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Creation of supramolecular materials based on curved pi-conjugated molecules

Research Project

Project/Area Number 16H06031
Research Category

Grant-in-Aid for Young Scientists (A)

Allocation TypeSingle-year Grants
Research Field Organic chemistry
Research InstitutionKyoto University (2017-2018)
Nagoya University (2016)

Principal Investigator

Hiroto Satoru  京都大学, 人間・環境学研究科, 准教授 (30547427)

Project Period (FY) 2016-04-01 – 2019-03-31
Project Status Completed (Fiscal Year 2018)
Budget Amount *help
¥25,740,000 (Direct Cost: ¥19,800,000、Indirect Cost: ¥5,940,000)
Fiscal Year 2018: ¥7,280,000 (Direct Cost: ¥5,600,000、Indirect Cost: ¥1,680,000)
Fiscal Year 2017: ¥7,280,000 (Direct Cost: ¥5,600,000、Indirect Cost: ¥1,680,000)
Fiscal Year 2016: ¥11,180,000 (Direct Cost: ¥8,600,000、Indirect Cost: ¥2,580,000)
Keywords曲面 / π共役分子 / ヘリセン / バッキーボウル / 外部刺激応答性 / アザバッキーボウル / アザヘリセン / キラリティー / 超分子ポリマー / ヘキサベンゾコロネン / ポルフィリン / 超分子 / キラル発光 / メカノクロミズム / 自己組織化 / 光捕集アンテナ
Outline of Final Research Achievements

The purpose of this research was to disclose effect of curved structures on molecular functionalities compared with planar pi-conjugated molecules. As a result, we discovered unique supramolecular assemblies based on curved pi-conjugated molecules. In particular, we have achieved a creation of novel two-photon absorption switching host-guest molecules based on azabuckybowl and C60. In addition, we found a formation of supramolecular polymer with azabuckybowl dimer in the presence of stoichiometric amount of C60. These phenomena have not been reported for planar pi-conjugated molecules.
Secondly, stimuli-responsibilities of three-dimentional molecules have been developed by dimerization of hexa-peri-hexabenzocoronene. The dicyanoethano-bridged dimer exhibited mechanochromic behaviors. Furthermore, fluoromechanochromism was also observed for the dicyanoetheno-bridged dimer. These results would lead to creation of novel molecular sensors based on curved pi-conjugated molecules.

Academic Significance and Societal Importance of the Research Achievements

本研究により、分子が曲面になることで平面より優れた、または平面分子にはない反応性を示すことを実験的に明らかにできた。これは、分子の曲面という構造的な要因の意義を実験的に初めて示した学術的に重要な結果である。さらに、三次元分子の柔軟性および集積による外部刺激応答性を発現したことは、分子センサーの新たな設計の指針を示す。また、曲面上の窒素元素の効果を示したことは、炭素材料におけるヘテロ元素導入の効果を実験的に解明する重要な手がかりとなり、今後の炭素材料の発展に貢献できる。以上のように、本研究は、曲面分子という新たな分子材料の創出とともに従来の炭素材料の発展の促進に繋がる意義深いものである。

Report

(4 results)
  • 2018 Annual Research Report   Final Research Report ( PDF )
  • 2017 Annual Research Report
  • 2016 Annual Research Report
  • Research Products

    (41 results)

All 2019 2018 2017 2016

All Journal Article (10 results) (of which Int'l Joint Research: 1 results,  Peer Reviewed: 10 results,  Open Access: 3 results,  Acknowledgement Compliant: 3 results) Presentation (31 results) (of which Int'l Joint Research: 10 results,  Invited: 9 results)

  • [Journal Article] Synthesis of dihydropyrazine-fused porphyrin dimers2019

    • Author(s)
      A. Takiguchi, M. Wakita, S. Hiroto, H. Shinokubo
    • Journal Title

      Chem. Lett.

      Volume: 48 Issue: 4 Pages: 371-373

    • DOI

      10.1246/cl.190002

    • NAID

      130007624435

    • Related Report
      2018 Annual Research Report
    • Peer Reviewed / Open Access
  • [Journal Article] Azabuckybowl-Based Molecular Tweezers as C60 and C70 Receptors2018

    • Author(s)
      Takeda Motoki、Hiroto Satoru、Yokoi Hiroki、Lee Sangsu、Kim Dongho、Shinokubo Hiroshi
    • Journal Title

      Journal of the American Chemical Society

      Volume: 140 Issue: 20 Pages: 6336-6342

    • DOI

      10.1021/jacs.8b02327

    • NAID

      120006517677

    • Related Report
      2018 Annual Research Report
    • Peer Reviewed / Int'l Joint Research
  • [Journal Article] Supramolecular assemblies of a nitrogen-embedded buckybowl dimer with C602018

    • Author(s)
      H. Yokoi, S. Hiroto, D. Sakamaki, S. Seki, H. Shinokubo
    • Journal Title

      Chem. Sci.

      Volume: 9 Issue: 4 Pages: 819-824

    • DOI

      10.1039/c7sc04453d

    • Related Report
      2018 Annual Research Report
    • Peer Reviewed / Open Access
  • [Journal Article] Reversible σ‐Bond Formation in Bowl-Shaped π‐Radical Cations: The Effects of Curved and Planar Structures2018

    • Author(s)
      H. Yokoi, S. Hiroto, H. Shinokubo
    • Journal Title

      J. Am. Chem. Soc.

      Volume: 140 Issue: 13 Pages: 4649-4655

    • DOI

      10.1021/jacs.8b00798

    • NAID

      120006491436

    • Related Report
      2018 Annual Research Report
    • Peer Reviewed
  • [Journal Article] 10-Silacorroles Exhibiting NIR Absorption and Emission2017

    • Author(s)
      H. Omori, S. Hiroto, H. Shinokubo
    • Journal Title

      Chem. Eur. J.

      Volume: 23 Issue: 33 Pages: 7866-7870

    • DOI

      10.1002/chem.201701474

    • NAID

      120006349126

    • Related Report
      2017 Annual Research Report
    • Peer Reviewed
  • [Journal Article] NIR Mechanochromic Behaviours of Tetracyanoethylene-Bridged Hexa-peri-Hexabenzocoronene Dimer and Trimer through Dissociation of C-C Bonds2017

    • Author(s)
      K. Oda, S. Hiroto, H. Shinokubo
    • Journal Title

      J. Mater. Chem. C

      Volume: 5 Issue: 22 Pages: 5310-5315

    • DOI

      10.1039/c7tc01270e

    • NAID

      120006337723

    • Related Report
      2017 Annual Research Report
    • Peer Reviewed
  • [Journal Article] π-Extended Dihydrophenazines with Three-State NIR Electrochromism Involving Large Conformational Changes2017

    • Author(s)
      J. Nagasaki, S. Hiroto, H. Shinokubo
    • Journal Title

      Chemistry an Asian Journal

      Volume: 12 Issue: 17 Pages: 2311-2317

    • DOI

      10.1002/asia.201700840

    • Related Report
      2017 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Synthesis of bright red-emissive dicyanoethenobridged hexa-peri-hexabenzocoronene dimers2017

    • Author(s)
      Kazuma Oda, Satoru Hiroto, Ichiro Hisaki, Hiroshi Shinokubo
    • Journal Title

      Org. Biomol. Chem.

      Volume: 15 Issue: 6 Pages: 1426-1434

    • DOI

      10.1039/c6ob02775j

    • NAID

      120006305604

    • Related Report
      2016 Annual Research Report
    • Peer Reviewed / Acknowledgement Compliant
  • [Journal Article] Synthesis of a figure-eight azahelicene dimer with high emission and CPL properties2017

    • Author(s)
      Ayako Ushiyama, Satoru Hiroto, Junpei Yuasa, Tsuyoshi Kawai, Hiroshi Shinokubo
    • Journal Title

      Organic Chemistry Frontiers

      Volume: 印刷中 Issue: 5 Pages: 664-667

    • DOI

      10.1039/c6qo00629a

    • Related Report
      2016 Annual Research Report
    • Peer Reviewed / Acknowledgement Compliant
  • [Journal Article] Synthesis and Functionalization of Porphyrins through Organometallic Methodologies2017

    • Author(s)
      S. Hiroto
    • Journal Title

      Chem. Rev.

      Volume: 117 Issue: 4 Pages: 2910-3043

    • DOI

      10.1021/acs.chemrev.6b00427

    • Related Report
      2016 Annual Research Report
    • Peer Reviewed / Open Access / Acknowledgement Compliant
  • [Presentation] アザ[5]ヘリセンの外部刺激応答性と置換基効果2019

    • Author(s)
      廣戸 聡
    • Organizer
      第99日本化学会春季年会
    • Related Report
      2018 Annual Research Report
  • [Presentation] Supramolecular assembly of nitrogen-embedded curved π-conjugated molecules2018

    • Author(s)
      Satoru Hiroto
    • Organizer
      EMN Auckland Meeting
    • Related Report
      2018 Annual Research Report
    • Int'l Joint Research / Invited
  • [Presentation] Chemistry of nitrogen-embedded buckybowl2018

    • Author(s)
      Satoru Hiroto
    • Organizer
      the 11th Japan-Taiwan Bilateral Symposium on“Architecture of Functional Organic Molecules
    • Related Report
      2018 Annual Research Report
    • Int'l Joint Research / Invited
  • [Presentation] Development of novel synthetic protocol of porphyrinoids based on distorted structures2018

    • Author(s)
      Satoru Hiroto
    • Organizer
      Tenth International Conference on Porphyrins and Phthalocyanines
    • Related Report
      2018 Annual Research Report
    • Int'l Joint Research / Invited
  • [Presentation] π平面をねじる:ヘテロ元素を含む 曲面π共役分子の創成2018

    • Author(s)
      廣戸 聡
    • Organizer
      京都大学大学院薬学研究科
    • Related Report
      2018 Annual Research Report
    • Invited
  • [Presentation] 縮環ポルフィリンの可逆的構造変化への試み2017

    • Author(s)
      瀧口あさひ・廣戸 聡・忍久保 洋
    • Organizer
      第7回CSJフェスタ2017
    • Related Report
      2017 Annual Research Report
  • [Presentation] 可逆的に構造変化する縮環ポルフィリンの合成2017

    • Author(s)
      瀧口あさひ・廣戸 聡・忍久保 洋
    • Organizer
      第48回中部化学関係学協会支部連合秋季大会
    • Related Report
      2017 Annual Research Report
  • [Presentation] メゾ位にヘテロ原子を含む新規ポルフィリノイドの合成2017

    • Author(s)
      大森裕土・廣戸 聡・武田洋平・南方聖司・忍久保 洋
    • Organizer
      第28回基礎有機化学討論会
    • Related Report
      2017 Annual Research Report
  • [Presentation] π拡張アザコラニュレンラジカルカチオンの二量化反応2017

    • Author(s)
      横井寛生・廣戸 聡・忍久保 洋
    • Organizer
      第28回基礎有機化学討論会
    • Related Report
      2017 Annual Research Report
  • [Presentation] アザヘリセン金属錯体の合成とその光物性2017

    • Author(s)
      武田基希・牛山綾子・廣戸 聡・忍久保 洋
    • Organizer
      第28回基礎有機化学討論会
    • Related Report
      2017 Annual Research Report
  • [Presentation] アミノピレンの酸化による窒素含有縮環π共役分子の合成法の開発2017

    • Author(s)
      早川 咲穂・横井 寛生・廣戸 聡・忍久保 洋
    • Organizer
      第28回基礎有機化学討論会
    • Related Report
      2017 Annual Research Report
  • [Presentation] アルキンの環化反応を利用した縮環ポルフィリン二量体の合成2017

    • Author(s)
      永井 智大・上田 真之・小田 一磨・廣戸 聡・忍久保 洋
    • Organizer
      第28回基礎有機化学討論会
    • Related Report
      2017 Annual Research Report
  • [Presentation] 可逆的に構造変化するポルフィリン二量体の合成とC60との包接挙動2017

    • Author(s)
      瀧口あさひ・廣戸 聡・忍久保 洋
    • Organizer
      第98日本化学会春季年会
    • Related Report
      2017 Annual Research Report
  • [Presentation] 金属配位部位をもつアザバッキーボウルの合成2017

    • Author(s)
      横田智也・廣戸 聡・忍久保 洋
    • Organizer
      第98日本化学会春季年会
    • Related Report
      2017 Annual Research Report
  • [Presentation] お椀型ドナーをもつドナー・アクセプター型分子の合成とその物性2017

    • Author(s)
      田中佑宜・廣戸 聡・忍久保 洋
    • Organizer
      第98日本化学会春季年会
    • Related Report
      2017 Annual Research Report
  • [Presentation] Reactivity and Assembling Behaviors of Heteroatom-Contained Curved π-Conjugated Molecules2017

    • Author(s)
      Satoru Hiroto
    • Organizer
      9th International Conference on Materials for Advanced Technologies (ICMAT2017), Singapore
    • Related Report
      2017 Annual Research Report
    • Int'l Joint Research / Invited
  • [Presentation] Synthesis and Multi-chromic Characteristics of Oligoene-bridged Polycyclic Aromatic Hydrocarbons2017

    • Author(s)
      Satoru Hiroto
    • Organizer
      9th International Conference on Materials for Advanced Technologies (ICMAT2017), Singapore
    • Related Report
      2017 Annual Research Report
    • Int'l Joint Research / Invited
  • [Presentation] π拡張ジヒドロフェナジンの合成とエレクトロクロミック特性2017

    • Author(s)
      廣戸 聡, 長崎 樹梨, 忍久保 洋
    • Organizer
      第28回基礎有機化学討論会
    • Related Report
      2017 Annual Research Report
  • [Presentation] Substituent Effect on Oxidative Dimerization of beta-aminoporphyrins2017

    • Author(s)
      廣戸 聡
    • Organizer
      日本化学会第98春季年会
    • Related Report
      2017 Annual Research Report
  • [Presentation] Impact of Graphitic Nitrogen on Bowl-Shaped π-Conjugated Molecules: Supramolecular Chemistry and Reactivity2017

    • Author(s)
      Satoru Hiroto, Hiroki Yokoi, Hiroshi Shinokubo
    • Organizer
      254th American Chemical Society National Meeting & Exposition
    • Related Report
      2017 Annual Research Report
    • Int'l Joint Research
  • [Presentation] Synthesis and Mechanochromism of hexa-peri-hexabenzocoronene dimers2017

    • Author(s)
      Satoru Hiroto, Kazuma Oda, Hiroshi Shinokubo
    • Organizer
      The 12th International Conference on Cutting-Edge Organic Chemistry in Asia
    • Related Report
      2017 Annual Research Report
    • Int'l Joint Research
  • [Presentation] π拡張アザヘリセンの反応性と発光特性2016

    • Author(s)
      廣戸 聡, 牛山 綾子, 忍久保 洋
    • Organizer
      第3回π造形科学若手研究会
    • Place of Presentation
      加賀
    • Year and Date
      2016-11-11
    • Related Report
      2016 Annual Research Report
  • [Presentation] 近赤外領域に吸収をもつ新規ポルフィリン二量体の合成2016

    • Author(s)
      永井 智大・上田 真之・小田 一磨・廣戸 聡・忍久保 洋
    • Organizer
      第47回中部化学関係学協会支部連合秋季大会
    • Place of Presentation
      豊橋
    • Year and Date
      2016-11-05
    • Related Report
      2016 Annual Research Report
  • [Presentation] Concise Synthesis of Curved-π Conjugated Molecules2016

    • Author(s)
      Satoru Hiroto
    • Organizer
      IUPAC 12th International Conference on Novel Materials and their Synthesis
    • Place of Presentation
      Changsha (China)
    • Year and Date
      2016-10-14
    • Related Report
      2016 Annual Research Report
    • Int'l Joint Research / Invited
  • [Presentation] アザコラヌレン二量体の合成とその性質2016

    • Author(s)
      横井 寛生, 廣戸 聡, 酒巻 大輔, 関 修平, 忍久保 洋
    • Organizer
      第27回基礎有機化学討論会
    • Place of Presentation
      広島
    • Year and Date
      2016-09-01
    • Related Report
      2016 Annual Research Report
  • [Presentation] メゾ位にケイ素およびリンを含む新規ポルフィリノイドの合成2016

    • Author(s)
      大森 裕土・廣戸 聡・武田 洋平・南方 聖司・忍久保 洋
    • Organizer
      第27回基礎有機化学討論会
    • Place of Presentation
      広島
    • Year and Date
      2016-09-01
    • Related Report
      2016 Annual Research Report
  • [Presentation] 転位反応を用いた反芳香族ノルコロールの位置選択的臭素化2016

    • Author(s)
      川島 弘之・廣戸 聡・忍久保 洋
    • Organizer
      第27回基礎有機化学討論会
    • Place of Presentation
      広島
    • Year and Date
      2016-09-01
    • Related Report
      2016 Annual Research Report
  • [Presentation] 芳香環架橋アザバッキーボウル二量体の合成2016

    • Author(s)
      武田 基希・横井 寛生・廣戸 聡・忍久保 洋
    • Organizer
      第27回基礎有機化学討論会
    • Place of Presentation
      広島
    • Year and Date
      2016-09-01
    • Related Report
      2016 Annual Research Report
  • [Presentation] Highly-twisted porphyrin oligomers: Synthesis, characterization and applications2016

    • Author(s)
      Satoru Hiroto, Hiroshi Shinokubo
    • Organizer
      Ninth International Conference on Porphyrins and Phthalocyanines
    • Place of Presentation
      Nanjing (China)
    • Year and Date
      2016-07-03
    • Related Report
      2016 Annual Research Report
    • Int'l Joint Research / Invited
  • [Presentation] Synthesis of Nitrogen-Embedded Buckybowl and Its Strong Association Behavior with C602016

    • Author(s)
      Satoru Hiroto
    • Organizer
      229th ECS Meeting
    • Place of Presentation
      San Diego (USA)
    • Year and Date
      2016-05-29
    • Related Report
      2016 Annual Research Report
    • Int'l Joint Research / Invited
  • [Presentation] π曲面分子の反応性・機能性:最近の研究から2016

    • Author(s)
      廣戸 聡
    • Organizer
      第4回構造有機化学若手研究者研究会
    • Place of Presentation
      北海道大学
    • Related Report
      2016 Annual Research Report

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Published: 2016-04-21   Modified: 2020-03-30  

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