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Development of quinoidal molecules with tuned biradical character and application to photodiode and thermoelectric devices

Research Project

Project/Area Number 20K21224
Research Category

Grant-in-Aid for Challenging Research (Exploratory)

Allocation TypeMulti-year Fund
Review Section Medium-sized Section 35:Polymers, organic materials, and related fields
Research InstitutionOsaka University

Principal Investigator

IE YUTAKA  大阪大学, 産業科学研究所, 教授 (80362622)

Project Period (FY) 2020-07-30 – 2022-03-31
Project Status Completed (Fiscal Year 2021)
Budget Amount *help
¥6,500,000 (Direct Cost: ¥5,000,000、Indirect Cost: ¥1,500,000)
Fiscal Year 2021: ¥3,250,000 (Direct Cost: ¥2,500,000、Indirect Cost: ¥750,000)
Fiscal Year 2020: ¥3,250,000 (Direct Cost: ¥2,500,000、Indirect Cost: ¥750,000)
Keywordsキノイド / 有機半導体 / 電子輸送材料 / 光ダイオード / 熱電変換 / 電子輸送型材料
Outline of Research at the Start

π共役分子に有機半導体としての機能を付与させる研究が注目されている。キノイド構造のオリゴチオフェンは低い最低空軌道レベルを持つことから、キャリアが電子のn型半導体への応用が期待されている。チオフェン環の芳香族化に起因して、キノイド構造はビラジカル構造との共鳴である。共役の鎖長伸長に伴ってビラジカル構造の寄与が高くなると化学的安定性が低下するため、n型半導体としての応用が困難となる。そこで本研究では、キノイド構造安定化させることでビラカル性を調節したキノイドオリゴチオフェンを系統的に開発し、ビラジカル性がn型の光ダイオード特性や熱電変換特性に及ぼす影響を解明する。

Outline of Final Research Achievements

Elucidating the nature of electronic structures in pi-extended quinoids is of considerable importance. In this study, we utilized the aromatic stabilization of the quinoidal form by introducing benzene-annelated isothianaphthene structures to shed light on the problem related to the development of long quinoidal systems with controlled quinoidal/aromatic contributions and stabilities. The electronic structures are controlled precisely by the number and position of benzene-annelations. These quinoidal pentathiophenes function as organic semiconductors in transistor and near infrared phototransistor devices. As a result, the combination of quinoidal structures with cross-conjugated units constitutes a novel approach to modulate the electronic properties of pi-extended quinoids.

Academic Significance and Societal Importance of the Research Achievements

キノイド構造分子は基底状態においてキノイドとビラジカルの共鳴構造であり、鎖長が伸長するにつれてビラジカル性の寄与が大きくなる。本研究では、ビラジカル性を精密に調節した長鎖キノイド構造オリゴチオフェンを系統的に創出し、その特異な基礎物性と半導体材料としての機能開拓に成功した。得られた知見は、近赤外光やビラジカル性を利用した新機軸の有機エレクトロニクス材料の開発に活かせると期待される。

Report

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

    (13 results)

All 2022 2021 2020 Other

All Int'l Joint Research (1 results) Journal Article (7 results) (of which Int'l Joint Research: 4 results,  Peer Reviewed: 7 results,  Open Access: 2 results) Presentation (5 results) (of which Int'l Joint Research: 1 results,  Invited: 3 results)

  • [Int'l Joint Research] University of Malaga(スペイン)

    • Related Report
      2020 Research-status Report
  • [Journal Article] Cross-conjugated Isothianaphthene Quinoids: A Versatile Strategy for Controlling Electronic Structures2022

    • Author(s)
      K. Yamamoto, S. M. Quintero, S. Jinnai, E. Jeong, K. Matsuo, M. Suzuki, H. Yamada, J. Casado, Y. Ie
    • Journal Title

      J. Mater. Chem. C

      Volume: 10 Issue: 11 Pages: 4424-4433

    • DOI

      10.1039/d1tc05794d

    • Related Report
      2021 Annual Research Report
    • Peer Reviewed / Int'l Joint Research
  • [Journal Article] Synthesis, Properties, and Photovoltaic Characteristics of Arch- and S-shaped Naphthobisthiadiazole-based Acceptors2021

    • Author(s)
      S. Jinnai, Y. Ie
    • Journal Title

      Journal of Photopolymer Science and Technology

      Volume: 34 Issue: 3 Pages: 285-290

    • DOI

      10.2494/photopolymer.34.285

    • NAID

      130008119605

    • ISSN
      0914-9244, 1349-6336
    • Year and Date
      2021-06-11
    • Related Report
      2021 Annual Research Report
    • Peer Reviewed / Int'l Joint Research
  • [Journal Article] Oligoene and Cyanine Features of Tetracyano Quinoidal Oligothiophenes2021

    • Author(s)
      S. Moles, Sergio; J. L. Zafra, K. Yamamoto, Y. Aso, Y. Ie, J. Casado
    • Journal Title

      J. Mater. Chem. C

      Volume: 9 Issue: 33 Pages: 10727-10740

    • DOI

      10.1039/d1tc01436f

    • Related Report
      2021 Annual Research Report
    • Peer Reviewed / Int'l Joint Research
  • [Journal Article] Electron-Accepting π-Conjugated Compound Containing Cyano-Substituted Naphthobisthiadiazole as Nonfullerene Acceptor in Organic Solar Cells2021

    • Author(s)
      S. Jinnai, A. Oi, T. Seo, T. Moriyama, R. Minami, S. Higashida, Y. Ie
    • Journal Title

      Synthesis

      Volume: 53 Issue: 18 Pages: 3390-3396

    • DOI

      10.1055/a-1528-1632

    • Related Report
      2021 Annual Research Report
    • Peer Reviewed / Int'l Joint Research
  • [Journal Article] Improving Intramolecular Hopping Charge Transport via Periodical Segmentation of π-Conjugation in a Molecule2021

    • Author(s)
      Y. Ie, Y. Okamoto, T. Inoue, T. Seo, T. Ohto, R. Yamada, H. Tada, Y. Aso
    • Journal Title

      J. Am. Chem. Soc.

      Volume: 143 Issue: 2 Pages: 599-603

    • DOI

      10.1021/jacs.0c10560

    • Related Report
      2020 Research-status Report
    • Peer Reviewed / Open Access
  • [Journal Article] Single-Molecule Conductance of a π-Hybridized Tripodal Anchor while Maintaining Electronic Communication2021

    • Author(s)
      T. Ohto, A. Tashiro, T. Seo, N. Kawaguchi, Y. Numai, J. Tokumoto, S. Yamaguchi, R. Yamada, H. Tada, Y. Aso, Y. Ie
    • Journal Title

      Small

      Volume: 17 Issue: 3 Pages: 2006709-2006709

    • DOI

      10.1002/smll.202006709

    • Related Report
      2020 Research-status Report
    • Peer Reviewed
  • [Journal Article] Correlation between the Dipole Moment of Nonfullerene Acceptors and the Active Layer Morphology of Green-Solvent-Processed P3HT-Based Organic Solar Cells2020

    • Author(s)
      S. Chatterjee, T. Ohto, H. Tada, S. Jinnai, Y. Ie
    • Journal Title

      ACS Sustainable Chem. Eng.

      Volume: 8 Issue: 51 Pages: 19013-19022

    • DOI

      10.1021/acssuschemeng.0c07114

    • Related Report
      2020 Research-status Report
    • Peer Reviewed / Open Access
  • [Presentation] 非フラーレン型アクセプターへの応用に向けた新規π共役分子の開発2021

    • Author(s)
      家 裕隆
    • Organizer
      2021年光化学討論会
    • Related Report
      2021 Annual Research Report
    • Invited
  • [Presentation] エレクトロニクス応用に向けた精密設計に基づく機能性pi共役分子の開発2021

    • Author(s)
      家 裕隆
    • Organizer
      M&BE 6月研究会
    • Related Report
      2021 Annual Research Report
    • Invited
  • [Presentation] Dipole Moment of Nonfullerene Acceptors: A Strategy for Green-Solvent Processed P3HT-Based Organic Solar Cells2021

    • Author(s)
      Yutaka Ie
    • Organizer
      239th ECS Meeting
    • Related Report
      2021 Annual Research Report
    • Int'l Joint Research / Invited
  • [Presentation] ビラジカル性を制御したベンゾ縮環型キノイドオリゴチオフェンの合成と物性2021

    • Author(s)
      山本 恵太郎、家 裕隆
    • Organizer
      日本化学会第100春季年会
    • Related Report
      2020 Research-status Report
  • [Presentation] キノイド構造の安定化に基づくキノイドオリゴチオフェンの機能化2020

    • Author(s)
      山本 恵太郎、安蘇 芳雄、家 裕隆
    • Organizer
      第69回高分子討論会
    • Related Report
      2020 Research-status Report

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Published: 2020-08-03   Modified: 2023-01-30  

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