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アシンメトリック配位空間を鋳型とした機能性ナノ材料創製

Planned

Project AreaCoordination Asymmetry: Design of Asymmetric Coordination Sphere and Anisotropic Assembly for the Creation of Functional Molecules
Project/Area Number 16H06517
Research Category

Grant-in-Aid for Scientific Research on Innovative Areas (Research in a proposed research area)

Allocation TypeSingle-year Grants
Review Section Science and Engineering
Research InstitutionThe University of Tokyo (2018-2020)
Kyoto University (2016-2017)

Principal Investigator

植村 卓史  東京大学, 大学院新領域創成科学研究科, 教授 (50346079)

Project Period (FY) 2016-06-30 – 2021-03-31
Project Status Granted (Fiscal Year 2020)
Budget Amount *help
¥90,740,000 (Direct Cost: ¥69,800,000、Indirect Cost: ¥20,940,000)
Fiscal Year 2020: ¥18,590,000 (Direct Cost: ¥14,300,000、Indirect Cost: ¥4,290,000)
Fiscal Year 2019: ¥19,500,000 (Direct Cost: ¥15,000,000、Indirect Cost: ¥4,500,000)
Fiscal Year 2018: ¥19,500,000 (Direct Cost: ¥15,000,000、Indirect Cost: ¥4,500,000)
Fiscal Year 2017: ¥16,120,000 (Direct Cost: ¥12,400,000、Indirect Cost: ¥3,720,000)
Fiscal Year 2016: ¥17,030,000 (Direct Cost: ¥13,100,000、Indirect Cost: ¥3,930,000)
Keywords多孔性金属錯体 / 高分子 / キラリティ / MOF / キラル / 複合体 / ポリチオフェン / 薄膜 / フラーレン / 太陽電池
Outline of Annual Research Achievements

本研究では、キラルMOFを用いることで、不斉炭素を持たずアキラルな平面構造を持つ多環芳香族炭化水素(polycyclic aromatic hydrocarbon、PAH)へのキラリティ付与に取り組んだ。PAHとしてアントラセンおよびテトラセンを用いた。また、ホストMOFとしてLaイオンと1,3,5-ベンゼントリスベンゾアート(BTB)から構成され、10.7×10.7Å2の一次元ナノ細孔を有するMOF, LaBTBを用いた。LaBTBは合成時にキラル指向剤を用いることでキラルな配位環境を有する鏡像異性体を作り分けることができる。
これまで行われてこなかった非修飾アセンへのキラリティ誘起をキラルMOFのナノ細孔内に導入することで行った。複合体のCDスペクトルから、L体とD体で鏡像関係のシグナルが観測されたことから、アントラセンおよびテトラセンのキラリティ発現を確認した。また、修飾によってねじれさせたアセンとの比較により、ゲスト分子がねじれている可能性が考えられる。今後、ねじれていることの確認として単結晶X線構造解析を行い、直接観測を行うことを考えている。
キラルMOFは、自己集合を利用することで、キラリティの制御された精密なナノ空間を簡便に作り出すことができる。このナノ空間内に拘束することでねじれが誘起されるのならば、その特異な構造ゆえに遅れていたねじれたアセンの物性の調査や応用が促進されることが期待される。また、ねじれることによって電子構造が変わるので、バルクでは不可能である新たな反応経路への応用も可能であると考えられる。

Current Status of Research Progress
Current Status of Research Progress

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

Reason

高分子だけにとどまらず、アセンなどのナノカーボン系材料へもキラリティ付与が可能と明らかになったため。

Strategy for Future Research Activity

この手法は様々な形の多環芳香族化合物に対して適用可能であり、グラフェンナノリボンやカーボンナノチューブ、あるいはさらに対称性の高い物質などへのキラル誘起が期待される。例えば、グラフェンナノリボンを細孔内でねじらせたのちに重合することで、キラルな構造制御のなされたカーボンナノチューブの精密合成ができる。このようにいままでは困難だったような様々なキラル材料の創製へとつながっていくことが期待でできる。

Report

(4 results)
  • 2019 Annual Research Report
  • 2018 Annual Research Report
  • 2017 Annual Research Report
  • 2016 Annual Research Report

Research Products

(20 results)

All 2020 2019 2018 2017 2016 Other

All Int'l Joint Research (1 results) Journal Article (9 results) (of which Int'l Joint Research: 3 results,  Peer Reviewed: 9 results,  Open Access: 4 results,  Acknowledgement Compliant: 2 results) Presentation (10 results) (of which Int'l Joint Research: 7 results,  Invited: 9 results)

  • [Int'l Joint Research] PSL Research University(フランス)

    • Related Report
      2018 Annual Research Report
  • [Journal Article] Supramolecular Chiral Nanoarchitectonics2020

    • Author(s)
      Katsuhiko Ariga, Taizo Mori, Takashi Kitao, Takashi Uemura
    • Journal Title

      Advanced Materials

      Volume: 32 Pages: 1905657-1905657

    • DOI

      10.1002/adma.201905657

    • Related Report
      2019 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Scalable and Precise Synthesis of Armchair-Edge Graphene Nanoribbon in Metal?Organic Framework2020

    • Author(s)
      Kitao Takashi、MacLean Michael W. A.、Nakata Kazuki、Takayanagi Masayoshi、Nagaoka Masataka、Uemura Takashi
    • Journal Title

      J. Am. Chem. Soc.

      Volume: 142 Pages: 5509-5514

    • DOI

      10.1021/jacs.0c00467

    • Related Report
      2019 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Transcription of Chirality from Metal?Organic Framework to Polythiophene2019

    • Author(s)
      Kitao Takashi、Nagasaka Yujiro、Karasawa Masanobu、Eguchi Toshiki、Kimizuka Nobuo、Ishii Kazuyuki、Yamada Teppei、Uemura Takashi
    • Journal Title

      J. Am. Chem. Soc.

      Volume: 141 Pages: 19565-19569

    • DOI

      10.1021/jacs.9b10880

    • Related Report
      2019 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Selective sorting of polymers with different terminal groups using metal-organic frameworks2018

    • Author(s)
      Benjamin Le Ouay, Chikara Watanabe, Shuto Mochizuki, Masayoshi Takayanagi, Masataka Nagaoka, Takashi Kitao, Takashi Uemura
    • Journal Title

      Nature Communications

      Volume: 9 Pages: 3635-3635

    • DOI

      10.1038/s41467-018-06099-z

    • Related Report
      2018 Annual Research Report
    • Peer Reviewed / Open Access / Int'l Joint Research
  • [Journal Article] A phase transformable ultrastable titanium-carboxylate framework for photoconduction2018

    • Author(s)
      Wang Sujing、Kitao Takashi、Guillou Nathalie、Wahiduzzaman Mohammad、Martineau-Corcos Charlotte、Nouar Farid、Tissot Antoine、Binet Laurent、Ramsahye Naseem、Devautour-Vinot Sabine、Kitagawa Susumu、Seki Shu、Tsutsui Yusuke、Briois Valerie、Steunou Nathalie、Maurin Guillaume、Uemura Takashi、Serre Christian
    • Journal Title

      Nature Commun.

      Volume: 9 Pages: 1660-1660

    • DOI

      10.1038/s41467-018-04034-w

    • NAID

      120006462497

    • Related Report
      2018 Annual Research Report
    • Peer Reviewed / Open Access / Int'l Joint Research
  • [Journal Article] Sequence-Regulated Copolymerization Based on Periodic Covalent Positioning of Monomers along One-Dimensional Nanochannels2018

    • Author(s)
      Shuto Mochizuki, Naoki Ogiwara, Masayoshi Takayanagi, Masataka Nagaoka, Susumu Kitagawa, Takashi Uemura
    • Journal Title

      Nat. Commun.

      Volume: 9 Pages: 329-329

    • DOI

      10.1038/s41467-017-02736-1

    • NAID

      120006380534

    • Related Report
      2017 Annual Research Report
    • Peer Reviewed / Open Access
  • [Journal Article] Opening of an Accessible Microporosity in an Otherwise Nonporous Metal-Organic Framework by Polymeric Guests2017

    • Author(s)
      Benjamin Le Ouay, Susumu Kitagawa, Takashi Uemura
    • Journal Title

      J. Am. Chem. Soc.

      Volume: 139 Pages: 7886-7892

    • DOI

      10.1021/jacs.7b02402

    • Related Report
      2017 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Preparation of Porous Polysaccharides Templated by Coordination Polymer with Three-Dimensional Nanochannels2017

    • Author(s)
      Yuichiro Kobayashi, Kayako Honjo, Susumu Kitagawa, Takashi Uemura
    • Journal Title

      ACS Appl. Mater. Interfaces

      Volume: 印刷中 Pages: 11373-11379

    • DOI

      10.1021/acsami.6b15936

    • Related Report
      2016 Annual Research Report
    • Peer Reviewed / Open Access / Acknowledgement Compliant
  • [Journal Article] Nanostructuration of PEDOT in Porous Coordination Polymers for Tunable Porosity and Conductivity2016

    • Author(s)
      Benjamin Le Ouay, Mickael Boudot, Takashi Kitao, Takeshi Yanagida, Susumu Kitagawa, Takashi Uemura
    • Journal Title

      Journal of the American Chemical Society

      Volume: 138 Pages: 10088-10091

    • DOI

      10.1021/jacs.6b05552

    • Related Report
      2016 Annual Research Report
    • Peer Reviewed / Int'l Joint Research / Acknowledgement Compliant
  • [Presentation] Polymer Chemistry in Metal-Organic Frameworks2019

    • Author(s)
      Takashi Uemura
    • Organizer
      EuroMOFs
    • Related Report
      2019 Annual Research Report
    • Int'l Joint Research / Invited
  • [Presentation] Polymer Chemistry in Metal-Organic Frameworks2018

    • Author(s)
      Takashi Uemura
    • Organizer
      6th International Conference on Metal-Organic Frameworks & Open Framework Compounds (MOF2018)
    • Related Report
      2018 Annual Research Report
    • Int'l Joint Research / Invited
  • [Presentation] Polymer Chemistry in Coordination Nanochannels2018

    • Author(s)
      Takashi Uemura
    • Organizer
      12th SPSJ International Polymer Conference (IPC 2018)
    • Related Report
      2018 Annual Research Report
    • Int'l Joint Research / Invited
  • [Presentation] Polymer Chemistry in MOFs2018

    • Author(s)
      Takashi Uemura
    • Organizer
      43rd International Conference on Coordination Chemistry (ICCC2018)
    • Related Report
      2018 Annual Research Report
    • Int'l Joint Research / Invited
  • [Presentation] Polymer Chemistry in Coordination Nanospaces2017

    • Author(s)
      Takashi Uemura
    • Organizer
      Emerging Polymer Technologies Summit
    • Related Report
      2017 Annual Research Report
    • Int'l Joint Research / Invited
  • [Presentation] Polymer Chemistry in Metal-Organic Frameworks2017

    • Author(s)
      Takashi Uemura
    • Organizer
      ChinaNANO
    • Related Report
      2017 Annual Research Report
    • Int'l Joint Research / Invited
  • [Presentation] Polymer Chemistry in MOFs2017

    • Author(s)
      Takashi Uemura
    • Organizer
      10th China-Japan Joint Symposium on Functional Supramolecular Architectures
    • Related Report
      2017 Annual Research Report
    • Int'l Joint Research / Invited
  • [Presentation] Controlled Polymerizations in Coordination Nanospaces2016

    • Author(s)
      Takashi Uemura
    • Organizer
      The 11th SPSJ International Polymer Conference (IPC 2016)
    • Place of Presentation
      福岡国際会議場
    • Year and Date
      2016-12-14
    • Related Report
      2016 Annual Research Report
    • Invited
  • [Presentation] ナノ空間を用いた高分子創製:一次構造制御からブレンド化まで2016

    • Author(s)
      植村卓史
    • Organizer
      第25回ポリマー材料フォーラム
    • Place of Presentation
      名古屋国際会議場
    • Year and Date
      2016-11-10
    • Related Report
      2016 Annual Research Report
    • Invited
  • [Presentation] 多孔性金属錯体を用いた無置換ポリチオフェンとC60との界面構造制御2016

    • Author(s)
      笹木陽太郎、北尾岳史、植村卓史、北川進
    • Organizer
      第65回高分子討論会
    • Place of Presentation
      神奈川大学横浜キャンパス
    • Year and Date
      2016-09-14
    • Related Report
      2016 Annual Research Report

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Published: 2016-07-04   Modified: 2021-01-27  

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