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Creation of Multifunctional Molecular Assembly from Macrocyclic Conjugated Systems

Research Project

Project/Area Number 17K05839
Research Category

Grant-in-Aid for Scientific Research (C)

Allocation TypeMulti-year Fund
Section一般
Research Field Functional solid state chemistry
Research InstitutionTokyo Metropolitan University

Principal Investigator

Iyoda Masahiko  東京都立大学, 理学研究科, 客員教授 (50115995)

Co-Investigator(Kenkyū-buntansha) 大谷 裕之  横浜国立大学, 大学院環境情報研究院, 教授 (30213763)
Project Period (FY) 2017-04-01 – 2021-03-31
Project Status Completed (Fiscal Year 2020)
Budget Amount *help
¥4,810,000 (Direct Cost: ¥3,700,000、Indirect Cost: ¥1,110,000)
Fiscal Year 2019: ¥910,000 (Direct Cost: ¥700,000、Indirect Cost: ¥210,000)
Fiscal Year 2018: ¥1,950,000 (Direct Cost: ¥1,500,000、Indirect Cost: ¥450,000)
Fiscal Year 2017: ¥1,950,000 (Direct Cost: ¥1,500,000、Indirect Cost: ¥450,000)
Keywords巨大有機環状共役系 / 超分子ナノ集積体 / ナノ構造 / スイッチ・デバイス機能 / モルフォロジー / πダイマー / 芳香族性 / 電磁誘導 / 超分子化学 / 超分子機能材料 / ナノ集積体 / 巨大πダイマー / アクチュエータ / 超分子
Outline of Final Research Achievements

We succeeded in the construction of supramolecular nanoaggregates prepared from giant macrocyclic organic π-electron systems. We first synthesized various macrocyclic π-electron systems composed of thienylene-ethynylene and thienylene-vinylene units by using the McMurry coupling reaction. These macrocyclic π-electron systems exhibit polymorphism based on nanophase separation between a large inner domain and an outer area. As a result, macrocycles produced nanoaggregates bearing functional properties such as molecular switch and device with light, heat, and organic vapor drive. Furthermore, radical salts derived from macrocycles produced a large 3-dimensional π-dimer with aromatic 70π-electrons. This π-dimer showed a large ring-current effect in a magnetic field by virtue of electromagnetic induction.

Academic Significance and Societal Importance of the Research Achievements

本申請研究では、巨大有機環状共役系が作る超分子ナノ構造を解明し、さらにそのスイッチ・デバイス機能ならびに磁場中での分子磁石としての挙動を明らかにした。これらの新規知見の学術的意義は非常に大きいと考えている。通常の有機環状共役系が作るナノ構造の研究は、構造化学的なアプローチが主であるが、本研究ではそのナノ構造の持つ機能の発現まで踏み込んだ研究を展開したので、幅広い分野の研究者の学術的好奇心を満たす内容であったと自負している。

Report

(5 results)
  • 2020 Annual Research Report   Final Research Report ( PDF )
  • 2019 Research-status Report
  • 2018 Research-status Report
  • 2017 Research-status Report
  • Research Products

    (31 results)

All 2020 2019 2018 2017 Other

All Journal Article (15 results) (of which Int'l Joint Research: 8 results,  Peer Reviewed: 15 results,  Open Access: 1 results) Presentation (15 results) (of which Int'l Joint Research: 5 results) Remarks (1 results)

  • [Journal Article] Reduction of Ethynylenes to Vinylenes in a Macrocyclic π-Extended Thiophene Skeleton Under McMurry Coupling Conditions2020

    • Author(s)
      Shirahata Keigo、Takashika Masataka、Hirabayashi Kazunori、Hasegawa Masashi、Otani Hiroyuki、Yamamoto Keitaro、Ie Yutaka、Shimizu Toshio、Aoyagi Shinobu、Iyoda Masahiko
    • Journal Title

      The Journal of Organic Chemistry

      Volume: 86 Issue: 1 Pages: 302-309

    • DOI

      10.1021/acs.joc.0c02080

    • Related Report
      2020 Annual Research Report
    • Peer Reviewed / Int'l Joint Research
  • [Journal Article] Reversible Color and Shape Changes of Nanostructured Fibers of a Macrocyclic π-Extended Thiophene Hexamer Promoted by Adsorption and Desorption of Organic Vapor2020

    • Author(s)
      Iyoda Masahiko、Takashika Masataka、Hasegawa Masashi、Otani Hiroyuki、Mizuno Saori、Miwa Kazuhira、Kariya Wakana、Fujiwara Toshihiro、Shimizu Hideyuki、Aoyagi Shinobu
    • Journal Title

      Journal of the American Chemical Society

      Volume: 142 Issue: 32 Pages: 13662-13666

    • DOI

      10.1021/jacs.0c05340

    • Related Report
      2020 Annual Research Report
    • Peer Reviewed / Int'l Joint Research
  • [Journal Article] Trapping a Pentagonal Molecule in a Self-Assembled Molecular Network: Alkoxylated Isosceles Triangular Molecule Does the Job2020

    • Author(s)
      M. Anzai, M. Iyoda, S. De Feyter, Y. Tobe, K. Tahara
    • Journal Title

      Chem. Comm.

      Volume: 56 Issue: 40 Pages: 5401-5404

    • DOI

      10.1039/d0cc01823f

    • Related Report
      2020 Annual Research Report 2019 Research-status Report
    • Peer Reviewed / Int'l Joint Research
  • [Journal Article] Preparation, Spectroscopic Characterization and Theoretical Study of a Three-Dimensional Conjugated 70 π-Electron Thiophene 6-Mer Radical Cation π-Dimer2020

    • Author(s)
      T. Fujiwara, A. Muranaka, T. Nishinaga, S. Aoyagi, N. Kobayashi, M. Uchiyama, H. Otani, M. Iyoda
    • Journal Title

      J. Am. Chem. Soc.

      Volume: 142 Issue: 13 Pages: 5933-5937

    • DOI

      10.1021/jacs.9b13573

    • Related Report
      2020 Annual Research Report 2019 Research-status Report
    • Peer Reviewed
  • [Journal Article] Self-assembly of Radially π-Extended Tetrathiafulvalene Tetramers for Visible and Near Infrared Electrochromic Nanofiber2020

    • Author(s)
      M. Hasegawa, M. Iyoda
    • Journal Title

      Bull. Chem. Soc. Jpn

      Volume: 93 Issue: 1 Pages: 154-162

    • DOI

      10.1246/bcsj.20190283

    • NAID

      130007784847

    • Related Report
      2020 Annual Research Report 2019 Research-status Report
    • Peer Reviewed
  • [Journal Article] A small structural change in the substituents of macrocyclic oligothiophenes causes a key effect on their stacking and functional properties2019

    • Author(s)
      T. Fujiwara, M. Takashika, M. Hasegawa, Y. Ie, Y. Aso, S. Aoyagi, H. Otani, M. Iyoda
    • Journal Title

      ChemPlusChem

      Volume: 84 Issue: 6 Pages: 694-703

    • DOI

      10.1002/cplu.201900062

    • Related Report
      2019 Research-status Report 2018 Research-status Report
    • Peer Reviewed
  • [Journal Article] Synthesis and Properties of a Tricyclic Hexaketone Monohydrate with Hexabutyl Side Chain2019

    • Author(s)
      M. Ishita, M. Ohkoshi, Y. Kuwatani, H. Otani, T. Nishinaga, M. Iyoda
    • Journal Title

      Heterocycles

      Volume: 99 Issue: 2 Pages: 1145-1153

    • DOI

      10.3987/com-18-s(f)85

    • Related Report
      2019 Research-status Report 2018 Research-status Report
    • Peer Reviewed
  • [Journal Article] Synthesis and structure of bis(ethylenedioxy)-1,4,5,8-tetraselenanaphthalene2018

    • Author(s)
      R. Watanabe, M. Hasegawa, M Iyoda
    • Journal Title

      Heteroatom Chem.

      Volume: 29 Issue: 5-6

    • DOI

      10.1002/hc.21479

    • Related Report
      2018 Research-status Report
    • Peer Reviewed
  • [Journal Article] Reversible Photoisomerization of Monolayers of π-Expanded Oligothiophene Macrocycles2018

    • Author(s)
      J. D. Cojal Gonzalez, M. Iyoda, J. P. Rabe
    • Journal Title

      Angew. Chem. Int. Ed.

      Volume: 57 Issue: 52 Pages: 17038-17042

    • DOI

      10.1002/anie.201809514

    • Related Report
      2018 Research-status Report
    • Peer Reviewed / Int'l Joint Research
  • [Journal Article] Polymorphism of Macrocyclic Oligothiophene 8-mers2018

    • Author(s)
      H. Shimizu, T. Haque, M. Takashika, H. Otani, M. Iyoda
    • Journal Title

      Heterocycles

      Volume: 97 Issue: 2 Pages: 1313-1318

    • DOI

      10.3987/com-18-s(t)92

    • Related Report
      2018 Research-status Report
    • Peer Reviewed / Int'l Joint Research
  • [Journal Article] A Saturn-like Complex Composed of Macrocyclic Oligothiophene and [60]fullerene: Structure, Stability, and Photophysical Properties in Solution and the Solid State2018

    • Author(s)
      Hideyuki Shimizu, Kyu Hyung Park, Hiroyuki Otani, Shinobu Aoyagi, Tohru Nishinaga, Yoshio Aso, Dongho Kim, Masahiko Iyoda
    • Journal Title

      Chem. Eur. J.

      Volume: 24 Issue: 15 Pages: 3793-3801

    • DOI

      10.1002/chem.201705565

    • Related Report
      2018 Research-status Report 2017 Research-status Report
    • Peer Reviewed / Int'l Joint Research
  • [Journal Article] 10-Mesityl-1,8-diphenylanthracene Dimer. Synthesis, Structure, and Properties2018

    • Author(s)
      A. Shirai, H. Sano, Y. Nakamura, M. Takashika, H. Otani, M. Hasegawa, S. Kato, M. Iyoda
    • Journal Title

      J. Org. Chem.

      Volume: 83 Issue: 7 Pages: 3857-3863

    • DOI

      10.1021/acs.joc.8b00200

    • Related Report
      2018 Research-status Report 2017 Research-status Report
    • Peer Reviewed
  • [Journal Article] Synthesis of Cyclic Oligomers of 4,4”-Diethynyl-4’,5’-dioctyl-o-terphenyl Using Eglington Coupling Reaction: Formation of Large Cyclic Oligomers as Major Products under Standard Conditions2017

    • Author(s)
      I. Sako, N. Kishimoto, H. Otani, T. Nishiuchi, H Shimizu, M. Iyoda
    • Journal Title

      Bull. Chem. Soc. Jpn.

      Volume: 90 Pages: 1244-1250

    • NAID

      130006201498

    • Related Report
      2017 Research-status Report
    • Peer Reviewed
  • [Journal Article] Pentadecaphenylenes: synthesis, self-assembly and complexation with fullerene C602017

    • Author(s)
      M. J. Rahman, H. Shimizu, M. Hasegawa, M. Iyoda
    • Journal Title

      Org. Chem. Frontiers

      Volume: 4 Issue: 5 Pages: 882-890

    • DOI

      10.1039/c7qo00258k

    • Related Report
      2017 Research-status Report
    • Peer Reviewed / Int'l Joint Research
  • [Journal Article] Templated bilayer self-assembly of fully conjugated pi-expanded macrocyclic oligothiophenes complexed with fullerenes2017

    • Author(s)
      J. D. Cojal González, M. Iyoda, J. P. Rabe
    • Journal Title

      Nature Commun.

      Volume: 8 Issue: 1 Pages: 14717-14717

    • DOI

      10.1038/ncomms14717

    • Related Report
      2017 Research-status Report
    • Peer Reviewed / Open Access / Int'l Joint Research
  • [Presentation] McMurry カップリング条件下でのエチニレンからビニレンへの還元を用いる新規大環状オリゴチオフェンの合成2020

    • Author(s)
      白畑圭悟,平林一徳、大谷裕之,長谷川真士,伊與田正彦
    • Organizer
      第47回有機典型元素化学討論会
    • Related Report
      2020 Annual Research Report
  • [Presentation] 1,8-ビス[(2-ドデシルアミノトロポン-5-イル)エチニル]-10-ドデシルアントラセン環状二量化錯体の合成、構造、および性質2020

    • Author(s)
      松原康太,伊與田正彦,大谷裕之
    • Organizer
      日本化学会第100春季年会
    • Related Report
      2020 Annual Research Report
  • [Presentation] 環状(ビニレンチエニレン)3量体および4量体の合成と性質2020

    • Author(s)
      大窪啓嵩,藤原稔大,大谷裕之,伊與田正彦
    • Organizer
      日本化学会第100春季年会
    • Related Report
      2020 Annual Research Report
  • [Presentation] ビニレンとエチニレンでπ拡張した環状チオフェン6量体の特異な結晶構造と電子物性2020

    • Author(s)
      白畑圭悟,大谷裕之,長谷川真士,伊與田正彦
    • Organizer
      日本化学会第100春季年会
    • Related Report
      2020 Annual Research Report
  • [Presentation] 大環状π拡張チオフェン類のジカチオンにおける電子状態と環状共役2020

    • Author(s)
      藤原稔大,村中厚哉,西長亨,大谷裕之,小林長夫,伊與田正彦
    • Organizer
      日本化学会第100春季年会
    • Related Report
      2020 Annual Research Report
  • [Presentation] The Effect of Alkyl Substituents on the Structure and Functional Properties of Macrocyclic Oligothiophene 6-mers2019

    • Author(s)
      Toshihiro Fujiwara, Hiroyuki Otani, Masahiko Iyoda
    • Organizer
      ISNA-18
    • Related Report
      2019 Research-status Report
    • Int'l Joint Research
  • [Presentation] Vapochromism and Vapor-Induced Shape Changes of Macrocyclic π-Extended Thiophene Oligomers2019

    • Author(s)
      Saori Mizuno, Masataka Takashika, Hiroyuki Otani, Shinobu Aoyagi, Masahiko Iyoda
    • Organizer
      ISNA-18
    • Related Report
      2019 Research-status Report
    • Int'l Joint Research
  • [Presentation] Synthesis of Macrocyclic Oligothiophene 6-Mer by McMurry Coupling Accompanied by Reduction of Acetylene Bond2019

    • Author(s)
      Keigo Shirahata, Masataka Takashika, Hiroyuki Otani, Masahiko Iyoda
    • Organizer
      ISNA-18
    • Related Report
      2019 Research-status Report
    • Int'l Joint Research
  • [Presentation] 大環状π拡張チオフェン6量体の酸化種の示す特異な光学および電子物性2019

    • Author(s)
      藤原稔大、村中厚哉、西長亨、青柳忍、大谷裕之、小林長夫 、伊與田正彦
    • Organizer
      第30回基礎有機化学討論会
    • Related Report
      2019 Research-status Report
  • [Presentation] Self-assembly of π-expanded oligothiophene macrocycles into functional supramolecular monolayers2019

    • Author(s)
      Jose D. Cojal Gonzalez, Masahiko Iyoda, Jürgen P. Rabe
    • Organizer
      Fpi-14
    • Related Report
      2019 Research-status Report
    • Int'l Joint Research
  • [Presentation] フェニル置換大環状オリゴチオフェン6量体ファイバーの溶媒蒸気による多彩な形状変化2018

    • Author(s)
      高鹿聖崇、青柳忍、大谷裕之、伊與田正彦
    • Organizer
      第45回有機典型元素化学討論会
    • Related Report
      2018 Research-status Report
  • [Presentation] アルキル置換大環状オリゴチオフェン6量体の物性の大きな置換基依存性2018

    • Author(s)
      藤原稔大、高鹿聖崇、家裕隆、安蘇芳雄、大谷裕之、伊與田正彦
    • Organizer
      第29回基礎有機化学討論会
    • Related Report
      2018 Research-status Report
  • [Presentation] Macrocyclic Oligothiophene 6-Mer with Alkyl Substituents; A Large π-Conjugated System with Supramolecular Properties2018

    • Author(s)
      Toshihiro Fujiwara, Hiroyuki Otani, Masahiko Iyoda
    • Organizer
      ISOCS-28
    • Related Report
      2018 Research-status Report
    • Int'l Joint Research
  • [Presentation] 大環状オリゴチオフェン6量体の固体構造、ベイポクロミズム、および可逆な形状変化2017

    • Author(s)
      高鹿聖崇、苅谷和佳奈、清水秀幸、長谷川真士、青柳忍、大谷裕之、伊與田正彦
    • Organizer
      第44回有機典型元素化学討論会
    • Related Report
      2017 Research-status Report
  • [Presentation] フェニル置換大環状オリゴチオフェン6量体の示す特異なモルフォロジーと機能2017

    • Author(s)
      高鹿聖崇、苅谷和佳奈、大谷裕之、長谷川真士、伊與田正彦
    • Organizer
      第28回基礎有機化学討論会
    • Related Report
      2017 Research-status Report
  • [Remarks] 伊與田研究室

    • URL

      http://www.comp.tmu.ac.jp/iyoda/

    • Related Report
      2018 Research-status Report

URL: 

Published: 2017-04-28   Modified: 2022-01-27  

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