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Creation and Development of Nanoscale Laboratory

Research Project

Project/Area Number 17H06119
Research Category

Grant-in-Aid for Scientific Research (S)

Allocation TypeSingle-year Grants
Research Field Nanostructural chemistry
Research InstitutionKyoto University

Principal Investigator

村田 靖次郎  京都大学, 化学研究所, 教授 (40314273)

Project Period (FY) 2017-05-31 – 2022-03-31
Project Status Granted (Fiscal Year 2021)
Budget Amount *help
¥208,130,000 (Direct Cost: ¥160,100,000、Indirect Cost: ¥48,030,000)
Fiscal Year 2021: ¥30,810,000 (Direct Cost: ¥23,700,000、Indirect Cost: ¥7,110,000)
Fiscal Year 2020: ¥29,640,000 (Direct Cost: ¥22,800,000、Indirect Cost: ¥6,840,000)
Fiscal Year 2019: ¥31,460,000 (Direct Cost: ¥24,200,000、Indirect Cost: ¥7,260,000)
Fiscal Year 2018: ¥37,700,000 (Direct Cost: ¥29,000,000、Indirect Cost: ¥8,700,000)
Fiscal Year 2017: ¥78,520,000 (Direct Cost: ¥60,400,000、Indirect Cost: ¥18,120,000)
Keywordsフラーレン / 開口フラーレン / 内包小分子 / 開口部変換反応 / 骨格拡張反応 / 拡張フラーレン / トリアジン / N-フェニルマレイミド / 単結晶構造解析 / 二量体 / ビス付加体 / 単結晶X線構造解析 / ピリダジン / 内包フラーレン / ヘテロフラーレン / 一酸化窒素 / 内包 / 分子錯体 / 1H NMR / ESR / 小分子 / 高次フラーレン / 遷移金属 / 水単分子 / 水素結合 / 緩和時間 / X線結晶構造解析 / ナノカーボン
Outline of Annual Research Achievements

フラーレンは主に炭素棒のアーク放電やベンゼン等の不完全燃焼といった過酷な条件下で生成し、C60やC70が主に生成し、C76以上の高次フラーレンの収率は極めて低いことが知られている。温和な条件下で既存のフラーレン骨格を自在に拡張する手法が開発できれば、高次フラーレンを大量合成する経路に発展できる可能性を有しており、またその過程において、拡張したフラーレン骨格にヘテロ原子を埋め込むことが出来れば、本来sp2混成の炭素のみで構成されるフラーレンに新たな機能を付与することが出来るものと期待できる。しかし、そのような例はほとんど報告されておらず、新しい手法の開発が待ち望まれていた。
本研究では、C60を原料としてC65NまたはC64N骨格へと拡張する手法を開発した。すなわち、まずピリジル基を有する1,2,4-トリアジン誘導体とフラーレンC60との熱反応により、8員環の開口部を有するフラーレンを合成した。これにN-フェニルマレイミドを反応させることによって脱有機官能基化によるC60の再生を試みたところ、そのような反応はほとんど進行せず、全く新しい化合物が高収率で生成することが明らかとなった。この化合物の構造は単結晶X線構造解析によって決定され、C60骨格にC5Nユニットが埋め込まれ、5員環と2つの7員環が新たに形成されていることを明らかにした。また、この化合物を酸で処理すると、骨格炭素が外部に放出された構造をもつC64Nへと構造が変化することが明らかとなった。さらにこのフラーレン骨格の拡張法がC70へも応用出来ることを示し、内部空間に水分子を内包させた場合、この水分子と拡張部分の窒素原子との間に磁気的な双極子相互作用が存在することを示した。

Current Status of Research Progress
Current Status of Research Progress

2: Research has progressed on the whole more than it was originally planned.

Reason

今年度の研究では、実験研究において新しい知見の発見があったため、次年度へ一部の資金を繰り越し、研究を継続させた。途中、コロナウィルスの影響があり、実験に必要な試薬や器具の調達が遅れたため、実験は若干遅れたものの、その間に大型計算機を用いた理論計算研究を進めることが可能であり、結果、おおむね順調に進展させることができた。

Strategy for Future Research Activity

当初の研究計画に従い、引き続きフラーレン骨格の骨格変換反応の開発を進め、分子内部への小分子や活性化学種の挿入を行う。また、内包種を保ったままでの開口部の閉環や、2種類の化学種の内包を検討する。さらに、得られた化合物の固体物性を明らかにする。

Assessment Rating
Result (Rating)

A-: Progress in the research is steadily towards the initial goal. However, further efforts are necessary as a part of the research progress is delayed.

Report

(8 results)
  • 2020 Annual Research Report   Abstract(Research Progress Assessment) ( PDF )   Research Progress Assessment (Result) ( PDF )
  • 2019 Annual Research Report
  • 2018 Annual Research Report
  • 2017 Abstract ( PDF )   Comments on the Screening Results ( PDF )   Annual Research Report

Research Products

(50 results)

All 2021 2020 2019 2018 2017 Other

All Int'l Joint Research (6 results) Journal Article (23 results) (of which Int'l Joint Research: 4 results,  Peer Reviewed: 23 results,  Open Access: 5 results,  Acknowledgement Compliant: 1 results) Presentation (19 results) (of which Int'l Joint Research: 11 results,  Invited: 12 results) Remarks (2 results)

  • [Int'l Joint Research] ベルリン自由大学(ドイツ)

    • Related Report
      2020 Annual Research Report
  • [Int'l Joint Research] Brown University(米国)

    • Related Report
      2018 Annual Research Report
  • [Int'l Joint Research] McGill University(カナダ)

    • Related Report
      2018 Annual Research Report
  • [Int'l Joint Research] Ruder Boskovic Institute(クロアチア)

    • Related Report
      2018 Annual Research Report
  • [Int'l Joint Research] University of East Anglia(英国)

    • Related Report
      2018 Annual Research Report
  • [Int'l Joint Research] プリンストン大学(米国)

    • Related Report
      2017 Annual Research Report
  • [Journal Article] Precise Fixation of an NO Molecule inside Carbon Nanopores: A Long‐Range Electron?Nuclear Interaction2021

    • Author(s)
      Hashikawa Yoshifumi、Hasegawa Shota、Murata Yasujiro
    • Journal Title

      Angewandte Chemie International Edition

      Volume: 60 Pages: 2866-2870

    • DOI

      10.1002/anie.202012538

    • Related Report
      2020 Annual Research Report
    • Peer Reviewed / Open Access
  • [Journal Article] Cage-Expansion of Fullerenes2021

    • Author(s)
      Zhang Sheng、Hashikawa Yoshifumi、Murata Yasujiro
    • Journal Title

      Journal of the American Chemical Society

      Volume: 143 Pages: 12450-12454

    • DOI

      10.1021/jacs.1c05778

    • Related Report
      2020 Annual Research Report
    • Peer Reviewed / Open Access
  • [Journal Article] A Single H<sub>2</sub>O Molecule inside Hydrophobic Carbon Nanocavities: Effect of Local Electrostatic Potential2020

    • Author(s)
      Hashikawa Yoshifumi、Murata Yasujiro
    • Journal Title

      Chem. Lett.

      Volume: 49 Issue: 3 Pages: 244-247

    • DOI

      10.1246/cl.190874

    • NAID

      130007805932

    • ISSN
      0366-7022, 1348-0715
    • Related Report
      2020 Annual Research Report 2019 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Organophosphorus zwitterions engaged in a conjugated macrocycle on fullerene2020

    • Author(s)
      Hashikawa Yoshifumi、Okamoto Shu、Murata Yasujiro
    • Journal Title

      Communications Chemistry

      Volume: 3 Pages: 90-90

    • DOI

      10.1038/s42004-020-00340-x

    • Related Report
      2020 Annual Research Report 2019 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Precise synthesis of double-armed polymers with fullerene C60 at the junction for controlled architecture2020

    • Author(s)
      Sakakibara Keita, Wakiuchi Araki, Murata Yasujiro, Tsujii Yoshinobu
    • Journal Title

      Polymer Chemistry

      Volume: 11 Pages: 4417-4425

    • DOI

      10.1039/d0py00458h

    • Related Report
      2020 Annual Research Report 2019 Annual Research Report
    • Peer Reviewed
  • [Journal Article] EPR study of NO radicals encased in modified open C&lt;sub&gt;60&lt;/sub&gt; fullerenes2020

    • Author(s)
      Dinse Klaus-Peter、Kato Tatsuhisa、Hasegawa Shota、Hashikawa Yoshifumi、Murata Yasujiro、Bittl Robert
    • Journal Title

      Magnetic Resonance

      Volume: 1 Pages: 197-207

    • DOI

      10.5194/mr-1-197-2020

    • Related Report
      2020 Annual Research Report 2019 Annual Research Report
    • Peer Reviewed / Int'l Joint Research
  • [Journal Article] An orifice design: water insertion into C602020

    • Author(s)
      Hashikawa Yoshifumi、Kizaki Kazuro、Hirose Takashi、Murata Yasujiro
    • Journal Title

      RSC Advances

      Volume: 10 Pages: 40406-40410

    • DOI

      10.1039/d0ra09067k

    • Related Report
      2020 Annual Research Report 2019 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Synthesis of a Dihydroxylated Open-Cage [70]Fullerene by a Reductive Ring-Closure Reaction2020

    • Author(s)
      Hashikawa Yoshifumi、Shimizu Yuma、Murata Yasujiro
    • Journal Title

      Organic Letters

      Volume: 22 Pages: 8624-8628

    • DOI

      10.1021/acs.orglett.0c03216

    • Related Report
      2020 Annual Research Report 2019 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Cation recognition on a fullerene-based macrocycle2020

    • Author(s)
      Hashikawa Yoshifumi、Murata Yasujiro
    • Journal Title

      Chemical Science

      Volume: 11 Pages: 12428-12435

    • DOI

      10.1039/d0sc05280a

    • Related Report
      2020 Annual Research Report 2019 Annual Research Report
    • Peer Reviewed / Open Access
  • [Journal Article] Double-Holed Fullerenes2020

    • Author(s)
      Hashikawa Yoshifumi、Fushino Teppei、Murata Yasujiro
    • Journal Title

      Journal of the American Chemical Society

      Volume: 142 Pages: 20572-20576

    • DOI

      10.1021/jacs.0c10676

    • Related Report
      2020 Annual Research Report 2019 Annual Research Report
    • Peer Reviewed / Open Access
  • [Journal Article] Probing the Regioselectivity with Encapsulated H2: Diels-Alder Reaction of an Open-Cage C60 Derivative with Anthracene2019

    • Author(s)
      Hashikawa Yoshifumi、Murata Yasujiro
    • Journal Title

      Chemistry A European Journal

      Volume: 25 Pages: 2482-2485

    • DOI

      10.1002/chem.201806030

    • Related Report
      2019 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Rotational Motion and Nuclear-Spin Interconversion of H2O Encapsulated in C60 Appeared in the Low-Temperature Heat Capacity2019

    • Author(s)
      H. Suzuki, M. Nakano, Y. Hashikawa, and Y. Murata
    • Journal Title

      The Journal of Physical Chemistry Letters

      Volume: 10 Pages: 1306-1311

    • DOI

      10.1021/acs.jpclett.9b00311

    • Related Report
      2019 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Tuneable Single-Molecule Electronic Conductance of C60 by Encapsulation2019

    • Author(s)
      S. Fujii, H. Cho, Y. Hashikawa, T. Nishino, Y. Murata, M. Kiguchi
    • Journal Title

      Physical Chemistry Chemical Physics

      Volume: 21 Pages: 12606-12610

    • DOI

      10.1039/c9cp02469g

    • Related Report
      2019 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Synthesis and properties of open-cage fullerene C60 derivatives: impact of the extended π-conjugation2018

    • Author(s)
      Hashikawa Yoshifumi、Yasui Hidefumi、Kurotobi Kei、Murata Yasujiro
    • Journal Title

      Mater. Chem. Front.

      Volume: 2 Pages: 206-213

    • DOI

      10.1039/c7qm00449d

    • Related Report
      2018 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Probing the interaction between the encapsulated water molecule and the fullerene cages in H2O@C60? and H2O@C59N?2018

    • Author(s)
      Zhu Guo-Zhu、Liu Yuan、Hashikawa Yoshifumi、Zhang Qian-Fan、Murata Yasujiro、Wang Lai-Sheng
    • Journal Title

      Chem. Sci.

      Volume: 9 Pages: 5666-5671

    • DOI

      10.1039/c8sc01031e

    • NAID

      120006537071

    • Related Report
      2018 Annual Research Report
    • Peer Reviewed / Int'l Joint Research
  • [Journal Article] Construction of a Metal-Free Electron Spin System by Encapsulation of an NO Molecule Inside an Open-Cage Fullerene C60 Derivative2018

    • Author(s)
      Hasegawa Shota、Hashikawa Yoshifumi、Kato Tatsuhisa、Murata Yasujiro
    • Journal Title

      Angew. Chem. Int. Ed.

      Volume: 57 Pages: 12804-12808

    • DOI

      10.1002/anie.201807823

    • Related Report
      2018 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Near- and Mid-IR Gas-Phase Absorption Spectra of H2@C60+-He2018

    • Author(s)
      Strelnikov Dmitry V.、 Jasik Juraj、Gerlich Dieter、Murata Michihisa、Murata Yasujiro、Komatsu Koichi、Roithova Jana
    • Journal Title

      J. Phys. Chem. A

      Volume: 122 Pages: 17088-17095

    • DOI

      10.1021/acs.jpca.8b06222

    • Related Report
      2018 Annual Research Report
    • Peer Reviewed / Int'l Joint Research
  • [Journal Article] A single but hydrogen-bonded water molecule confined in an anisotropic subnanospace2018

    • Author(s)
      Hashikawa Yoshifumi、Hasegawa Shota、Murata Yasujiro
    • Journal Title

      Chem. Commun.

      Volume: 54 Pages: 13686-13689

    • DOI

      10.1039/c8cc07339b

    • Related Report
      2018 Annual Research Report 2017 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Wavelength-Dependent Efficiency of Sequential Photooxygenation: C=C Bond Cleavage on Open-Cage C60 Derivatives2018

    • Author(s)
      Hashikawa Yoshifumi、Murata Yasujiro
    • Journal Title

      ChemPlusChem

      Volume: 83 Pages: 1179-1183

    • DOI

      10.1002/cplu.201800464

    • Related Report
      2018 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Single Molecular Junction Study on H2O@C60: H2O is "Electrostatically Isolated"2017

    • Author(s)
      Satoshi Kaneko, Yoshifumi Hashikawa, Shintaro Fujii, Yasujiro Murata, Manabu Kiguchi
    • Journal Title

      ChemPhysChem

      Volume: 18 Pages: 1229-1233

    • DOI

      10.1002/cphc.201700173

    • Related Report
      2017 Annual Research Report
    • Peer Reviewed / Open Access / Acknowledgement Compliant
  • [Journal Article] Palladium-Catalyzed Cyclization: Regioselectivity and Structure of Arene-Fused C60 Derivatives2017

    • Author(s)
      Hashikawa, Y.; Murata, M.; Wakamiya, A.; Murata, Y.
    • Journal Title

      Journal of the American Chemical Society

      Volume: 139 Pages: 16350-16358

    • DOI

      10.1021/jacs.7b09459

    • Related Report
      2017 Annual Research Report
    • Peer Reviewed
  • [Journal Article] High-Resolution Photoelectron Imaging of Cryogenically-Cooled C59N? and (C59N)22? Azafullerene Anions2017

    • Author(s)
      Zhu Guo-Zhu、Hashikawa Yoshifumi、Liu Yuan、Zhang Qian-Fan、Cheung Ling Fung、Murata Yasujiro、Wang Lai-Sheng
    • Journal Title

      J. Phys. Chem. Lett.

      Volume: 8 Pages: 6220-6225

    • DOI

      10.1021/acs.jpclett.7b03091

    • Related Report
      2017 Annual Research Report
    • Peer Reviewed / Int'l Joint Research
  • [Journal Article] Facile Access to Azafullerenyl Cation C59N+ and Specific Interaction with Entrapped Molecules2017

    • Author(s)
      Hashikawa, Y.; Murata, Y.
    • Journal Title

      Journal of the American Chemical Society

      Volume: 139 Pages: 18468-18471

    • DOI

      10.1021/jacs.7b11322

    • Related Report
      2017 Annual Research Report
    • Peer Reviewed
  • [Presentation] Synthesis of Open-Cage Fullerene C60 Derivatives Encapsulating a Hydrogen Peroxide Molecule2021

    • Author(s)
      Guanglin Huang, Shota Hasegawa, Yuki Ide, Yoshifumi Hashikawa, Takashi Hirose, Yasujiro Murata
    • Organizer
      日本化学会第101春季年会
    • Related Report
      2020 Annual Research Report
  • [Presentation] ジメチル-o-フェニレンジアミンによるフラーレンC60誘導体の開口部拡大反応2021

    • Author(s)
      李輝、橋川祥史、廣瀬崇至、村田靖次郎
    • Organizer
      日本化学会第101春季年会
    • Related Report
      2020 Annual Research Report
  • [Presentation] 貞井俊平、橋川祥史、廣瀬崇至、村田靖次郎2021

    • Author(s)
      二開口型フラーレンC60誘導体の合成と反応性
    • Organizer
      日本化学会第101春季年会
    • Related Report
      2020 Annual Research Report
  • [Presentation] Synthesis and Properties of an Open-Cage Fullerene C60 Derivative Having a Carboxylic Anhydride Moiety2021

    • Author(s)
      Jiayue Li, Yoshifumi Hashikawa, Takashi Hirose, Yasujiro Murata
    • Organizer
      日本化学会第101春季年会
    • Related Report
      2020 Annual Research Report
  • [Presentation] Open-Cage Fullerene C60 Derivatives Encapsulating a Paramagnetic Molecule2019

    • Author(s)
      Yasujiro Murata
    • Organizer
      235th ECS Meeting
    • Related Report
      2019 Annual Research Report
    • Int'l Joint Research / Invited
  • [Presentation] Holey Bucky: Synthesis, Structure, and Properties2019

    • Author(s)
      Yasujiro Murata
    • Organizer
      The 18th International Symposium on Novel Aromatic Compounds
    • Related Report
      2019 Annual Research Report
    • Int'l Joint Research / Invited
  • [Presentation] Putting Small Molecules into Open-Cage Fullerenes2019

    • Author(s)
      Yasujiro Murata
    • Organizer
      1st International Conference on Noncovalent Interactions
    • Related Report
      2019 Annual Research Report
    • Int'l Joint Research / Invited
  • [Presentation] Holey Bucky: Synthesis, Structure, and Properties2019

    • Author(s)
      Yasujiro Murata
    • Organizer
      π-System Figuration European-Japanese Workshop 2019
    • Related Report
      2019 Annual Research Report
    • Int'l Joint Research / Invited
  • [Presentation] Yasujiro MURATA2019

    • Author(s)
      Realization of Isolated Chemical Species by Organic Synthesis of Endohedral Fullerenes
    • Organizer
      日本化学会第99春季年会、2019年3月16ー19日、甲南大学岡本キャンパス
    • Related Report
      2018 Annual Research Report
    • Invited
  • [Presentation] Synthesis and Properties of Open-Cage Fullerene Derivatives2018

    • Author(s)
      Yasujiro Murata
    • Organizer
      233rd ECS Meeting, 13-17 May 2018, Seattle Sheraton and Washington State Convention Center, Seattle, USA
    • Related Report
      2018 Annual Research Report
    • Int'l Joint Research / Invited
  • [Presentation] Organic Synthesis of Endohedral Fullerenes Encapsulating Small Molecules2018

    • Author(s)
      Yasujiro Murata
    • Organizer
      The 19th International Symposium on Small Particles and Inorganic Clusters, 12-17 August 2018, Hangzhou International Conference Center, Hangzhou, China
    • Related Report
      2018 Annual Research Report
    • Int'l Joint Research / Invited
  • [Presentation] Endohedral Fullerenes Encapsulating Small Molecules2018

    • Author(s)
      Yasujiro Murata
    • Organizer
      The 3rd PKU-WuXi AppTec Symposium of Organic Chemistry, 20 October 2018, Peking University, Beijing, P.R.China
    • Related Report
      2018 Annual Research Report
    • Int'l Joint Research / Invited
  • [Presentation] Open-Cage Fullerene Derivatives Having a Functional Molecule inside the Cage2018

    • Author(s)
      Yasujiro Murata
    • Organizer
      The Workshop Pi-EJ2018, 4-7 Nov 2018, Hotel Ariston, Dubrovnik, Croatia
    • Related Report
      2018 Annual Research Report
    • Int'l Joint Research
  • [Presentation] Open-Cage Fullerenes toward the Synthesis of Endofullerenes and Heterofullerenes2018

    • Author(s)
      Yasujiro Murata
    • Organizer
      Aromaticity 2018, 28 Nov-1 Dec 2018, Hotel Barcelo Maya Palace Deluxe, Cancun, Mexico
    • Related Report
      2018 Annual Research Report
    • Int'l Joint Research / Invited
  • [Presentation] Organic Synthesis of Endohedral Fullerenes2017

    • Author(s)
      Yasujiro Murata
    • Organizer
      Invited Lecture at Central South University
    • Related Report
      2017 Annual Research Report
    • Int'l Joint Research / Invited
  • [Presentation] Organic Synthesis of Endohedral Fullerenes by Molecular Surgery2017

    • Author(s)
      Yasujiro Murata
    • Organizer
      International Symposium on Pure & Applied Chemistry 2017
    • Related Report
      2017 Annual Research Report
    • Int'l Joint Research / Invited
  • [Presentation] Synthesis of Endofullerenes by Molecular Surgery2017

    • Author(s)
      Yasujiro Murata
    • Organizer
      2nd International Symposium on NanoCarbons
    • Related Report
      2017 Annual Research Report
    • Invited
  • [Presentation] Synthesis and Properties of Endohedral C70 Co-Encapsulating HF and H2O Molecules2017

    • Author(s)
      Yasujiro Murata, Rui Zhang, Michihisa Murata, Atsushi Wakamiya
    • Organizer
      17th International Symposium on Novel Aromatics
    • Related Report
      2017 Annual Research Report
  • [Presentation] Palladium-Catalyzed Regioselective Functionalization of C602017

    • Author(s)
      Yoshifumi Hashikawa, Michihisa Murata, Atsushi Wakamiya, Yasujiro Murata
    • Organizer
      17th International Symposium on Novel Aromatics
    • Related Report
      2017 Annual Research Report
  • [Remarks] https://www.scl.kyoto-u.ac.jp/~kouzou/index.html

    • Related Report
      2020 Annual Research Report
  • [Remarks] 論文・著書

    • URL

      https://www.scl.kyoto-u.ac.jp/~kouzou/2010_late.html

    • Related Report
      2018 Annual Research Report

URL: 

Published: 2017-06-01   Modified: 2022-12-28  

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