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Stabilization of antiaromatic molecules by polymerization

Research Project

Project/Area Number 20K21190
Research Category

Grant-in-Aid for Challenging Research (Exploratory)

Allocation TypeMulti-year Fund
Review Section Medium-sized Section 33:Organic chemistry and related fields
Research InstitutionNagoya University

Principal Investigator

Shinokubo Hiroshi  名古屋大学, 工学研究科, 教授 (50281100)

Project Period (FY) 2020-07-30 – 2023-03-31
Project Status Completed (Fiscal Year 2022)
Budget Amount *help
¥6,500,000 (Direct Cost: ¥5,000,000、Indirect Cost: ¥1,500,000)
Fiscal Year 2021: ¥2,470,000 (Direct Cost: ¥1,900,000、Indirect Cost: ¥570,000)
Fiscal Year 2020: ¥4,030,000 (Direct Cost: ¥3,100,000、Indirect Cost: ¥930,000)
Keywordsノルコロール / 反芳香族性 / 重合 / 水素結合 / 超分子 / 有機半導体 / 電荷輸送特性 / 超分子重合
Outline of Research at the Start

最近、反芳香族π電子系化合物であるノルコロールが固体中で極めて近接した距離で積層し、安定化することを見いだした。本研究では、反芳香族化合物を高分子化することで積層化し格段の安定化を実現するともに、反芳香族高分子の機能開拓を行う。反芳香族化合物を主鎖や側鎖にもつ高分子はこれまでに前例がなく、未踏の物質群である。単に前例がないだけではなく、反芳香族化合物を高分子化することにより近接して積層化させ、安定化しようという挑戦は学術的に独創性が高い。反芳香族化合物を安定化できれば、有機半導体や有機二次電池への利用といった応用展開にも道を拓くことができる。

Outline of Final Research Achievements

In this research, we demonstrated the construction of a supramolecular polymer consisting of an antiaromatic π-system. An amide-functionalized Ni(II) norcorrole derivative formed a one-dimensional supramolecular polymer through π-π stacking and hydrogen-bonding interactions. The antiaromatic supramolecular polymer exhibited higher charge mobility than that of the aromatic analogue composed of Zn(II) porphyrins.

Academic Significance and Societal Importance of the Research Achievements

本研究では、反芳香族ポルフィリンであるノルコロールの側鎖に水素結合部位を導入することにより超分子ポリマーを形成できることを明らかにした。反芳香族分子を構成単位とする超分子ポリマーは芳香族分子を構成単位とする超分子ポリマーよりも優れた電荷輸送特性を示すことが分かった。反芳香族分子の積層が優れた電子機能の発現につながる可能性を示す結果である。

Report

(4 results)
  • 2022 Annual Research Report   Final Research Report ( PDF )
  • 2021 Research-status Report
  • 2020 Research-status Report
  • Research Products

    (45 results)

All 2023 2022 2021 2020 Other

All Int'l Joint Research (5 results) Journal Article (8 results) (of which Int'l Joint Research: 4 results,  Peer Reviewed: 8 results,  Open Access: 5 results) Presentation (30 results) (of which Int'l Joint Research: 8 results,  Invited: 10 results) Remarks (2 results)

  • [Int'l Joint Research] Yonsei University(韓国)

    • Related Report
      2022 Annual Research Report
  • [Int'l Joint Research] Yonsei University(韓国)

    • Related Report
      2021 Research-status Report
  • [Int'l Joint Research] Western Washington University(米国)

    • Related Report
      2021 Research-status Report
  • [Int'l Joint Research] Karlsruhe Institute of Technology(ドイツ)

    • Related Report
      2021 Research-status Report
  • [Int'l Joint Research] Yonsei University(韓国)

    • Related Report
      2020 Research-status Report
  • [Journal Article] Planarization of a bowl-shaped molecule by triple-decker stacking2022

    • Author(s)
      Kawashima Hiroyuki、Fukui Norihito、Phung Quan Manh、Yanai Takeshi、Shinokubo Hiroshi
    • Journal Title

      Cell Reports Physical Science

      Volume: 3 Issue: 9 Pages: 101045-101045

    • DOI

      10.1016/j.xcrp.2022.101045

    • Related Report
      2022 Annual Research Report
    • Peer Reviewed / Open Access / Int'l Joint Research
  • [Journal Article] Realization of Stacked-Ring Aromaticity in a Water-Soluble Micellar Capsule2022

    • Author(s)
      Liu Si-Yu、Kishida Natsuki、Kim Jinseok、Fukui Norihito、Haruki Rie、Niwa Yasuhiro、Kumai Reiji、Kim Dongho、Yoshizawa Michito、Shinokubo Hiroshi
    • Journal Title

      Journal of the American Chemical Society

      Volume: 145 Issue: 4 Pages: 2135-2141

    • DOI

      10.1021/jacs.2c08795

    • Related Report
      2022 Annual Research Report
    • Peer Reviewed / Open Access / Int'l Joint Research
  • [Journal Article] A Supramolecular Polymer Constituted of Antiaromatic Ni(II) Norcorroles2022

    • Author(s)
      S. Ukai, A. Takamatsu, M. Nobuoka, Y. Tsutsui, N. Fukui, S. Ogi, S. Seki, S. Yamaguchi, H. Shinokubo
    • Journal Title

      Angew. Chem. Int. Ed.

      Volume: 61 Issue: 6 Pages: 202114230-202114230

    • DOI

      10.1002/anie.202114230

    • Related Report
      2021 Research-status Report
    • Peer Reviewed
  • [Journal Article] Isolation and Structure Analysis of a Ni(II) Norcorrole Radical Anion2022

    • Author(s)
      Ukai Shusaku、Fukui Norihito、Ikeue Takahisa、Shinokubo Hiroshi
    • Journal Title

      Chemistry Letters

      Volume: 51 Issue: 2 Pages: 182-184

    • DOI

      10.1246/cl.210715

    • NAID

      130008161612

    • Related Report
      2021 Research-status Report
    • Peer Reviewed / Open Access
  • [Journal Article] Antiaromatic 1,5‐Diaza‐s‐indacenes2021

    • Author(s)
      Hanida Kensuke、Kim Jinseok、Fukui Norihito、Tsutsui Yusuke、Seki Shu、Kim Dongho、Shinokubo Hiroshi
    • Journal Title

      Angewandte Chemie International Edition

      Volume: 60 Issue: 38 Pages: 20765-20770

    • DOI

      10.1002/anie.202109003

    • NAID

      120007192017

    • Related Report
      2021 Research-status Report
    • Peer Reviewed / Int'l Joint Research
  • [Journal Article] Determinant Factors of Three-Dimensional Aromaticity in Antiaromatic Cyclophanes2021

    • Author(s)
      Kawashima Hiroyuki、Ukai Shusaku、Nozawa Ryo、Fukui Norihito、Fitzsimmons Garrett、Kowalczyk Tim、Fliegl Heike、Shinokubo Hiroshi
    • Journal Title

      Journal of the American Chemical Society

      Volume: 143 Issue: 28 Pages: 10676-10685

    • DOI

      10.1021/jacs.1c04348

    • NAID

      120007192016

    • Related Report
      2021 Research-status Report
    • Peer Reviewed / Open Access / Int'l Joint Research
  • [Journal Article] Redox-induced reversible [2 + 2] cycloaddition of an etheno-fused diporphyrin2021

    • Author(s)
      Miyagawa Kazuya、Hisaki Ichiro、Fukui Norihito、Shinokubo Hiroshi
    • Journal Title

      Chemical Science

      Volume: 12 Issue: 14 Pages: 5224-5229

    • DOI

      10.1039/d1sc00438g

    • Related Report
      2020 Research-status Report
    • Peer Reviewed / Open Access
  • [Journal Article] Synthesis and electron-transport properties of a stable antiaromatic NiII norcorrole with the smallest meso-substituent2020

    • Author(s)
      Ukai Shusaku、Koo Yun Hee、Fukui Norihito、Seki Shu、Shinokubo Hiroshi
    • Journal Title

      Dalton Transactions

      Volume: 49 Issue: 41 Pages: 14383-14387

    • DOI

      10.1039/d0dt03143g

    • NAID

      120007145963

    • Related Report
      2020 Research-status Report
    • Peer Reviewed
  • [Presentation] meso位にエステル基をもつジピリン錯体からのポルフィリノイド合成2023

    • Author(s)
      平松 永伍、木野 翔太、劉 思雨、忍久保 洋
    • Organizer
      日本化学会第103回春季年会
    • Related Report
      2022 Annual Research Report
  • [Presentation] 反芳香族化合物の近接積層2022

    • Author(s)
      忍久保 洋
    • Organizer
      第16回物性科学領域横断研究会
    • Related Report
      2022 Annual Research Report
    • Invited
  • [Presentation] ボリル基をもつノルコロールニッケル錯体の合成2022

    • Author(s)
      冨田 諒弥・鵜飼 修作・福井 識人・忍久保 洋
    • Organizer
      第53回中部化学関係学協会支部連合秋季大会
    • Related Report
      2022 Annual Research Report
  • [Presentation] ポルフィリンのちょい足しとちょい引きの化学:芳香族性をひっくり返す2022

    • Author(s)
      忍久保 洋
    • Organizer
      CSJ化学フェスタ2022
    • Related Report
      2022 Annual Research Report
    • Invited
  • [Presentation] 反芳香族ポルフィリン:ノルコロールの化学2022

    • Author(s)
      忍久保 洋
    • Organizer
      化学部門特別講演会, 北海道大学
    • Related Report
      2022 Annual Research Report
    • Invited
  • [Presentation] Switching off antiaromaticity by stacking: close stacking of norcorroles2022

    • Author(s)
      忍久保 洋
    • Organizer
      Lecture at Hunan Normal University
    • Related Report
      2022 Annual Research Report
    • Int'l Joint Research / Invited
  • [Presentation] ボリル基をもつノルコロールニッケル錯体の合成2022

    • Author(s)
      冨田 諒弥・鵜飼 修作・福井 識人・忍久保 洋
    • Organizer
      第32回基礎有機化学討論会
    • Related Report
      2022 Annual Research Report
  • [Presentation] アミド基をもつテトラフェニル-2,7-ジアザピレンの合成および性質2022

    • Author(s)
      小田原 正浩・溝上 諒平・原 光生・芥川 智行・関 隆広・忍久保 洋・三宅 由寛
    • Organizer
      第32回基礎有機化学討論会
    • Related Report
      2022 Annual Research Report
  • [Presentation] Synthesis and Properties of Covalently Linked Norcorrole Dimers2022

    • Author(s)
      Si-Yu Liu, Norihito Fukui, and Hiroshi Shinokubo
    • Organizer
      第32回基礎有機化学討論会
    • Related Report
      2022 Annual Research Report
  • [Presentation] ペンタフルオロフェニル基をもつノルコロールニッケル錯体の物性2022

    • Author(s)
      木野翔太・鵜飼 修作・福井 識人・忍久保 洋
    • Organizer
      第32回基礎有機化学討論会
    • Related Report
      2022 Annual Research Report
  • [Presentation] Realization of Stacked-Ring Aromaticity in a Water-Soluble Micellar Capsule2022

    • Author(s)
      Siyu Liu, Natsuki Kishida, Norihito Fukui, Michito Yoshizawa, Hiroshi Shinokubo
    • Organizer
      11th International Conference on Porphyrins and Phthalocyanines (ICPP-11)
    • Related Report
      2022 Annual Research Report
    • Int'l Joint Research
  • [Presentation] Close stacking of antiaromatic norcorrole complexes2022

    • Author(s)
      忍久保 洋
    • Organizer
      19th International Symposium on Novel Aromatic Compounds (ISNA 19)
    • Related Report
      2022 Annual Research Report
    • Int'l Joint Research / Invited
  • [Presentation] 反芳香族ポルフィリン:ノルコロールの化学2022

    • Author(s)
      忍久保 洋
    • Organizer
      大阪公立大学大学院工学研究科講演会
    • Related Report
      2022 Annual Research Report
    • Invited
  • [Presentation] 水溶性ミセル型カプセルによる積層反芳香族ノルコロールの内包2022

    • Author(s)
      劉 思雨, 岸田 夏月, 福井 識人, 吉沢 道人, 忍久保 洋
    • Organizer
      日本化学会第102春季年会
    • Related Report
      2021 Research-status Report
  • [Presentation] ペンタフルオロフェニル基をもつノルコロールニッケル錯体の合成と物性2022

    • Author(s)
      木野 翔太・鵜飼 修作・福井 識人・忍久保 洋
    • Organizer
      日本化学会第102春季年会
    • Related Report
      2021 Research-status Report
  • [Presentation] 一次元積層したノルコロール超分子ポリマーの形成および機能2021

    • Author(s)
      鵜飼 修作, 高松 愛子, 信岡 正樹, 筒井 祐介, 大城 宗一郎, 福井 識人, 関 修平, 山口 茂弘, 忍久保 洋
    • Organizer
      第31回基礎有機化学討論会
    • Related Report
      2021 Research-status Report
  • [Presentation] Encapsulation of Antiaromatic Norcorrole Ni(II) Complexes in a Water-Soluble Micellar Capsule2021

    • Author(s)
      劉 思雨, 岸田 夏月, 福井 識人, 吉沢 道人, 忍久保 洋
    • Organizer
      第31回基礎有機化学討論会
    • Related Report
      2021 Research-status Report
  • [Presentation] Three-Dimensional Aromaticity of Closely Stacked Norcorrole Dimers2021

    • Author(s)
      忍久保 洋
    • Organizer
      11th International Conference on Porphyrins and Phthalocyanines (ICPP-11)
    • Related Report
      2021 Research-status Report
    • Int'l Joint Research / Invited
  • [Presentation] Investigation of Kinetic Stabilization Effect at meso-Positions of Norcorrole Ni(II) Complexes2021

    • Author(s)
      飼 修作, Yun Hee Koob, 福井 識人, 関 修平, 忍久保 洋
    • Organizer
      11th International Conference on Porphyrins and Phthalocyanines (ICPP-11)
    • Related Report
      2021 Research-status Report
    • Int'l Joint Research
  • [Presentation] Synthesis of Covalently Linked Norcorrole Dimers and Their Association Behavior2021

    • Author(s)
      劉 思雨, 鵜飼 修作, 福井 識人, 忍久保 洋
    • Organizer
      11th International Conference on Porphyrins and Phthalocyanines (ICPP-11)
    • Related Report
      2021 Research-status Report
    • Int'l Joint Research
  • [Presentation] 反芳香族分子の近接積層による高密度共役2021

    • Author(s)
      忍久保 洋
    • Organizer
      CSJ化学フェスタ2021_
    • Related Report
      2021 Research-status Report
    • Invited
  • [Presentation] 反芳香族ポルフィリン:ノルコロールの化学2021

    • Author(s)
      忍久保 洋
    • Organizer
      東北大学大学院理学研究科講演会
    • Related Report
      2021 Research-status Report
    • Invited
  • [Presentation] ジメチルシロキサンで架橋されたノルコロール二量体の合成と物性2021

    • Author(s)
      木野 翔太・鵜飼 修作・福井 識人・忍久保 洋
    • Organizer
      第52回中部化学関係学協会支部連合秋季大会
    • Related Report
      2021 Research-status Report
  • [Presentation] Three-dimensional aromaticity of closely stacked antiaromatic porphyrins2021

    • Author(s)
      忍久保 洋
    • Organizer
      The International Chemical Congress of Pacific Basin Societies 2021
    • Related Report
      2021 Research-status Report
    • Int'l Joint Research / Invited
  • [Presentation] Redox-Induced Reversible [2+2] Cycloaddition of Etheno-Fused Diporphyrin2021

    • Author(s)
      宮川 和弥, 福井 識人, 忍久保 洋
    • Organizer
      11th International Conference on Porphyrins and Phthalocyanines (ICPP-11)
    • Related Report
      2021 Research-status Report
    • Int'l Joint Research
  • [Presentation] 超分子的アプローチによる反芳香族ノルコロールの一次元積層体形2021

    • Author(s)
      Shusaku Ukai, Aiko Takamatsu, Soichiro Ogi, Norihito Fukui, Shu Seki, Shigehiro Yamaguchi, Hiroshi Shinokubo
    • Organizer
      日本化学会第101春季年会
    • Related Report
      2020 Research-status Report
  • [Presentation] Synthesis of Covalently Linked Norcorrole Dimers and Their Association Behavior2021

    • Author(s)
      Si-Yu Liu, Shusaku Ukai, Norihito Fukui, Hiroshi Shinokubo
    • Organizer
      日本化学会第101春季年会
    • Related Report
      2020 Research-status Report
  • [Presentation] Supramolecular assembly of antiaromatic norcorrole2021

    • Author(s)
      Shusaku Ukai, Aiko Takamatsu, Soichiro Ogi, Norihito Fukui, Shu Seki, Shigehiro Yamaguchi, Hiroshi Shinokubo
    • Organizer
      GTR年次報告会
    • Related Report
      2020 Research-status Report
  • [Presentation] A 2-to-2' 18-to-18' Doubly Linked Ni(II) Norcorrole Dimer: An Effectively Conjugated Antiaromatic Dyad2020

    • Author(s)
      Si-Yu Liu, Hiroyuki Kawashima, Norihito Fukui, Hiroshi Shinokubo
    • Organizer
      第10回CSJ化学フェスタ2020
    • Related Report
      2020 Research-status Report
  • [Presentation] ジアザ-s-インダセンの合成と物性2020

    • Author(s)
      Kensuke Hanida, Norihito Fukui, Hiroshi Shinokubo
    • Organizer
      若手オンラインシンポジウム
    • Related Report
      2020 Research-status Report
  • [Remarks] 忍久保研究室

    • URL

      http://www.chembio.nagoya-u.ac.jp/labhp/organic1/index.html

    • Related Report
      2022 Annual Research Report 2020 Research-status Report
  • [Remarks] 忍久保研究室ホームページ

    • URL

      http://www.chembio.nagoya-u.ac.jp/labhp/organic1/index.html

    • Related Report
      2021 Research-status Report

URL: 

Published: 2020-08-03   Modified: 2024-01-30  

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