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2023 Fiscal Year Annual Research Report

Modulation of optoelectronic properties of conjugated polymers containing hyper valent heavy elements

Research Project

Project/Area Number 21H02001
Research InstitutionKyoto University

Principal Investigator

田中 一生  京都大学, 地球環境学堂, 教授 (90435660)

Project Period (FY) 2021-04-01 – 2024-03-31
Keywords共役系高分子 / 近赤外 / 発光
Outline of Annual Research Achievements

近赤外光の有用性から、近赤外発光性高分子の開発が近年益々望まれている。ここで近赤外発光を得るには狭エネルギーギャップの電子構造が必要であるが、既存の分子設計では骨格が大型となるため溶媒への溶解性が乏しく、化学修飾が困難であることや高分子化も極めて困難であった。特に、拡張π共役系間の強い分子間相互作用により濃度消光が引き起こされ、固体発光性の低下が起こる。以上、拡張π共役系に基づく既存の分子設計では近赤外発光材料開発は限界を迎えていた。このような状況で、アゾベンゼンホウ素錯体を足場として様々な共役系高分子を合成した。まず、共役系を伸長せずに最低空軌道(LUMO)のみを引き下げ、狭ギャップ構造を実現するという我々が最近提唱している新しい設計指針について、実際に様々な共役系分子・高分子を合成することで、その有効性を実証した。得られた材料により溶解性や製膜性など既存の材料における諸問題を解決することができ、そして様々な機能性近赤外発光性高分子の開発に成功した。ここで、有機化合物で1,000 nm以上の長波長領域で発光を示すものはポルフィリン錯体など一部の分子に限られており、選択肢は少ない。これらの分子は汎用溶媒への溶解性が低く、高分子化することは困難である。そこで上記の成果をもとに研究を進め、最終的には従来の高分子では実現が極めて困難な1200 nm以上に発光極大を持つ高輝度材料の開発に成功した。さらに、元素の特性を活かして新奇の刺激応答性材料の構築を達成した。UV光照射により高分子鎖が分解する反応を見出し、これを利用することで光駆動型の分子放出システムの構築が可能となった。以上、共役系を拡張しない近赤外発光性高分子材料の新しい設計指針の確立に重要な実証データを数多く得ることに成功したことに加え、様々な刺激応答性材料を開発したことから、十二分に成果を挙げることができたといえる。

Research Progress Status

令和5年度が最終年度であるため、記入しない。

Strategy for Future Research Activity

令和5年度が最終年度であるため、記入しない。

  • Research Products

    (20 results)

All 2024 2023

All Journal Article (17 results) (of which Peer Reviewed: 16 results) Presentation (3 results) (of which Int'l Joint Research: 3 results,  Invited: 3 results)

  • [Journal Article] Synthesis of Regioregular and Random Boron‐Fused Azomethine Conjugated Polymers for Film Morphology Control2024

    • Author(s)
      Ohtani Shunsuke、Gon Masayuki、Tanaka Kazuo、Chujo Yoshiki
    • Journal Title

      Chemistry An Asian Journal

      Volume: - Pages: e202301136

    • DOI

      10.1002/asia.202301136

    • Peer Reviewed
  • [Journal Article] Synthesis, cation exchange, and optical properties of pyrene-based chromophores containing [CB9H9]? and [CB11H11]? cluster units2024

    • Author(s)
      Ochi Junki、Yanagihara Takumi、Tanaka Kazuo、Chujo Yoshiki
    • Journal Title

      Bulletin of the Chemical Society of Japan

      Volume: 97 Pages: uoae005

    • DOI

      10.1093/bulcsj/uoae005

    • Peer Reviewed
  • [Journal Article] UV-to-NIR Wavelength Conversion of π-Conjugated Polymers Based on Pyrene-Substituted Boron-Fused Azobenzene Complexes2023

    • Author(s)
      Nakamura Masashi、Yamauchi Momona、Gon Masayuki、Tanaka Kazuo
    • Journal Title

      Macromolecules

      Volume: 56 Pages: 7571~7578

    • DOI

      10.1021/acs.macromol.3c01124

    • Peer Reviewed
  • [Journal Article] Highly efficient luminescence from boron β-dialdiminates and their π-conjugated polymers in both solutions and solids: significant impact of the substituent position on luminescence behavior2023

    • Author(s)
      Ito Shunichiro、Hashizume Miyako、Taka Hideo、Kita Hiroshi、Tanaka Kazuo、Chujo Yoshiki
    • Journal Title

      Materials Chemistry Frontiers

      Volume: 7 Pages: 4971~4983

    • DOI

      10.1039/D3QM00761H

    • Peer Reviewed
  • [Journal Article] Design for a Pure-Blue-Emissive Polymer Film through the Selective Perturbation of the Energy Level of the Highest Occupied Molecular Orbital in a Boron Complex2023

    • Author(s)
      Suenaga Kazumasa、Watanabe Aoi、Tanaka Kazuo、Chujo Yoshiki
    • Journal Title

      Macromolecules

      Volume: 56 Pages: 6419~6425

    • DOI

      10.1021/acs.macromol.3c01115

    • Peer Reviewed
  • [Journal Article] Enhancement of Near-Infrared Emission Based on Hypervalent Germanium(IV)-Fused Azobenzene Compounds with Electron-Donating Groups2023

    • Author(s)
      Gon Masayuki、Yaegashi Misao、Tanaka Kazuo
    • Journal Title

      Bulletin of the Chemical Society of Japan

      Volume: 96 Pages: 778~784

    • DOI

      10.1246/bcsj.20230120

    • Peer Reviewed
  • [Journal Article] Design and Synthesis of Far‐Red to Near‐Infrared Chromophores with Pyrazine‐Based Boron Complexes2023

    • Author(s)
      Takahashi Hiromasa、Watanabe Hiroyuki、Ito Shunichiro、Tanaka Kazuo、Chujo Yoshiki
    • Journal Title

      Chemistry ? An Asian Journal

      Volume: 18 Pages: e202300489

    • DOI

      10.1002/asia.202300489

    • Peer Reviewed
  • [Journal Article] Stimuli-Responsive π-Conjugated Polymers Showing Solid-State Emission Based on Boron-Fused Azomethine Complexes with NNO-Tridentate Ligands2023

    • Author(s)
      Kanjo Misato、Gon Masayuki、Tanaka Kazuo
    • Journal Title

      ACS Applied Materials & Interfaces

      Volume: 15 Pages: 31927~31934

    • DOI

      10.1021/acsami.3c06277

    • Peer Reviewed
  • [Journal Article] Selective modulation of energy levels of frontier orbitals in solid-state luminescent boron-fused azomethine polymers with orthogonal orientations to the main chains2023

    • Author(s)
      Gon Masayuki、Kanjo Misato、Ohtani Shunsuke、Tanaka Kazuo、Chujo Yoshiki
    • Journal Title

      Polymer Chemistry

      Volume: 14 Pages: 2893~2901

    • DOI

      10.1039/D3PY00335C

    • Peer Reviewed
  • [Journal Article] Facile Preparation of Near Infrared-Luminescent Protein Complexes with Conjugated Polymers Consisting of Boron Azobenzene Units2023

    • Author(s)
      Yoo Dahye、Nakamura Masashi、Kanjo Misato、Gon Masayuki、Watanabe Hiroyuki、Kita Hiroshi、Tanaka Kazuo
    • Journal Title

      Bulletin of the Chemical Society of Japan

      Volume: 96 Pages: 659~662

    • DOI

      10.1246/bcsj.20230083

    • Peer Reviewed
  • [Journal Article] Enhancement of the Lowering Effect on Energy Levels of LUMO by the Formation of B?N Dative Bond for Near‐infrared Light Absorption Properties Based on 1,3,4,6,8,9?b‐Hexaazaphenalene2023

    • Author(s)
      Watanabe Hiroyuki、Ito Yoshinori、Tanaka Kazuo、Chujo Yoshiki
    • Journal Title

      Asian Journal of Organic Chemistry

      Volume: 12 Pages: e202300156

    • DOI

      10.1002/ajoc.202300156

  • [Journal Article] Effects of Central Elements on the Properties of Group 13 Dialdiminate Complexes2023

    • Author(s)
      Aoyama Yuto、Sakai Yuki、Ito Shunichiro、Tanaka Kazuo
    • Journal Title

      Chemistry ? A European Journal

      Volume: 29 Pages: e202300654

    • DOI

      10.1002/chem.202300654

    • Peer Reviewed
  • [Journal Article] Synthesis, Characterization, and Photoluminescence Properties of Boron Tropolonate Complexes: From Fluorescence to Room Temperature Phosphorescence2023

    • Author(s)
      Ogoshi Hikari、Ito Shunichiro、Tanaka Kazuo
    • Journal Title

      Bulletin of the Chemical Society of Japan

      Volume: 96 Pages: 452~460

    • DOI

      10.1246/bcsj.20230058

    • Peer Reviewed
  • [Journal Article] Solid-State Near-Infrared Emission of π-Conjugated Polymers Consisting of Boron Complexes with Vertically Projected Steric Substituents2023

    • Author(s)
      Nakamura Masashi、Gon Masayuki、Tanaka Kazuo、Chujo Yoshiki
    • Journal Title

      Macromolecules

      Volume: 56 Pages: 2709~2718

    • DOI

      10.1021/acs.macromol.2c02578

    • Peer Reviewed
  • [Journal Article] Effects of Hypervalent Bismuth on Electronic Properties of the Azobenzene Tridentate Ligand and Roles of Lewis Acidity in Controlling Optical Properties2023

    • Author(s)
      Tanimura Kazuya、Gon Masayuki、Tanaka Kazuo
    • Journal Title

      Inorganic Chemistry

      Volume: 62 Pages: 4590~4597

    • DOI

      10.1021/acs.inorgchem.2c04478

    • Peer Reviewed
  • [Journal Article] Vapochromic films of π-conjugated polymers based on coordination and desorption at hypervalent tin(<scp>iv</scp>)-fused azobenzene compounds2023

    • Author(s)
      Gon Masayuki、Morisaki Yusuke、Tanimura Kazuya、Tanaka Kazuo、Chujo Yoshiki
    • Journal Title

      Materials Chemistry Frontiers

      Volume: 7 Pages: 1345~1353

    • DOI

      10.1039/D2QM01295B

    • Peer Reviewed
  • [Journal Article] Near‐Infrared Emissive Hypervalent Compounds with Germanium(IV)‐Fused Azobenzene π‐Conjugated Systems2023

    • Author(s)
      Gon Masayuki、Yaegashi Misao、Tanaka Kazuo、Chujo Yoshiki
    • Journal Title

      Chemistry ? A European Journal

      Volume: 29 Pages: e202203423

    • DOI

      10.1002/chem.202203423

    • Peer Reviewed
  • [Presentation] Design for NIR AIE-active materials without expanding π-conjugated systems2023

    • Author(s)
      Kazuo Tanaka
    • Organizer
      Aggregation forum 2023
    • Int'l Joint Research / Invited
  • [Presentation] Logical Design for Functional NIR Materials Based on AIE-Active Element-Blocks2023

    • Author(s)
      Kazuo Tanaka
    • Organizer
      2023 MRS Spring Meeting & Exhibit
    • Int'l Joint Research / Invited
  • [Presentation] Design and Application of Boron-Containing AIEgens2023

    • Author(s)
      Kazuo Tanaka
    • Organizer
      Tutorial lecture, 2023 MRS Spring Meeting & Exhibit
    • Int'l Joint Research / Invited

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Published: 2024-12-25  

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