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Synthesis of supramolecular polymer under the condition of controlled equilibrium

Research Project

Project/Area Number 20K15335
Research Category

Grant-in-Aid for Early-Career Scientists

Allocation TypeMulti-year Fund
Review Section Basic Section 35010:Polymer chemistry-related
Research InstitutionHiroshima University

Principal Investigator

Hirao Takehiro  広島大学, 先進理工系科学研究科(理), 助教 (20825343)

Project Period (FY) 2020-04-01 – 2022-03-31
Project Status Completed (Fiscal Year 2021)
Budget Amount *help
¥4,160,000 (Direct Cost: ¥3,200,000、Indirect Cost: ¥960,000)
Fiscal Year 2021: ¥2,080,000 (Direct Cost: ¥1,600,000、Indirect Cost: ¥480,000)
Fiscal Year 2020: ¥2,080,000 (Direct Cost: ¥1,600,000、Indirect Cost: ¥480,000)
Keywords超分子ポリマー / ポルフィリン / 自己集合 / 超分子重合 / 刺激応答性
Outline of Research at the Start

超分子ポリマーは混合するだけで自発的に重合が進行するため,その重合度を制御することは容易ではない。申請者はこれまで,ビスポルフィリンとトリニトロフルオレノンの選択的会合体形成を利用して,直鎖状ポリマーをを合成してきた。その過程で,超分子ポリマーの重合過程には,ポリマーの生長過程に加えて環状構造形成が拮抗することを詳細に突き止めた。今回申請者は,この環状構造形成を巧みに利用して,超分子ポリマーの重合度の制御に挑戦する。

Outline of Final Research Achievements

Supramolecular polymers have attracted great attention due to their unique dynamic nature. The dynamic nature allows access to develop stimuli-responsive supramolecular polymeric materials. Haino’s group reported a successful construction of supramolecular porphyrin polymers relying on a host-guest interaction between a bisporphyrin cleft (bisPor) and trinitrofluorenone (TNF). The bisPor-TNF host-guest complex is known to be formed via charge-transfer interactions. We thus envisioned that the supramolecular porphyrin polymers would respond to both oxidation and reduction inputs to interconversion between the polymeric and the monomeric states.

Academic Significance and Societal Importance of the Research Achievements

本研究成果では,ビスポルフィリンクレフトとトリニトロフルオレノンを連結した分子を用いて,酸化と還元,二つの外部刺激に応答して「集合状態」と「解離状態」を変換可能な超分子ポリマーの構築に成功した。「集合状態」と「解離状態」の変換を自在に制御することができれば,物理物性を自在に変換することのできる外部刺激応答性ポリマー材料への応用が期待される。本研究で用いた電荷移動相互作用は,様々な超分子ポリマー構築の駆動力に使用可能な相互作用であることから,酸化還元応答性超分子ポリマー構築へ向けた道筋を示したと言える。

Report

(3 results)
  • 2021 Annual Research Report   Final Research Report ( PDF )
  • 2020 Research-status Report
  • Research Products

    (54 results)

All 2022 2021 2020 Other

All Journal Article (18 results) (of which Int'l Joint Research: 2 results,  Peer Reviewed: 17 results,  Open Access: 1 results) Presentation (35 results) (of which Int'l Joint Research: 6 results,  Invited: 2 results) Remarks (1 results)

  • [Journal Article] Chiral Supramolecular Polymer Formed via Host-Guest Complexation of an Octaphosphonate Biscavitand and a Chiral Diammonium Guest2022

    • Author(s)
      Hamada Koki、Shimoyama Daisuke、Hirao Takehiro、Haino Takeharu
    • Journal Title

      Bulletin of the Chemical Society of Japan

      Volume: 95 Issue: 4 Pages: 621-627

    • DOI

      10.1246/bcsj.20210452

    • Related Report
      2021 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Non-Racemically Twisted Supramolecular Fullerene Polymers2022

    • Author(s)
      Takehiro Hirao
    • Journal Title

      高分子

      Volume: 71 Pages: 6-6

    • Related Report
      2021 Annual Research Report
  • [Journal Article] Self-Assembling Behavior and Chiroptical Properties of Carbazole-Cored Phenyl Isoxazolyl Benzenes2021

    • Author(s)
      Ono Yudai、Hirao Takehiro、Ikeda Toshiaki、Haino Takeharu
    • Journal Title

      The Journal of Organic Chemistry

      Volume: 86 Issue: 8 Pages: 5499-5505

    • DOI

      10.1021/acs.joc.0c03005

    • Related Report
      2021 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Polymerization of a biscalix[5]arene derivative2021

    • Author(s)
      Takehiro Hirao, Kazushi Fukuta, Takeharu Haino
    • Journal Title

      RSC Advances

      Volume: 11 Issue: 29 Pages: 17587-17594

    • DOI

      10.1039/d1ra02276h

    • Related Report
      2021 Annual Research Report
    • Peer Reviewed / Open Access
  • [Journal Article] Supramolecular chemistry of fullerenes2021

    • Author(s)
      Takeharu Haino, Takehiro Hirao
    • Journal Title

      Handbook of Fullerene Science and Technology

      Volume: - Pages: 1-31

    • DOI

      10.1007/978-981-13-3242-5_36-1

    • ISBN
      9789811332425
    • Related Report
      2021 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Negative Cooperativity in Guest Binding of Ditopic Self-Folding Biscavitand2021

    • Author(s)
      Haruna Fujimoto, Daisuke Shimoyama, Katsuo Katayanagi, Naomi Kawata, Takehiro Hirao, Takeharu Haino
    • Journal Title

      Organic Letters

      Volume: 23 Issue: 16 Pages: 6217-6221

    • DOI

      10.1021/acs.orglett.1c01837

    • Related Report
      2021 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Self-Complementary Structure of Bisporphyrin Dimer2021

    • Author(s)
      Naoyuki Hisano, Takehiro Hirao, Takeharu Haino
    • Journal Title

      Chemistry Letters

      Volume: 50 Issue: 11 Pages: 1844-1847

    • DOI

      10.1246/cl.210393

    • NAID

      130008113712

    • Related Report
      2021 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Gas-Phase UV Spectroscopy of Chemical Intermediates Produced in Solution: Oxidation Reactions of Phenylhydrazines by DDQ2021

    • Author(s)
      Shiori Machida, Motoki Kida, Satoru Muramatsu, Takehiro Hirao, Takeharu Haino, Yoshiya Inokuchi
    • Journal Title

      The Journal of Physical Chemistry A

      Volume: 125 Issue: 31 Pages: 6697-6702

    • DOI

      10.1021/acs.jpca.1c04669

    • Related Report
      2021 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Solvent-Directed Formation of Helically Twisted Stacking Constructs via Self-Assembly of Tris(phenylisoxazolyl)benzene Dimers2021

    • Author(s)
      Yudai Ono, Takehiro Hirao, Takeharu Haino
    • Journal Title

      Organic & Biomolecular Chemistry

      Volume: 19 Issue: 33 Pages: 7165-7171

    • DOI

      10.1039/d1ob01277k

    • Related Report
      2021 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Self-Sorting Behavior in Supramolecular Fullerene Polymerization Directed by Host-Guest Complexation between Calix[5]arene and C602021

    • Author(s)
      Takehiro Hirao, Naoka Fujii, Yoshiki Iwabe, Takeharu Haino
    • Journal Title

      Chemical Communications

      Volume: 57 Issue: 89 Pages: 11831-11834

    • DOI

      10.1039/d1cc05118k

    • Related Report
      2021 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Supramolecular fluorescent sensors: An historical overview and update2021

    • Author(s)
      Guo Chenxing、Sedgwick Adam C.、Hirao Takehiro、Sessler Jonathan L.
    • Journal Title

      Coordination Chemistry Reviews

      Volume: 427 Pages: 213560-213560

    • DOI

      10.1016/j.ccr.2020.213560

    • Related Report
      2020 Research-status Report
    • Peer Reviewed / Int'l Joint Research
  • [Journal Article] Stereoselectivity in dehydrative cyclic trimerization of substituted 4-alkylaminobenzoic acids2021

    • Author(s)
      Takagi Koji、Yamaguchi Hinako、Miyamoto Daiki、Deguchi Yuka、Hirao Takehiro、Haino Takeharu
    • Journal Title

      New Journal of Chemistry

      Volume: 45 Issue: 3 Pages: 1187-1193

    • DOI

      10.1039/d0nj05368f

    • Related Report
      2020 Research-status Report
    • Peer Reviewed
  • [Journal Article] Helically Organized Fullerene Array in a Supramolecular Polymer Main Chain2021

    • Author(s)
      Hirao Takehiro、Iwabe Yoshiki、Fujii Naoka、Haino Takeharu
    • Journal Title

      Journal of the American Chemical Society

      Volume: 143 Issue: 11 Pages: 4339-4345

    • DOI

      10.1021/jacs.0c13326

    • Related Report
      2020 Research-status Report
    • Peer Reviewed
  • [Journal Article] Columnar Organization of Carbo[5]helicene Directed by Peripheral Steric Perturbation2020

    • Author(s)
      Hirao Takehiro、Ono Yudai、Kawata Naomi、Haino Takeharu
    • Journal Title

      Organic Letters

      Volume: 22 Issue: 14 Pages: 5294-5298

    • DOI

      10.1021/acs.orglett.0c01421

    • Related Report
      2020 Research-status Report
    • Peer Reviewed
  • [Journal Article] Helicity of a polyacetylene directed by molecular recognition of biscalixarene and fullerene2020

    • Author(s)
      Hirao Takehiro、Iwabe Yoshiki、Hisano Naoyuki、Haino Takeharu
    • Journal Title

      Chemical Communications

      Volume: 56 Issue: 49 Pages: 6672-6675

    • DOI

      10.1039/d0cc02506b

    • Related Report
      2020 Research-status Report
    • Peer Reviewed
  • [Journal Article] A dual redox-responsive supramolecular polymer driven by molecular recognition between bisporphyrin and trinitrofluorenone2020

    • Author(s)
      Hisano Naoyuki、Hirao Takehiro、Haino Takeharu
    • Journal Title

      Chemical Communications

      Volume: 56 Issue: 55 Pages: 7553-7556

    • DOI

      10.1039/d0cc02474k

    • Related Report
      2020 Research-status Report
    • Peer Reviewed
  • [Journal Article] Self‐Healing Supramolecular Materials Constructed by Copolymerization via Molecular Recognition of Cavitand‐Based Coordination Capsules2020

    • Author(s)
      Nitta Natsumi、Takatsuka Mei、Kihara Shin‐ichi、Hirao Takehiro、Haino Takeharu
    • Journal Title

      Angewandte Chemie International Edition

      Volume: 59 Issue: 38 Pages: 16690-16697

    • DOI

      10.1002/anie.202006604

    • Related Report
      2020 Research-status Report
    • Peer Reviewed
  • [Journal Article] A Light‐Harvesting/Charge‐Separation Model with Energy Gradient Made of Assemblies of meta ‐Pyridyl Zinc Porphyrins2020

    • Author(s)
      Otsuki Joe、Okumura Takumi、Sugawa Kosuke、Kawano Shin‐ichiro、Tanaka Kentaro、Hirao Takehiro、Haino Takeharu、Lee Yu Jin、Kang Seongsoo、Kim Dongho
    • Journal Title

      Chemistry ? A European Journal

      Volume: 27 Issue: 12 Pages: 4053-4063

    • DOI

      10.1002/chem.202003327

    • Related Report
      2020 Research-status Report
    • Peer Reviewed / Int'l Joint Research
  • [Presentation] Development of helical supramolecular fullerene polymers2022

    • Author(s)
      Takehiro Hirao
    • Organizer
      2022 International Conference on Modern Challenges in Polymer Science and Technology (2022 MCPST)
    • Related Report
      2021 Annual Research Report
    • Int'l Joint Research / Invited
  • [Presentation] キラルな溶媒中における超分子ポルフィリンポリマーのらせん構造2022

    • Author(s)
      岸野晴・ 平尾岳大・ 灰野岳晴
    • Organizer
      日本化学会第102春季年会
    • Related Report
      2021 Annual Research Report
  • [Presentation] 親水側鎖を導入したビス(フェニルイソオキサゾリル)ベンゼン配位子をもつ白金(Ⅱ)錯体の自己集合2022

    • Author(s)
      吉田真也・平尾岳大・灰野岳晴
    • Organizer
      日本化学会第102春季年会
    • Related Report
      2021 Annual Research Report
  • [Presentation] Self-Assembling Behavior and Negative Non-Linear Dependence of Hydrogen-Bonded Tris(phenylisoxazolyl)benzene Dimers2022

    • Author(s)
      小野雄大・平尾岳大・灰野岳晴
    • Organizer
      日本化学会第102春季年会
    • Related Report
      2021 Annual Research Report
  • [Presentation] 特異な分子認識を駆動力とした超分子ポリマーの合成2021

    • Author(s)
      平尾岳大
    • Organizer
      第36回中国四国地区高分子若手研究会
    • Related Report
      2021 Annual Research Report
    • Invited
  • [Presentation] キラルな溶媒によって制御される超分子ポルフィリンポリマーのらせん構造2021

    • Author(s)
      岸野晴・平尾岳大・灰野岳晴
    • Organizer
      2021年日本化学会中国四国支部大会高知大会
    • Related Report
      2021 Annual Research Report
  • [Presentation] ビスキャビタンド分子の自己集合により生じる超分子らせんポリマー2021

    • Author(s)
      浜田幸希・下山大輔・平尾岳大・灰野岳晴
    • Organizer
      2021年日本化学会中国四国支部大会高知大会
    • Related Report
      2021 Annual Research Report
  • [Presentation] キラルな溶媒中におけるテトラキスポルフィリン超分子ポリマーのらせん構造2021

    • Author(s)
      岸野晴・平尾岳大・灰野岳晴
    • Organizer
      第18回ホストーゲスト・超分子化学シンポジウム
    • Related Report
      2021 Annual Research Report
  • [Presentation] ビスキャビタンドの自己集合を駆動力とした超分子らせんポリマーの合成2021

    • Author(s)
      浜田幸希・下山大輔・平尾岳大・灰野岳晴
    • Organizer
      第18回ホストーゲスト・超分子化学シンポジウム
    • Related Report
      2021 Annual Research Report
  • [Presentation] 末端にカリックス[5]アレーン部位を有するポリアルキルメタクリレートの合成2021

    • Author(s)
      平尾岳大・福田和志・灰野岳晴
    • Organizer
      第37回有機合成セミナー
    • Related Report
      2021 Annual Research Report
  • [Presentation] トリス(フェニルイソオキサゾリル)ベンゼン二量体の自己集合によるらせん超分子ポリマーの合成2021

    • Author(s)
      小野雄大・平尾岳大・灰野岳晴
    • Organizer
      第31回基礎有機化学討論会
    • Related Report
      2021 Annual Research Report
  • [Presentation] キラルな溶媒によるポルフィリン超分子ポリマーの構造制御2021

    • Author(s)
      岸野晴・平尾岳大・灰野岳晴
    • Organizer
      第31回基礎有機化学討論会
    • Related Report
      2021 Annual Research Report
  • [Presentation] Rebek キャビタンドを導入したビスレゾルシンアレーンホスト分子の合成と協同的分子認識2021

    • Author(s)
      藤本陽菜・下山大輔・平尾岳大・灰野岳晴
    • Organizer
      第31回基礎有機化学討論会
    • Related Report
      2021 Annual Research Report
  • [Presentation] ビス(フェニルイソオキサゾリル)ベンゼン部位をもつ白金(Ⅱ)錯体の自己集合により生じる超分子ポリマーの特異な溶液物性2021

    • Author(s)
      吉田真也・平尾岳大・灰野岳晴
    • Organizer
      第31回基礎有機化学討論会
    • Related Report
      2021 Annual Research Report
  • [Presentation] ビスキャビタンドの金属配位により生じる超分子らせんポリマー2021

    • Author(s)
      浜田幸希・下山大輔・平尾岳大・灰野岳晴
    • Organizer
      第31回基礎有機化学討論会
    • Related Report
      2021 Annual Research Report
  • [Presentation] アキラル側鎖を導入したビス(フェニルイソオキサゾリル)ベンゼン配位子をもつ白金(Ⅱ)錯体の自己集合により生じる超分子ポリマーの特異な溶液物性2021

    • Author(s)
      吉田真也・平尾岳大・灰野岳晴
    • Organizer
      モレキュラーキラリティー2021
    • Related Report
      2021 Annual Research Report
  • [Presentation] トリス(フェニルイソオキサゾリル)ベンゼン二量体の自己集合と負の非線形キラル応答2021

    • Author(s)
      小野雄大・平尾岳大・灰野岳晴
    • Organizer
      モレキュラーキラリティー2021
    • Related Report
      2021 Annual Research Report
  • [Presentation] Helically organized fullerene array within the supramolecular polymer chain2021

    • Author(s)
      Takehiro Hirao, Yoshiki Iwabe, Naoka Fujii, Takeharu Haino
    • Organizer
      The 70th SPSJ Annual Meeting
    • Related Report
      2021 Annual Research Report
  • [Presentation] Development of Non-racemic Helical Polymers with Fullerene Array on the Polymer Backbone2021

    • Author(s)
      Takehiro Hirao, Yoshiki Iwabe, Naoka Fujii, Takeharu Haino
    • Organizer
      MIRAI 2.0 Digital Research and Innovation Week
    • Related Report
      2021 Annual Research Report
    • Int'l Joint Research
  • [Presentation] 親水性側鎖を導入したアセチレン配位子をもつプラチナ(II)錯体の自己集合2021

    • Author(s)
      吉田真也、平尾岳大、灰野岳晴
    • Organizer
      第14回有機π電子系シンポジウム
    • Related Report
      2020 Research-status Report
  • [Presentation] トリス(フェニルイソオキサゾリル)ベンゼンを導入した[5]ヘリセンの複雑な会合挙動の制御2021

    • Author(s)
      小野雄大、平尾岳大、灰野岳晴
    • Organizer
      日本化学会第101春季年会
    • Related Report
      2020 Research-status Report
  • [Presentation] 親水側鎖を導入したビス(フェニルイソオキサゾリル)ベンゼン配位子をもつ白金(II)錯体の自己集合2021

    • Author(s)
      吉田真也、平尾岳大、灰野岳晴
    • Organizer
      日本化学会第101春季年会
    • Related Report
      2020 Research-status Report
  • [Presentation] カリックス[5]アレーンとフラーレンの分子認識を用いた超分子分岐ポリマーの合成2021

    • Author(s)
      福田和志、平尾岳大、灰野岳晴
    • Organizer
      日本化学会第101春季年会
    • Related Report
      2020 Research-status Report
  • [Presentation] Synthesis and Cooperative Molecular Recognition of Homoditopic Host Molecule with Rebek's Cavitands2021

    • Author(s)
      Haruna Fujimoto, Daisuke Shimoyama, Takehiro Hirao, Takeharu Haino
    • Organizer
      日本化学会第101春季年会
    • Related Report
      2020 Research-status Report
  • [Presentation] Helical fullerene polymers accessed via molecular recognition2020

    • Author(s)
      Takehiro Hirao, Yoshiki Iwabe, Takeharu Haino
    • Organizer
      第69回高分子学会年次大会
    • Related Report
      2020 Research-status Report
  • [Presentation] クレフト型ビスポルフィリンを基盤としたホスト-ゲスト相互作用および金属配位により形成される超分子ネットワークポリマーの開発2020

    • Author(s)
      久野尚之、ラナンズイ、平尾岳大、灰野岳晴
    • Organizer
      第69回高分子学会年次大会
    • Related Report
      2020 Research-status Report
  • [Presentation] フラーレンとカリックス[5] アレーンの分子認識により制御されるPMMA の構造2020

    • Author(s)
      福田和志、平尾岳大、灰野岳晴
    • Organizer
      第69回高分子学会年次大会
    • Related Report
      2020 Research-status Report
  • [Presentation] トリス (フェニルイソオキサゾリル)ベンゼンを導入したヘリセンの特異な会合挙動の制御2020

    • Author(s)
      小野雄大、平野喬平、平尾岳大、灰野岳晴
    • Organizer
      第69回高分子学会年次大会
    • Related Report
      2020 Research-status Report
  • [Presentation] アミノ酸で修飾されたテトラキスポルフィリンの自己会合により形成されるらせん超分子ポリマー2020

    • Author(s)
      藤井直香、灰野岳晴、平尾岳大
    • Organizer
      第69回高分子学会年次大会
    • Related Report
      2020 Research-status Report
  • [Presentation] Helically Organized Supramolecular Polymer Formed via Self-Assembly of Tetrakisporphyrin with Chiral Side Chain2020

    • Author(s)
      Naoka Fujii, Tekehiro Hirao, Takeharu Haino
    • Organizer
      3rd GLowing Polymer Symposium in KANTO
    • Related Report
      2020 Research-status Report
    • Int'l Joint Research
  • [Presentation] A Switchable Dual Redox-Responsive Supramolecular Polymer Possessing Bisporphyrin Cleft and Trinitrofluorenone2020

    • Author(s)
      Naoyuki Hisano, Takehiro Hirao, Takeharu Haino
    • Organizer
      3rd GLowing Polymer Symposium in KANTO
    • Related Report
      2020 Research-status Report
    • Int'l Joint Research
  • [Presentation] Non-racemic helical polymers with fullerene array on the polymer backbone2020

    • Author(s)
      Takehiro Hirao, Yoshiaki Iwabe, Naoka Fujii, Takeharu Haino
    • Organizer
      3rd GLowing Polymer Symposium in KANTO
    • Related Report
      2020 Research-status Report
    • Int'l Joint Research
  • [Presentation] Redoxで制御される超分子ポルフィリンポリマーの構造2020

    • Author(s)
      久野尚之、平尾岳大、灰野岳晴
    • Organizer
      日本化学会中国四国大会 島根大会
    • Related Report
      2020 Research-status Report
  • [Presentation] キラルな親水性側鎖を導入したビス(フェニルオキサゾリル)ベンゼン誘導体を配位子にもつプラチナ(II)錯体の合成と機能2020

    • Author(s)
      吉田真也、平尾岳大、灰野岳晴
    • Organizer
      日本化学会中国四国大会 島根大会
    • Related Report
      2020 Research-status Report
  • [Presentation] Self-assembling behaviors of platinum (II) complexes possessing hydrophilic triethylene glycol chains2020

    • Author(s)
      Masaya Yoshida, Takehiro Hirao, Takeharu Haino
    • Organizer
      The 17th Nano Bio Info Chemistry Symposium
    • Related Report
      2020 Research-status Report
    • Int'l Joint Research
  • [Remarks]

    • URL

      https://orgchem.hiroshima-u.ac.jp/

    • Related Report
      2020 Research-status Report

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Published: 2020-04-28   Modified: 2023-01-30  

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