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Chemistry of Boron-Containing pi-Electron Materials

Research Project

Project/Area Number 18H05261
Research Category

Grant-in-Aid for Scientific Research (S)

Allocation TypeSingle-year Grants
Review Section Broad Section E
Research InstitutionNagoya University

Principal Investigator

山口 茂弘  名古屋大学, 物質科学国際研究センター(WPI), 教授 (60260618)

Project Period (FY) 2018-06-11 – 2023-03-31
Project Status Granted (Fiscal Year 2022)
Budget Amount *help
¥193,700,000 (Direct Cost: ¥149,000,000、Indirect Cost: ¥44,700,000)
Fiscal Year 2022: ¥29,900,000 (Direct Cost: ¥23,000,000、Indirect Cost: ¥6,900,000)
Fiscal Year 2021: ¥34,580,000 (Direct Cost: ¥26,600,000、Indirect Cost: ¥7,980,000)
Fiscal Year 2020: ¥37,960,000 (Direct Cost: ¥29,200,000、Indirect Cost: ¥8,760,000)
Fiscal Year 2019: ¥39,910,000 (Direct Cost: ¥30,700,000、Indirect Cost: ¥9,210,000)
Fiscal Year 2018: ¥51,350,000 (Direct Cost: ¥39,500,000、Indirect Cost: ¥11,850,000)
Keywordsπ電子系 / ホウ素 / 蛍光 / 超分子ポリマー / パイ電子系 / 近赤外色素 / 蛍光イメージング / 有機電界発光素子 / ルイス酸性 / ラジカル / 超分子重合 / 半導体 / 超分子 / 有機半導体 / 安定性
Outline of Annual Research Achievements

本研究では,多様な元素の中でもホウ素に着目し,ホウ素の電子欠損性の活用により,秀逸な光電子機能性分子の創製を目的としている.最近我々は,トリアリールボラン骨格の平面固定化により,ホウ素の立体保護が無くても十分に安定化できることを示し,ホウ素ドープグラフェンのモデル系ともいえる「平面ホウ素π電子系」の合成と物性の理解、機能開拓について検討してきた.本研究では,これをさらに一段進め,ホウ素の特性を最大限活かすことにより,近赤外蛍光や,両極性半導体特性,フォトクロミック特性などの点で突出した特性をもつ分子系を創出に挑戦している.また,ホウ素とピリジン配位子との錯形成平衡の活用により,平面π電子系の超分子重合の制御にも挑んでいる.この高次構造制御をもとに,有機半導体材料の機能発現に適した薄膜構造の形成や,多重刺激応答性超分子材料の創製,細胞内での超分子化学の実現など,他の分子系では困難な物質機能を実現し,有機エレクトロニクスや生命科学研究の進展に寄与することが究極の目標である.この中で本年度は,3つの異なるアリール基を導入した平面固定化ホウ素π電子系の合成法の開発に取り組むとともに,一連のホウ素π電子系の構造とLewis酸性との相関を精査し,顕著なLewis賛成をもつ新骨格の創出を達成した.また,蛍光波長の長波長化にも取り組み,ホウ素を含むD-A-A型π骨格からなる近赤外蛍光分子を新たに創出した.ホウ素により極度に安定化した平面固定ラジカルに関しては,有機LEDへの応用を検討し,二重項励起状態に由来した高い効率を実現し,その潜在的有用性を示した.また,平面固定ホウ素パイ電子系の平面性を活かした自己組織化についても検討し,速度論的制御による超分子ポリマーの合成にも成功した.

Current Status of Research Progress
Current Status of Research Progress

2: Research has progressed on the whole more than it was originally planned.

Reason

ホウ素の電子欠損性の活用を基軸とした光・電子機能性分子の創製を目指し,本年度は以下の4点に重点的に取り組み,進展を得た.
i) 平面固定トリアリールボラン骨格の合成法の開発:ホウ素上に3つの異なるアリール基を導入し,異なる役割をアリール基にもたせることにより,より緻密にデザインされたホウ素コア骨格を創り出せる.この観点から,非対称平面固定トリアリールボラン骨格の合成法の確立に取み,3つのアリール基を事前に連結した前駆体を経由する合成法を用いることで,合成を可能にした.この合成法をもとに,顕著なLewis酸性をもつ新骨格の創製にも取り組んだ.
ii) 近赤外蛍光骨格の創出:近赤外領域で吸収・発光をもつ分子の開発を狙い,電子受容性のホウ素π骨格と,電子受容性スペーサー部位を組み合わせたD-A-A型骨格を創ることにより,高輝度の近赤外蛍光の実現に成功した.
iii) ホウ素安定化ラジカルの物性と応用:ホウ素で極度に安定化したπラジカルが強い赤色蛍光を示すことに焦点を当て,構造―物性相関の検討によりその起源と修飾の可能性を明らかにした.また,このπラジカルの有機ELへの応用についても検討し,πラジカルを発光性ドーパントとして用い,電子構造のバランスのとれた一連の材料と組み合わせた素子作製を塗布プロセスにより行い,高い励起子生成効率を達成した.
iv) ホウ素π電子系からなる超分子ポリマーの創製:平面固定化ホウ素π電子系の平面構造とLewis酸性を活用することにより,ホウ素π電子系からなる超分子ポリマーの種重合に取り組んだ.自発的な会合の抑制部位としてジアミド骨格を導入したホウ素π電子系の精密超分子重合を検討し,螺旋状の一次元集合体をもつ超分子ポリマーの形成に成功した.また,同じ形をもつ平面固定トリアリールボランとトリアリールアミンπ電子系とのブロック超分子共重合体の形成にも成功した.

Strategy for Future Research Activity

ホウ素を含む光・電子機能性分子の創製を目指し,以下の点に継続して取り組む
1) 構造固定ホウ素π電子系のコア骨格の合成・物性評価:3つの異なるアリール基を導入した構造固定トリアリールボラン骨格の創製を引き続き行う.役割の異なる3つのアリール基の導入や,構造固定を広義に捉えた骨格の合成法の確立を行い,それらのコア骨格としての有用性,潜在性を明らかにする.得られるπ電子系のパッキング様式,光物性,ルイス酸性等の基礎物性の評価を進め,各々に特有の機能を追求する.
2) ホウ素π電子系の物性の追求:ホウ素骨格部位をacceptor部位に用いたD-A-A型もしくはA-D-A型構造の構築により,引き続き近赤外蛍光特性を追求する.また,ホウ素安定化ラジカルにおいても,まだ赤色発光にとどまっているので,この長波長化を実現する新骨格の合成を行う.ホウ素π電子系の光反応についても引き続き検討を行い,フォトクロミック分子系の創製を狙う.
3) ホウ素π電子系からなる超分子ポリマーの機能開拓:ジアミド側鎖を導入した平面固定ホウ素π電子系の超分子重合を引き続き追求する.平面ホウ素π電子系のπスタック能,ルイス酸性,ジアミド部位の水素結合形成といった特性の相乗的活用により,高度な配向手法の確立を目指す.また,これらの種重合による精密超分子重合にも取り組み,超分子ポリマーの分子量・長さが物性に及ぼす効果について精査する.
4) ホウ素π電子系の有機エレクトロニクスへの展開:ホウ素安定化πラジカルの両極性電荷輸送特性と赤色発光特性に着目し,近赤外有機ELの発光材料としての有用性を引き続き検討する.
5) ホウ素π電子系のバイオイメージングへの展開:ホウ素π電子系の蛍光イメージングへの応用の可能性を引き続き精査する.特に上記で得られる近赤外蛍光色素骨格を用い,深部イメージングへの応用の可能性を追求する.

Assessment Rating
Interim Assessment Comments (Rating)

A: In light of the aim of introducing the research area into the research categories, the expected progress has been made in research.

Report

(6 results)
  • 2020 Abstract (Interim Assessment) ( PDF )   Interim Assessment (Comments) ( PDF )
  • 2019 Annual Research Report
  • 2018 Abstract ( PDF )   Comments on the Screening Results ( PDF )   Annual Research Report

Research Products

(35 results)

All 2020 2019 2018 Other

All Int'l Joint Research (2 results) Journal Article (7 results) (of which Int'l Joint Research: 3 results,  Peer Reviewed: 7 results,  Open Access: 2 results) Presentation (26 results) (of which Int'l Joint Research: 20 results,  Invited: 15 results)

  • [Int'l Joint Research] University of Wuerzburg(ドイツ)

    • Related Report
      2019 Annual Research Report
  • [Int'l Joint Research] Eindhoven University of Technology(オランダ)

    • Related Report
      2019 Annual Research Report
  • [Journal Article] The Effect of Branching on the One- and Two-Photon Absorption, Cell Viability, and Localization of Cationic Triarylborane Chromophores with Dipolar versus Octupolar Charge Distributions for Cellular Imaging2019

    • Author(s)
      Griesbeck S., Michail E., Rauch F., Ogasawara H., Wang C., Sato Y., Edkins R. M., Zhang Z., Taki M., Lambert C., Yamaguchi S., Marder T. B.
    • Journal Title

      Chemistry-A European Journal

      Volume: 25 Pages: 13164-13175

    • DOI

      10.1002/chem.201902461

    • Related Report
      2019 Annual Research Report
    • Peer Reviewed / Open Access / Int'l Joint Research
  • [Journal Article] Near-infrared fluorescein dyes containing a tricoordinate boron atom2019

    • Author(s)
      Ando Naoki、Soutome Hiroki、Yamaguchi Shigehiro
    • Journal Title

      Chemical Science

      Volume: 10 Pages: 7816-7821

    • DOI

      10.1039/c9sc02314c

    • Related Report
      2019 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Planarized B,N-phenylated dibenzoazaborine with a carbazole substructure: electronic impact of the structural constraint2019

    • Author(s)
      Ando Mikinori、Sakai Mika、Ando Naoki、Hirai Masato、Yamaguchi Shigehiro
    • Journal Title

      Organic & Biomolecular Chemistry

      Volume: 17 Pages: 5500-5504

    • DOI

      10.1039/c9ob00934e

    • Related Report
      2019 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Tuning the pi-bridge of quadrupolar triarylborane chromophores for one- and two-photon excited fluorescence imaging of lysosomes in live cells2019

    • Author(s)
      Griesbeck S., Michail E., Wang C., Ogasawara H., Lorenzen S., Gerstner L., Zang T., Nitsch J., Sato Y., Bertermann R., Taki M., Lambert C., Yamaguchi S., Marder T. B.
    • Journal Title

      Chem. Sci.

      Volume: 10 Pages: 5405-5422

    • DOI

      10.1039/c9sc00793h

    • Related Report
      2019 Annual Research Report 2018 Annual Research Report
    • Peer Reviewed / Open Access / Int'l Joint Research
  • [Journal Article] Structurally Constrained Boron-, Nitrogen-, Silicon-, and Phosphorus-Centered Polycyclic π-Conjugated Systems2019

    • Author(s)
      Hirai Masato、Tanaka Naoki、Sakai Mika、Yamaguchi Shigehiro
    • Journal Title

      Chem. Rev.

      Volume: -

    • DOI

      10.1021/acs.chemrev.8b00637

    • Related Report
      2018 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Optimization of Aqueous Stability versus pi-Conjugation in Tetracationic Bis(triarylborane) Chromophores : Applications in Live-Cell Fluorescence Imaging2019

    • Author(s)
      Griesbeck S., Ferger M., Czernetzi C., Wang C. G., Bertermann R., Friedrich A., Haehnel M., Sieh D., Taki M., Yamaguchi S., Marder T. B.
    • Journal Title

      Chem. Eur. J.

      Volume: 25 Pages: 7679-7688

    • DOI

      10.1002/chem.201900723

    • Related Report
      2018 Annual Research Report
    • Peer Reviewed / Int'l Joint Research
  • [Journal Article] Donor-π-Acceptor Type Unsymmetrical Triarylborane-Based Fluorophores: Synthesis, Fluorescence Properties, and Photostability2018

    • Author(s)
      Ito Masato、Ito Emi、Hirai Masato、Yamaguchi Shigehiro
    • Journal Title

      The Journal of Organic Chemistry

      Volume: 83 Pages: 8449-8456

    • DOI

      10.1021/acs.joc.8b01015

    • Related Report
      2018 Annual Research Report
    • Peer Reviewed
  • [Presentation] Main-group π-materials for organic electronics and bioimaging2020

    • Author(s)
      Shigehiro Yamaguchi
    • Organizer
      17th European Workshop on Phosphorus Chemistry
    • Related Report
      2019 Annual Research Report
    • Int'l Joint Research / Invited
  • [Presentation] Main-group π-materials for organic electronics and bioimaging2019

    • Author(s)
      Shigehiro Yamaguchi
    • Organizer
      2019 Russell Lecture, Queen’s University, Canada
    • Related Report
      2019 Annual Research Report
    • Int'l Joint Research / Invited
  • [Presentation] Main-Group Strategy toward Functional pi-Materials2019

    • Author(s)
      Shigehiro Yamaguchi
    • Organizer
      The 4th PKU-WuXi AppTec Symposium of Organic Chemistry
    • Related Report
      2019 Annual Research Report
    • Int'l Joint Research / Invited
  • [Presentation] Main-Group Approach toward Functional pi-Electon Materials2019

    • Author(s)
      Shigehiro Yamaguchi
    • Organizer
      8th SolTech Workshop
    • Related Report
      2019 Annual Research Report
    • Int'l Joint Research / Invited
  • [Presentation] Planarized Boron-Containing pi-Electron Materials2019

    • Author(s)
      Shigehiro Yamaguchi
    • Organizer
      The 2nd International Conference on Boron Chemistry (ICBC-2)
    • Related Report
      2019 Annual Research Report
    • Int'l Joint Research / Invited
  • [Presentation] Main Group Strategy toward Functional pi-Electron Materials2019

    • Author(s)
      Shigehiro Yamaguchi
    • Organizer
      The 6th EOC Symposium, Nankai University
    • Related Report
      2019 Annual Research Report
    • Int'l Joint Research / Invited
  • [Presentation] Main Group Strategy toward Functional pi-Electron Materials2019

    • Author(s)
      Shigehiro Yamaguchi
    • Organizer
      International C-H Functionalization Workshop, KAIST, Korea
    • Related Report
      2019 Annual Research Report
    • Int'l Joint Research / Invited
  • [Presentation] Main Group Strategy for Functional pi-Electron Materials2019

    • Author(s)
      Shigehiro Yamaguchi
    • Organizer
      NU-UoE JD and JSPS Core-to-Core Joint-Workshop
    • Related Report
      2019 Annual Research Report
    • Int'l Joint Research / Invited
  • [Presentation] Main Group-Containing pi-Electron Materials with Structural Constraint2019

    • Author(s)
      Shigehiro Yamaguchi
    • Organizer
      14th International Symposium on Functional π-Electron Systems
    • Related Report
      2019 Annual Research Report
    • Int'l Joint Research / Invited
  • [Presentation] ホウ素安定化発光性ラジカルの有機電界発光素子への応用2019

    • Author(s)
      伊藤正人,Xie Yongfa,安藤直紀,櫛田知克,白井秀典,早乙女広樹,田畑顕一,宮田康生,北弘志,山口茂弘
    • Organizer
      第46回有機典型元素化学討論会
    • Related Report
      2019 Annual Research Report
  • [Presentation] 平面固定フェニルジチエニルボランからなるπ電子系の合成と光物性2019

    • Author(s)
      坂井美佳,平井正人,森正義,安藤直紀,山口茂弘
    • Organizer
      第46回有機典型元素化学討論会
    • Related Report
      2019 Annual Research Report
  • [Presentation] 極性溶媒中で高効率発光を示すD-A-A型近赤外蛍光色素の開発2019

    • Author(s)
      杉原圭亮,Thomas Baumgartner,山口茂弘
    • Organizer
      第30回基礎有機化学討論会
    • Related Report
      2019 Annual Research Report
  • [Presentation] ベンジル位水素をもたないアリール基が置換したジチエニルボランの光反応2019

    • Author(s)
      鍛治田浩史,安藤直紀,山口茂弘
    • Organizer
      第30回基礎有機化学討論会
    • Related Report
      2019 Annual Research Report
  • [Presentation] ボラフルオレン骨格をもつ平面固定ホウ素π電子系の合成と物性2019

    • Author(s)
      安藤直紀,山口茂弘
    • Organizer
      第30回基礎有機化学討論会
    • Related Report
      2019 Annual Research Report
  • [Presentation] Emissive Radicals Stabilized by a Boron Atom at a Distant Position2019

    • Author(s)
      Masato Ito, Shunsuke Shirai, Yongfa Xie, Naoki Ando, Hiroki Soutome, Shigehiro Yamaguchi
    • Organizer
      The 18th International Symposium on Novel Aromatic Compounds (ISNA-18)
    • Related Report
      2019 Annual Research Report
    • Int'l Joint Research
  • [Presentation] CH/π Interaction-driven Self-assembly of Biphenylanthracene-based Amphiphiles in Aqueous Media2019

    • Author(s)
      Hiroki Narita, Tsuyoshi Nishikawa, Soichiro Ogi, Shigehiro Yamaguchi
    • Organizer
      18th International Symposium on Novel Aromatic Compounds (ISNA-18)
    • Related Report
      2019 Annual Research Report
    • Int'l Joint Research
  • [Presentation] The Structural Effects of the Red Fluorescent Radicals Stabilized by a Boron Atom at a Distant Position2019

    • Author(s)
      Masato Ito, Shunsuke Shirai, Yongfa Xie, Naoki Ando, Hiroki Soutome, Shigehiro Yamaguchi
    • Organizer
      ITbM-GTR Pre-ISNA Symposium “Toward Advanced Functions form New pi-Skeletons”
    • Related Report
      2019 Annual Research Report
    • Int'l Joint Research
  • [Presentation] Synthesis, Derivatization and Photophysical Properties of Planarized Phenyldithienylborane2019

    • Author(s)
      Mika Sakai, Masato Hirai, Masayoshi Mori, Naoki Ando, Shigehiro Yamaguchi
    • Organizer
      ITbM-GTR Pre-ISNA Symposium "Toward Advanced Functions form New pi-Skeletons"
    • Related Report
      2019 Annual Research Report
    • Int'l Joint Research
  • [Presentation] Photoreaction of Dithienylborane Stabilized by Bis(trimethylsilyl)phenyl Group2019

    • Author(s)
      Hirofumi Kajita, Naoki Ando, and Shigehiro Yamaguchi
    • Organizer
      ITbM-GTR Pre-ISNA Symposium "Toward Advanced Functions form New pi-Skeletons"
    • Related Report
      2019 Annual Research Report
    • Int'l Joint Research
  • [Presentation] Synthesis and Properties of Planarized B, N-Embedded Polycyclic Compounds with a Carbazole Substructure2019

    • Author(s)
      Mika Sakai, Mikinori Ando, Masato Hirai, Shigehiro Yamaguchi
    • Organizer
      14th International Symposium on Functional π-Electron Systems
    • Related Report
      2019 Annual Research Report
    • Int'l Joint Research
  • [Presentation] Phosphorus-Containing Fluorophores for Bioimaging2018

    • Author(s)
      Shigehiro Yamaguchi
    • Organizer
      ACS National Meeting
    • Related Report
      2018 Annual Research Report
    • Int'l Joint Research / Invited
  • [Presentation] Photostable and Near IR Phosphorus Fluorophores for Bioimaging2018

    • Author(s)
      Shigehiro Yamaguchi
    • Organizer
      22nd International Conference on Phosphorus Chemistry
    • Related Report
      2018 Annual Research Report
    • Int'l Joint Research / Invited
  • [Presentation] Planarized Boron-Containing pi-Electron Materials2018

    • Author(s)
      Shigehiro Yamaguchi
    • Organizer
      BORAM XVI
    • Related Report
      2018 Annual Research Report
    • Int'l Joint Research / Invited
  • [Presentation] Main-Group Strategy for NIR and Photostable Fluorescent Dyes2018

    • Author(s)
      Shigehiro Yamaguchi
    • Organizer
      The Chinese University of Hong Kong
    • Related Report
      2018 Annual Research Report
    • Invited
  • [Presentation] Main-Group Strategy for New pi-Electron Materials2018

    • Author(s)
      Shigehiro Yamaguchi
    • Organizer
      GRC Hybrid Electronic and Photonic Materials and Phenomena
    • Related Report
      2018 Annual Research Report
    • Int'l Joint Research / Invited
  • [Presentation] Main-Group Strategy toward NIR and Photostable Fluorescent Dyes for Bioimaging2018

    • Author(s)
      Shigehiro Yamaguchi
    • Organizer
      Burgenstock Conference 2018
    • Related Report
      2018 Annual Research Report
    • Int'l Joint Research / Invited

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Published: 2018-06-12   Modified: 2022-12-28  

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