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Construction of novel fluorescent materials based on the self-assembly of curved pi-conjugated surfaces

Research Project

Project/Area Number 19K23623
Research Category

Grant-in-Aid for Research Activity Start-up

Allocation TypeMulti-year Fund
Review Section 0501:Physical chemistry, functional solid state chemistry, organic chemistry, polymers, organic materials, biomolecular chemistry, and related fields
Research InstitutionTokyo Institute of Technology

Principal Investigator

Yamashina Masahiro  東京工業大学, 理学院, 助教 (80847153)

Project Period (FY) 2019-08-30 – 2021-03-31
Project Status Completed (Fiscal Year 2020)
Budget Amount *help
¥2,860,000 (Direct Cost: ¥2,200,000、Indirect Cost: ¥660,000)
Fiscal Year 2020: ¥1,430,000 (Direct Cost: ¥1,100,000、Indirect Cost: ¥330,000)
Fiscal Year 2019: ¥1,430,000 (Direct Cost: ¥1,100,000、Indirect Cost: ¥330,000)
Keywords分子内包 / 湾曲したπ共役系 / ホスト-ゲスト / ケージ分子 / 湾曲したパイ共役系 / ホストーゲスト / パイ共役系 / ホストゲスト / 超分子化学 / 自己集合 / アントラセン / 蛍光
Outline of Research at the Start

本研究では新規蛍光材料の開発を目指し、アントラセン環のπ共役系をジインとベンゼン環で拡張・湾曲させた、新規ボウル状ホスト分子の合成と機能開拓を実施する。当該ホスト分子はアントラセンに基づく特異蛍光性に加え、お椀状な内部空間への高い分子内包能が期待できる。また、疎水性のボウル状分子の末端に親水基を導入することで、水中で両親媒性分子として振る舞うことも見込まれる。本研究ではまず①湾曲したπ共役面を有するボウル状ホスト分子の合成を行う。次に②ゲスト包接と包摂錯体の蛍光特性評価を行い、最後に③自己集合を利用した高次な集合体形成と蛍光性制御を行う。

Outline of Final Research Achievements

In this study, we could demonstrate the construction of an antiaromatic-walled nanospace within a self-assembled cage composed of four metal ions with six identical antiaromatic walls. Although norcorrole has flat structure, each norcorrole wall displays a 165.4°bend inwards. Calculations indicate that the magnetic effects of the antiaromatic moieties surrounding this nanospace reinforce each other. This prediction is confirmed by 1H nuclear magnetic resonance (NMR) signals of bound guest molecules, which are observed at chemical shift values of up to 24 parts per million (ppm), owing to the combined antiaromatic deshielding effect of the surrounding rings.

Academic Significance and Societal Importance of the Research Achievements

本研究では、湾曲した反芳香族分子と自己集合の手法を利用することで、これまで確認されたことのない「反芳香族壁のナノ空間」を有する分子ケージを構築し、その性質を明らかにすることに成功した。これらの成果は、新しいタイプの分子ケージのコンセプトを提案するだけではなく、反芳香族分子との相互作用など、未解明の部分が多い反芳香族分子の性質を解き明かす重要な手段の一つになることが期待される。

Report

(3 results)
  • 2020 Annual Research Report   Final Research Report ( PDF )
  • 2019 Research-status Report
  • Research Products

    (10 results)

All 2021 2020 2019 Other

All Int'l Joint Research (2 results) Journal Article (3 results) (of which Int'l Joint Research: 1 results,  Peer Reviewed: 3 results,  Open Access: 1 results) Presentation (2 results) Remarks (2 results) Patent(Industrial Property Rights) (1 results)

  • [Int'l Joint Research] University of Cambridge/Department of Chemistry(英国)

    • Related Report
      2019 Research-status Report
  • [Int'l Joint Research] University of Copenhagen/Department of Chemistry(デンマーク)

    • Related Report
      2019 Research-status Report
  • [Journal Article] Open versus Closed Polyaromatic Nanocavity: Enhanced Host Abilities toward Large Dyes and Pigments2019

    • Author(s)
      Tsutsui Takahiro、Kusaba Shunsuke、Yamashina Masahiro、Akita Munetaka、Yoshizawa Michito
    • Journal Title

      Chemistry A European Journal

      Volume: 25 Issue: 17 Pages: 4320-4324

    • DOI

      10.1002/chem.201806409

    • Related Report
      2019 Research-status Report
    • Peer Reviewed
  • [Journal Article] A polyaromatic receptor with high androgen affinity2019

    • Author(s)
      Yamashina Masahiro、Tsutsui Takahiro、Sei Yoshihisa、Akita Munetaka、Yoshizawa Michito
    • Journal Title

      Science Advances

      Volume: 5 Issue: 4 Pages: 3179-3179

    • DOI

      10.1126/sciadv.aav3179

    • Related Report
      2019 Research-status Report
    • Peer Reviewed / Open Access
  • [Journal Article] An antiaromatic-walled nanospace2019

    • Author(s)
      Yamashina Masahiro、Tanaka Yuya、Lavendomme Roy、Ronson Tanya K.、Pittelkow Michael、Nitschke Jonathan R.
    • Journal Title

      Nature

      Volume: 574 Issue: 7779 Pages: 511-515

    • DOI

      10.1038/s41586-019-1661-x

    • Related Report
      2019 Research-status Report
    • Peer Reviewed / Int'l Joint Research
  • [Presentation] アザイリド形成を契機とした新規有機リン両親媒性分子の開発2021

    • Author(s)
      山科雅裕・豊田真司
    • Organizer
      日本化学会 第101春季年会
    • Related Report
      2020 Annual Research Report
  • [Presentation] Development of a Coordination Cage with an Antiaromatic Nanospace2019

    • Author(s)
      Masahiro Yamashina, Jonathan R. Nitschke
    • Organizer
      日本化学会 第99春季年会
    • Related Report
      2019 Research-status Report
  • [Remarks] ナノサイズの「異空間」をもつ新物質

    • URL

      https://www.titech.ac.jp/news/2019/045521.html

    • Related Report
      2019 Research-status Report
  • [Remarks] 性ホルモンの男女を見分ける分子カプセル

    • URL

      https://www.titech.ac.jp/news/2019/044169.html

    • Related Report
      2019 Research-status Report
  • [Patent(Industrial Property Rights)] 両親媒性分子及びその製造方法2020

    • Inventor(s)
      山科雅裕、豊田真司
    • Industrial Property Rights Holder
      東京工業大学
    • Industrial Property Rights Type
      特許
    • Filing Date
      2020
    • Related Report
      2020 Annual Research Report

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Published: 2019-09-03   Modified: 2022-01-27  

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