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Development of stimulus-responsive optically active quaternary silanes: Investigation of circularly polarized phosphorescence properties and application to thin film materials

Research Project

Project/Area Number 19K05627
Research Category

Grant-in-Aid for Scientific Research (C)

Allocation TypeMulti-year Fund
Section一般
Review Section Basic Section 35030:Organic functional materials-related
Research InstitutionThe University of Tokyo

Principal Investigator

Yamanoi Yoshinori  東京大学, 大学院理学系研究科(理学部), 准教授 (20342636)

Project Period (FY) 2019-04-01 – 2023-03-31
Project Status Completed (Fiscal Year 2022)
Budget Amount *help
¥4,290,000 (Direct Cost: ¥3,300,000、Indirect Cost: ¥990,000)
Fiscal Year 2021: ¥1,040,000 (Direct Cost: ¥800,000、Indirect Cost: ¥240,000)
Fiscal Year 2020: ¥1,300,000 (Direct Cost: ¥1,000,000、Indirect Cost: ¥300,000)
Fiscal Year 2019: ¥1,950,000 (Direct Cost: ¥1,500,000、Indirect Cost: ¥450,000)
Keywordsジシラン結合 / 外部刺激応答性 / 円偏光発光 / 環状化合物 / CPL / 外部刺激 / 発光 / 白金錯体 / 不斉ケイ素原子 / 燐光
Outline of Research at the Start

本研究では燐光を発する官能基(具体的には白金錯体)を芳香環側鎖に導入した光学活性芳香族4級シランを合成することで強輝度のCPL材料を開発する。これらは固体状態や薄膜状態における金属-金属間の分子間相互作用の強度が外部環境によって変化すると予測されるので、外部刺激応答性CPL材料への展開が可能である。微弱な圧力変化、温度変化など外部刺激でCPL特性が変化する分子を開発し、内視鏡へ導入すれば3次元映像手術に展開できるので医療分野へも貢献できる。本研究が成功すると単純分子から手軽に高性能3次元映像を作り出すことができ、その波及効果は大きい。

Outline of Final Research Achievements

Most of the research reports on circularly polarized light-emitting compounds have so far been made in aggregated states such as atropisomers and π-conjugated polymers, and examples showing good results in the monomolecular state are not well known. On the other hand, many organosilicon compounds having π-conjugated substituents exhibit good light-emitting properties. If a π-conjugated substituent is attached to an asymmetric silicon atom, a chiral conjugated system can be constructed via the asymmetric silicon atom. I can expect it. In this application, we synthesized an optically active silicon compound that has both good fluorescence quantum yield and circularly polarized luminescence properties in a monomolecular state, based on a new method for constructing asymmetric silicon atoms.

Academic Significance and Societal Importance of the Research Achievements

(1) ランタノイド錯体やアトロプ異性体は多工程合成経路であるのに対し、本研究における合成方法は単工程反応である。 (2) 反応で使用する基質が容易に入手できる。本研究における触媒的不斉カップリング反応では配位子の不斉源が安価な酒石酸由来であり、どちらの光学活性体も入手可能であるので、(R)体、(S)体両方の不斉ケイ素原子を構築できる。 (3)従来の円偏光発光材料では高蛍光量子収率、もしくは高円偏光発光特性のどちらかしか満たすことができなかった。本研究における化合物群は他グループの研究と比較し蛍光量子収率、円偏光発光特性のどちらも高い値を示すと期待できる。

Report

(5 results)
  • 2022 Annual Research Report   Final Research Report ( PDF )
  • 2021 Research-status Report
  • 2020 Research-status Report
  • 2019 Research-status Report
  • Research Products

    (25 results)

All 2023 2022 2021 2020 2019 Other

All Journal Article (14 results) (of which Int'l Joint Research: 3 results,  Peer Reviewed: 13 results,  Open Access: 7 results) Presentation (8 results) (of which Int'l Joint Research: 1 results,  Invited: 6 results) Remarks (3 results)

  • [Journal Article] “15N CP/MAS NMR as a Tool for the Mechanistic Study of Mechanical Stimuli-Responsive Materials: Evidence for the Conformational Change of an Emissive Dimethylacridane Derivative”,2023

    • Author(s)
      Nakae, T.; Hattori, M.*; Yamanoi, Y.*
    • Journal Title

      ACS Omega

      Volume: 8 Issue: 14 Pages: 12922-12927

    • DOI

      10.1021/acsomega.3c00099

    • Related Report
      2022 Annual Research Report
    • Peer Reviewed / Open Access
  • [Journal Article] Reversible Transition between Discrete and 1D Infinite Architectures: a Temperature-Responsive Cu(I) Complex with a Flexible Disilane-bridged Bis(pyridine) Ligand2023

    • Author(s)
      Zhao, Y.; Nakae, T.; Takeya, S.; Hattori, M.; Saito, D.; Kato, M.; Ohmasa, Y.; Sato, S.; Yamamuro, O.; Galica, T.; Nishibori, E.; Kobayashi, S.; Seki, T.; Yamada, T.; Yamanoi, Y.*
    • Journal Title

      Chem. Eur. J.

      Volume: 29 Issue: 38

    • DOI

      10.1002/chem.202204002

    • Related Report
      2022 Annual Research Report
    • Peer Reviewed / Open Access / Int'l Joint Research
  • [Journal Article] Thermosalient phenomena in molecular crystals: A case study of representative molecules2023

    • Author(s)
      Yamanoi, Y.; Omoto, K.; Nakae, T.; Nishio, M.
    • Journal Title

      “Soft Crystals: Flexible Response Systems with High Structural Order”, Kato, M., Ishii, K. Eds. Springer, Singapore,

      Volume: 2023 Pages: 131-153

    • Related Report
      2022 Annual Research Report
    • Peer Reviewed / Open Access
  • [Journal Article] Luminescent Behavior Elucidation of a Disilane‐Bridged D?A?D Triad Composed of Phenothiazine and Thienopyrazine2021

    • Author(s)
      Nakae Toyotaka、Nishio Masaki、Usuki Tsukasa、Ikeya Minako、Nishimoto Chika、Ito Suguru、Nishihara Hiroshi、Hattori Mineyuki、Hayashi Shigenobu、Yamada Teppei、Yamanoi Yoshinori
    • Journal Title

      Angewandte Chemie International Edition

      Volume: 60 Issue: 42 Pages: 22871-22878

    • DOI

      10.1002/anie.202108089

    • Related Report
      2021 Research-status Report
    • Peer Reviewed
  • [Journal Article] Synthesis, Structure, and Photophysical Properties of Yellow-Green and Blue Photoluminescent Dinuclear and Octanuclear Copper(I) Iodide Complexes with a Disilanylene-Bridged Bispyridine Ligand2021

    • Author(s)
      Nakae Toyotaka、Miyabe Hiroto、Nishio Masaki、Yamada Teppei、Yamanoi Yoshinori
    • Journal Title

      Molecules

      Volume: 26 Issue: 22 Pages: 6852-6852

    • DOI

      10.3390/molecules26226852

    • Related Report
      2021 Research-status Report
    • Peer Reviewed / Open Access
  • [Journal Article] Thermosalience in macrocycle-based soft crystals via anisotropic deformation of disilanyl architecture2020

    • Author(s)
      Omoto, K.; Nakae, T.; Nishio, M.; Yamanoi, Y.;* Kasai, H.; Nishibori, E.; Mashimo, T.; Seki, T.; Ito, H.; Nakamura, K.; Kobayashi, N.; Nishihara, H.*
    • Journal Title

      J. Am. Chem. Soc.

      Volume: 142 Issue: 29 Pages: 12651-12657

    • DOI

      10.1021/jacs.0c03643

    • Related Report
      2020 Research-status Report
    • Peer Reviewed / Open Access
  • [Journal Article] Selective Formation and SHG Intensity of Noncentrosymmetric and Centrosymmetric 1,1,2,2-Tetramethyl-1-(4-(N,N-dimethylamino)phenyl)-2-(2′-cyanophenyl)disilane Crystals under External Stimuli2020

    • Author(s)
      Nishio Masaki、Shimada Masaki、Omoto Kenichiro、Nakae Toyotaka、Maeda Hiroaki、Miyachi Mariko、Yamanoi Yoshinori、Nishibori Eiji、Nakayama Naofumi、Goto Hitoshi、Matsushita Tomonori、Kondo Takashi、Hattori Mineyuki、Jimura Keiko、Hayashi Shigenobu、Nishihara Hiroshi
    • Journal Title

      The Journal of Physical Chemistry C

      Volume: 124 Issue: 32 Pages: 17450-17458

    • DOI

      10.1021/acs.jpcc.0c03139

    • Related Report
      2020 Research-status Report
    • Peer Reviewed / Open Access
  • [Journal Article] Photoelectric Conversion System Composed of Gene-Recombined Photosystem I and Platinum Nanoparticle Nanosheet2020

    • Author(s)
      Zhu Wenchao、Salles Raphal、Miyachi Mariko、Yamanoi Yoshinori、Tomo Tatsuya、Takahashi Hiromi、Nishihara Hiroshi
    • Journal Title

      Langmuir

      Volume: 36 Issue: 23 Pages: 6429-6435

    • DOI

      10.1021/acs.langmuir.0c00647

    • Related Report
      2020 Research-status Report
    • Peer Reviewed / Int'l Joint Research
  • [Journal Article] Effect of Tris(trimethylsilyl)silyl Group on the Fluorescence and Triplet Yields of Oligothiophenes2020

    • Author(s)
      Hirata, S.;* Nishio, M.; Uchida, H.; Usuki, T.; Nakae, T.; Miyachi, M.; Yamanoi, Y.;* Nishihara, H.*
    • Journal Title

      J. Phys. Chem. C

      Volume: 124 Issue: 5 Pages: 3277-3286

    • DOI

      10.1021/acs.jpcc.9b10718

    • Related Report
      2020 Research-status Report 2019 Research-status Report
    • Peer Reviewed
  • [Journal Article] Enhancement of Photofunction of Phosphorescent Pt(II) Cyclometalated Complexes Driven by Substituents: Solid-state Luminescence and Circularly Polarized Luminescence2019

    • Author(s)
      Usuki, T.; Uchida, H.; Omoto, K.; Yamanoi, Y.;* Yamada, A.; Iwamura, M.; Nozaki, K.; Nishihara, H.*
    • Journal Title

      J. Org. Chem.

      Volume: 84 Issue: 17 Pages: 10749-10756

    • DOI

      10.1021/acs.joc.9b01285

    • Related Report
      2019 Research-status Report
    • Peer Reviewed
  • [Journal Article] Photosensing system using photosystem I and gold nanoparticle on graphene field-effect transistor2019

    • Author(s)
      Nishiori, D.; Zhu, W.; Salles, R.; Miyachi, M.;* Yamanoi, Y.;* Ikuta, T.; Maehashi, K.; Tomo, T.; Nishihara, H.*
    • Journal Title

      ACS Appl. Mater. Inter.

      Volume: 11 Issue: 45 Pages: 42773-42779

    • DOI

      10.1021/acsami.9b14771

    • Related Report
      2019 Research-status Report
    • Peer Reviewed / Int'l Joint Research
  • [Journal Article] Effects of Substituents on the Blue Luminescence of Disilane-Linked Donor-Acceptor-Donor Triads2019

    • Author(s)
      Usuki Tsukasa、Omoto Kenichiro、Shimada Masaki、Yamanoi Yoshinori、Kasai Hidetaka、Nishibori Eiji、Nishihara Hiroshi
    • Journal Title

      Molecules

      Volume: 24 Issue: 3 Pages: 521-521

    • DOI

      10.3390/molecules24030521

    • NAID

      120007128246

    • Related Report
      2019 Research-status Report
    • Peer Reviewed / Open Access
  • [Journal Article] Dioxacyclophanes as a Scaffold for Silicon-based Circularly Polarized Luminescent Materials2019

    • Author(s)
      Yamanoi, Y.;* Usuki, T.; Omoto, K.; Shimada, M.; Koike, H.; Iwamura, M.; Nozaki, K.; Saito, D.;
    • Journal Title

      Tetrahedron Lett.

      Volume: 60 Issue: 16 Pages: 1108-1112

    • DOI

      10.1016/j.tetlet.2019.03.033

    • Related Report
      2019 Research-status Report
    • Peer Reviewed
  • [Journal Article] 芳香族ケイ素化合物の新規合成プロセスの開拓と固体光物性2019

    • Author(s)
      山野井 慶徳
    • Journal Title

      化学工業

      Volume: 4 Pages: 12-18

    • Related Report
      2019 Research-status Report
  • [Presentation] ジシラン架橋 ドナー(D)アクセプター(A)ドナー(D)分子のメカノクロミック発光に関する研究2022

    • Author(s)
      山野井 慶徳
    • Organizer
      新学術領域研究「ソフトクリスタル」 第8回公開シンポジウム
    • Related Report
      2021 Research-status Report
    • Invited
  • [Presentation] 外部刺激で光物性が変化する直鎖状芳香族ジシラン分子の開発2021

    • Author(s)
      山野井 慶徳
    • Organizer
      ケイ素化学協会 オンライン講演会
    • Related Report
      2021 Research-status Report
    • Invited
  • [Presentation] Effects of Substituents on the Luminescence of disilane-linked donor/acceptor/donor triads2021

    • Author(s)
      Yamanoi, Y.
    • Organizer
      The 3rd International Symposium on Soft Crystals (the 3rd ISSC) joint with the 4th International Symposium on Photofunctional Chemistry of Complex Systems (ISPCCS 2021)
    • Related Report
      2021 Research-status Report
    • Int'l Joint Research / Invited
  • [Presentation] Thermosalience in macrocycle-based soft crystals via anisotropic deformation of disilanyl architecture2021

    • Author(s)
      Yamanoi, Y.
    • Organizer
      The Electrochemical Society 235th ECS Meeting
    • Related Report
      2021 Research-status Report
  • [Presentation] 山野井 慶徳2021

    • Author(s)
      外部刺激で光物性が変化する直鎖状芳香族ジシラン分子の開発
    • Organizer
      新学術領域研究「ソフトクリスタル」 第7回公開シンポジウム
    • Related Report
      2020 Research-status Report
  • [Presentation] 「ジシラン結合の柔軟性に基づくソフトクリスタル」2020

    • Author(s)
      山野井 慶徳
    • Organizer
      新学術領域研究「ソフトクリスタル」 第5回公開シンポジウム
    • Related Report
      2019 Research-status Report
    • Invited
  • [Presentation] 「シアノバクテリアの光化学系Iを活用した電極の作製と物性評価」2020

    • Author(s)
      山野井 慶徳
    • Organizer
      日本板硝子材料工学助成会 第37回無機材料に関する最近の研究成果発表会-材料研究に新しい風を-
    • Related Report
      2019 Research-status Report
    • Invited
  • [Presentation] 「ケイ素を含む機能性有機結晶」2019

    • Author(s)
      山野井 慶徳
    • Organizer
      柏崎高校SSH高大連携プログラム
    • Related Report
      2019 Research-status Report
    • Invited
  • [Remarks]

    • URL

      http://www.chem.s.u-tokyo.ac.jp/users/inorg/index.html

    • Related Report
      2020 Research-status Report
  • [Remarks] 東京大学 大学院理学系研究科 化学専攻 無機化学研究室

    • URL

      http://www.chem.s.u-tokyo.ac.jp/users/inorg/index.html

    • Related Report
      2019 Research-status Report
  • [Remarks] 新学術領域研究「ソフトクリスタル」

    • URL

      https://www.softcrystal.org/

    • Related Report
      2019 Research-status Report

URL: 

Published: 2019-04-18   Modified: 2024-01-30  

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