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A strategy toward isolation of ultra-unstable chemical species: Step-by-step insertion of atoms/molecules into fullerene inside

Research Project

Project/Area Number 21H01737
Research Category

Grant-in-Aid for Scientific Research (B)

Allocation TypeSingle-year Grants
Section一般
Review Section Basic Section 28010:Nanometer-scale chemistry-related
Research InstitutionTohoku University

Principal Investigator

Ueno Hiroshi  東北大学, 学際科学フロンティア研究所, 助教 (00775752)

Co-Investigator(Kenkyū-buntansha) 村田 靖次郎  京都大学, 化学研究所, 教授 (40314273)
青柳 忍  名古屋市立大学, 大学院理学研究科, 教授 (40360838)
Project Period (FY) 2021-04-01 – 2024-03-31
Project Status Completed (Fiscal Year 2023)
Budget Amount *help
¥17,940,000 (Direct Cost: ¥13,800,000、Indirect Cost: ¥4,140,000)
Fiscal Year 2023: ¥3,380,000 (Direct Cost: ¥2,600,000、Indirect Cost: ¥780,000)
Fiscal Year 2022: ¥3,380,000 (Direct Cost: ¥2,600,000、Indirect Cost: ¥780,000)
Fiscal Year 2021: ¥11,180,000 (Direct Cost: ¥8,600,000、Indirect Cost: ¥2,580,000)
Keywords内包フラーレン / 不安定化学種 / 分子手術 / プラズマ / フラーレン / ナノ炭素 / リチウムイオン / クラスター
Outline of Research at the Start

隔離された不活性空間として知られるフラーレン内部へ段階的に原子・分子を挿入することで,不安定な分子や原子集合体をボトムアップ的に構築・単離する手法を確立する.具体的には,プラズマを用いた原子・イオン挿入法,および有機合成による小分子配置手法を駆使することで,『単離が極めて困難な不安定化学種』を内包したフラーレンの合成を実現する.フラーレン内部に配置されることで定常的に存在可能となった不安定化学種の構造,構成原子間相互作用の詳細にアプローチし,これらに起因する物性を探索する.本研究により,未踏構造の積極利用へと導く『不安定化学種の新科学』の開拓・拡大へ向けた研究基盤を構築する.

Outline of Final Research Achievements

We have established a method to construct unstable molecules/clusters at the inner space of fullerene, known as a highly inert environment. With this approach, now we can stabilize and therefore isolate various unstable chemical species that have been previously studied only in specific environments, in vacuum. By stabilizing the structure and physicochemical properties of these species, it becomes possible to explore and utilize their properties as stable bulk materials. For example, we successfully achieved on-site construction of Li+-H2O clusters inside C60, which have been traditionally studied in gas phase science. Through measurements in solid and solution phases, we demonstrated the detailed characterization of the structure and properties of these chemical species and their potential for practical applications.

Academic Significance and Societal Importance of the Research Achievements

安定化が困難な不安定分子は,気相実験や極低温下をはじめとする特殊な条件における実験の対象となっている。これらの実験によって得られる基礎的な知見は,反応デザイン,材料設計指針を与えうる点で重要であるが,直接物性応用へと繋げることは,安定性・単離の観点から極めて困難とされている。このような不安定分子を安定化する手法の開発(=不安定な構造を如何に安定化するかという化学全般にわたる大課題に対する回答)は,未知の構造・物性相関を発見・理解・応用する上で重要な意義を持つ。

Report

(4 results)
  • 2023 Annual Research Report   Final Research Report ( PDF )
  • 2022 Annual Research Report
  • 2021 Annual Research Report
  • Research Products

    (21 results)

All 2024 2023 2022 2021

All Journal Article (5 results) (of which Int'l Joint Research: 2 results,  Peer Reviewed: 4 results,  Open Access: 3 results) Presentation (16 results) (of which Int'l Joint Research: 5 results,  Invited: 3 results)

  • [Journal Article] Enhanced Reactivity of Li+@C60 toward Thermal [2+2]Cycloaddition by Encapsulated Li+ Lewis Acid2024

    • Author(s)
      Hiroshi Ueno, Yu Yamazaki, Hiroshi Okada, Fuminori Misaizu, Ken Kokubo, Hidehiro Sakurai
    • Journal Title

      Beilstein J. Org. Chem.

      Volume: 20 Pages: 653-660

    • DOI

      10.3762/bjoc.20.58

    • Related Report
      2023 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Synthesis and Characterization of Ionic Li<sup>+</sup>@C<sub>70</sub> Endohedral Fullerene2023

    • Author(s)
      Ueno Hiroshi、Kitabatake Daiki、Mabuchi Takuya、Aoyagi Shinobu、Itoh Takashi、Deng Ting、Misaizu Fuminori
    • Journal Title

      Chemistry - A European Journal

      Volume: 30 Issue: 7

    • DOI

      10.1002/chem.202303908

    • Related Report
      2023 Annual Research Report
    • Peer Reviewed / Open Access / Int'l Joint Research
  • [Journal Article] 特異な包接分子『内包フラーレン』の科学―新しい内包フラーレンファミリー:イオン内包フラーレン―2023

    • Author(s)
      上野 裕
    • Journal Title

      化学と工業(日本化学会)

      Volume: 76-4 Pages: 238-239

    • Related Report
      2023 Annual Research Report
  • [Journal Article] Synthesis of Neutral Li-Endohedral PCBM: An n-Dopant for Fullerene Derivatives2022

    • Author(s)
      H. Ueno, D. Kitabatake, H. S. Lin, Y. Ma, I. Jeon, S. Izawa, M. Hiramoto, F. Misaizu, S. Maruyama, Y. Matsuo
    • Journal Title

      Chem. Commun.

      Volume: 58 Issue: 73 Pages: 10190-10193

    • DOI

      10.1039/d2cc03678a

    • Related Report
      2022 Annual Research Report
    • Peer Reviewed / Open Access / Int'l Joint Research
  • [Journal Article] Facile Multiple Alkylations of C60 Fullerene2022

    • Author(s)
      Miwa Kazuhira、Aoyagi Shinobu、Sasamori Takahiro、Morisako Shogo、Ueno Hiroshi、Matsuo Yutaka、Yorimitsu Hideki
    • Journal Title

      Molecules

      Volume: 27 Issue: 2 Pages: 450-450

    • DOI

      10.3390/molecules27020450

    • Related Report
      2022 Annual Research Report
    • Peer Reviewed / Open Access
  • [Presentation] Chemistry of Ionic Endofullerenes2024

    • Author(s)
      Hiroshi Ueno
    • Organizer
      International Cross-disciplinary Symposium
    • Related Report
      2023 Annual Research Report
    • Int'l Joint Research / Invited
  • [Presentation] Synthesis and Structure Analysis of Ionic Na+@C60 Endohedral Fullerene2024

    • Author(s)
      Hiroshi Ueno, Hiroshi Okada, Kaoru Hiramoto, Takuya Mabuchi, Koichi Utsugi, Eunsang Kwon, Fuminori Misaizu
    • Organizer
      The 66th Fullerene-Nanotube-Graphene General Symposium
    • Related Report
      2023 Annual Research Report
    • Int'l Joint Research
  • [Presentation] Synthesis of Ion-Endohedral Fullerenes by Plasma Implantation2023

    • Author(s)
      Hiroshi Ueno, Daiki Kitabatake, Koichi Utsugi, Takuya Mabuchi, Shinobu Aoyagi, Fuminori, Misaizu
    • Organizer
      243rd ECS Meeting
    • Related Report
      2023 Annual Research Report
    • Int'l Joint Research / Invited
  • [Presentation] プラズマシャワー後のクルード中に含まれる Li イオン内包フラーレンの抽出効率の向上2023

    • Author(s)
      那須川錦, 笠間泰彦, 河地和彦, 佐藤撤雄, 武田光博, 松原正樹, 柳生穂高, 上野裕, 權垠相, 吉田慎一朗
    • Organizer
      第50回炭素材料学会
    • Related Report
      2023 Annual Research Report
  • [Presentation] Monomer-Dimer Equilibrium of Li-Endohedral [70]Fullerene Studied by Variable Temperature ESR Spectroscopy2022

    • Author(s)
      Daiki Kitabatake, Hiroshi Ueno, Fuminori Misaizu
    • Organizer
      The 63rd Fullerene-Nanotube-Graphene General Symposium
    • Related Report
      2022 Annual Research Report
  • [Presentation] Synthesis of Sodium-Ion-Endohedral [60]Fullerene Na+@C60 by Plasma Implantation2022

    • Author(s)
      Koichi Utsugi, Hiroshi Ueno, Fuminori Misaizu
    • Organizer
      The 63rd Fullerene-Nanotube-Graphene General Symposium
    • Related Report
      2022 Annual Research Report
  • [Presentation] Plasma-CVD Enabling Seeded Growth of Nanocarbons from a Single Carbon-Nanoring2022

    • Author(s)
      Rikizo Hatakeyama, Hiroshi Ueno, Eunsang Kwon, Fuminori Misaizu
    • Organizer
      75th Annual The Gaseous Electronics Conference / The 11th International Conference on Reactive Plasmas
    • Related Report
      2022 Annual Research Report
  • [Presentation] Proof-of-Principle Plasma Processing on the Growth of Single-Walled Carbon Nanotubes Originating from a Single Carbon-Nanoring2022

    • Author(s)
      Rikizo Hatakeyama, Hiroshi Ueno, Eunsang Kwon, Fuminori Misaizu
    • Organizer
      6th Asia-Pacific Conference on Plasma Physics
    • Related Report
      2022 Annual Research Report
  • [Presentation] Li@C70の超原子分子軌道(SAMO)計測 ー 基板依存性 ー2022

    • Author(s)
      山田 洋一, 北畠 大樹, 延山 知弘, 大橋 左和, 清水 好葉, 佐々木 正洋, 河地 和彦, 笠間 泰彦, 美齊津 文, 上野 裕
    • Organizer
      第83回応用物理学会秋季学術講演会
    • Related Report
      2022 Annual Research Report
  • [Presentation] 不安定化学種の新科学2022

    • Author(s)
      上野 裕
    • Organizer
      FRIS/TI-FRIS Hub Meeting
    • Related Report
      2022 Annual Research Report
  • [Presentation] Direct Observation of Superatom Molecular Orbitals (SAMOs) of Li@C70 (2)2022

    • Author(s)
      清水好葉,佐々木正洋,北畠大樹,河地和彦,笠間泰彦,美齊津文典,上野裕,山田洋一
    • Organizer
      第69回応用物理学会
    • Related Report
      2021 Annual Research Report
  • [Presentation] Isolation of C70-Based Endohedral Fulleride Li@C702022

    • Author(s)
      Daiki Kitabatake, Hiroshi Ueno, Fuminori Misaizu
    • Organizer
      62nd Fullerenes, Nanotubes, and Graphene General Symposium
    • Related Report
      2021 Annual Research Report
  • [Presentation] Facile synthesis of icosapropyl [60]fullerene2022

    • Author(s)
      Kazuhira Miwa, Shinobu Aoyagi, Takahiro Sasamori, Shogo Morisako, Hiroshi Ueno, Yutaka Matsuo, Hideki Yorimitsu
    • Organizer
      62nd Fullerenes, Nanotubes, and Graphene General Symposium
    • Related Report
      2021 Annual Research Report
  • [Presentation] Synthesis and Characterization of Li+-Encapsulated C70 (Li+@C70): A New Ionic Endohedral Fullerene2021

    • Author(s)
      Hiroshi Ueno, Kazuhiko Kawachi, Daiki Kitabatake, Keijiro Ohshimo, Hiroshi Okada, Eunsang Kwon, Shinobu Aoyagi, Yasuhiko Kasama, Fuminori Misaizu
    • Organizer
      Pacifichem2021
    • Related Report
      2021 Annual Research Report
    • Int'l Joint Research
  • [Presentation] Chemistry of Ionic Endohedral Fullerenes2021

    • Author(s)
      Hiroshi Ueno
    • Organizer
      Fall Meeting of Polymer Society of Korea (Molecular Electronics Division)
    • Related Report
      2021 Annual Research Report
    • Int'l Joint Research / Invited
  • [Presentation] Synthesis and Characterization of Li-Encapsulated PCBM (Li@PCBM): the First Li@C60 Derivative2021

    • Author(s)
      Hiroshi Ueno, Daiki Kitabatake, Hao-Sheng Lin, Yue Ma, Il Jeon, Fuminori Misaizu, Shigeo Maruyama, Yutaka Matsuo
    • Organizer
      61st Fullerenes, Nanotubes, and Graphene General Symposium
    • Related Report
      2021 Annual Research Report

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Published: 2021-04-28   Modified: 2025-01-30  

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