Allotropes: Organic Nanomaterials Based on Endohedral Metallofullerenes2012

    • Author(s)
      Takeshi Akasaka
    • Organizer
      9th International Conference on Nanosciences & Nanotechnologies
    • Place of Presentation
      Thessaloniki, Greece
    • Year and Date
      2012-07-03
  • [Presentation] New Vistas in Chemistry of Synthetic Carbon Allotropes: Organic Nanomaterials Based on Endohedral Metallofullerenes2012

    • Author(s)
      Takeshi Akasaka
    • Organizer
      49th Outstanding Scholors Forum in Huazhong University of Science and Technology
    • Place of Presentation
      Wuhan, China
    • Year and Date
      2012-06-05
  • [Book] Stability Computations for Fullerenes and Metallofullerenes In "Handbook of Carbon Nano Materials2012

    • Author(s)
      Z. Slanina, F. Uhlik, S-L. Lee, T. Akasaka, S. Nagase
    • Total Pages
      49 (pp. 381-429)
    • Publisher
      World Scientific
  • [Book] Endohedral Metallofullerene Functionalization, In "Advances in Carbon Nanomaterials: Science and Applications2012

    • Author(s)
      Y. Maeda, T. Akasaka, S. Nagase
    • Total Pages
      30 (pp. 269-298)
    • Publisher
      Pan Stanford Publishing
  • [Remarks] 赤阪研究室HP

    • URL

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

URL: 

Published: 2018-02-02  

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