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Development of organic mechanochromic materials with room-temperature phosphorescence utilizing chalcogen bonding

Research Project

Project/Area Number 19K15542
Research Category

Grant-in-Aid for Early-Career Scientists

Allocation TypeMulti-year Fund
Review Section Basic Section 33010:Structural organic chemistry and physical organic chemistry-related
Research InstitutionOsaka University

Principal Investigator

Tani Yosuke  大阪大学, 理学研究科, 助教 (00769383)

Project Period (FY) 2019-04-01 – 2021-03-31
Project Status Completed (Fiscal Year 2020)
Budget Amount *help
¥4,290,000 (Direct Cost: ¥3,300,000、Indirect Cost: ¥990,000)
Fiscal Year 2020: ¥1,950,000 (Direct Cost: ¥1,500,000、Indirect Cost: ¥450,000)
Fiscal Year 2019: ¥2,340,000 (Direct Cost: ¥1,800,000、Indirect Cost: ¥540,000)
Keywords室温りん光 / 刺激応答発光 / アモルファス / メカノクロミズム / カルコゲン結合 / 有機結晶 / りん光 / 刺激応答性 / 同形結晶 / 非対称化
Outline of Research at the Start

こする、ひっかくなどの弱い機械刺激によって発光色が変化する現象を、発光性メカノクロミズム(MCL)と呼ぶ。この現象は、目に見える物質に与えた力が目に見えない分子の性質を変える様子を、発光を通して観察することができる。本研究では、特徴的な発光現象である「りん光」を示すMCL材料を開発し、その分子の構造と発光特性の関係を明らかにすることで、分子レベルから材料設計指針を見出すことを目的とする。同時に、りん光を利用した様々な新材料、例えばこすると光るインクや生体中の圧力を可視化するセンサーなどの開発が期待される。

Outline of Final Research Achievements

Luminescent mechanochromism is the phenomenon in which weak mechanical stimuli such as rubbing or scratching change the luminescence properties. In this study, we have found a thienyl diketone derivative which exhibits the first room temperature phosphorescent mechanochromism as organic molecules. In addition, two derivatives were synthesized by desymmetrizing the C2-symmetric diketone and characterized in detail. As a result, we succeeded in developing (i) the first mechanoresponsive turn-on phosphorescent molecule and (ii) a liquid chromophore that exhibits phosphorescence at room temperature.
Thus, we herein developed a novel phosphorescent functional molecular skeleton, and provided interesting insights into the symmetry of molecules and the properties of aggregated systems.

Academic Significance and Societal Importance of the Research Achievements

身の回りのほとんどの材料は、結晶ではなく非晶質材料である。しかし、結晶と異なり構造解析の困難な非晶質材料の設計・開発は容易でなく、メカノクロミズムや有機りん光材料においても、非晶質状態の物性制御は挑戦的課題である。本研究では特に非結晶相におけるチエニルジケトンのりん光について多くの知見を得ることができ、アモルファス固体および液体において室温りん光を示す特徴的な(あるいは世界初の)機能性分子を開発することに成功した。配座的に柔軟な骨格が優れたりん光機能を示すという本研究の結果は従来の直感に反するものであり、今後の材料開発における分子設計に大きく影響を与えるものと期待される。

Report

(3 results)
  • 2020 Annual Research Report   Final Research Report ( PDF )
  • 2019 Research-status Report
  • Research Products

    (30 results)

All 2021 2020 2019 Other

All Journal Article (6 results) (of which Peer Reviewed: 5 results,  Open Access: 1 results) Presentation (23 results) (of which Int'l Joint Research: 3 results,  Invited: 2 results) Remarks (1 results)

  • [Journal Article] Structure-property relationship in contrasting aggregation-induced enhancement/quenching of emission in rigid aromatic molecules2021

    • Author(s)
      Tani Yosuke、Ogawa Takuji
    • Journal Title

      Journal of Materials Chemistry C

      Volume: 9 Issue: 12 Pages: 4281-4288

    • DOI

      10.1039/d0tc06083f

    • Related Report
      2020 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Room-Temperature Phosphorescence of a Supercooled Liquid: Kinetic Stabilization by Desymmetrization2021

    • Author(s)
      Komura Mao, Ogawa Takuji, Tani Yosuke
    • Journal Title

      ChemRxiv

      Volume: -

    • DOI

      10.26434/chemrxiv.14527002

    • Related Report
      2020 Annual Research Report
    • Open Access
  • [Journal Article] Mechanoresponsive turn-on phosphorescence by a desymmetrization approach2020

    • Author(s)
      Tani Yosuke、Komura Mao、Ogawa Takuji
    • Journal Title

      Chemical Communications

      Volume: 56 Issue: 50 Pages: 6810-6813

    • DOI

      10.1039/d0cc01949f

    • Related Report
      2020 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Single-Molecular Bridging in Static Metal Nanogap Electrodes Using Migrations of Metal Atoms2020

    • Author(s)
      Naitoh Yasuhisa、Tani Yosuke、Koyama Emiko、Nakamura Tohru、Sumiya Touru、Ogawa Takuji、Misawa Guento、Shima Hisashi、Sugawara Kota、Suga Hiroshi、Akinaga Hiroyuki
    • Journal Title

      The Journal of Physical Chemistry C

      Volume: 124 Issue: 25 Pages: 14007-14015

    • DOI

      10.1021/acs.jpcc.0c02109

    • NAID

      130007959457

    • Related Report
      2020 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Structure determination and negative differential resistance of tetraarylporphyrin/polyoxometalate 2?:?1 complexes2020

    • Author(s)
      Yamazaki Yoshito、Yamashita Ken-ichi、Tani Yosuke、Aoyama Tomoya、Ogawa Takuji
    • Journal Title

      Journal of Materials Chemistry C

      Volume: 8 Issue: 41 Pages: 14423-14430

    • DOI

      10.1039/d0tc04052e

    • Related Report
      2020 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Room-temperature phosphorescence-to-phosphorescence mechanochromism of a metal-free organic 1,2-diketone2019

    • Author(s)
      Tani Yosuke、Terasaki Morihisa、Komura Mao、Ogawa Takuji
    • Journal Title

      Journal of Materials Chemistry C

      Volume: 7 Issue: 38 Pages: 11926-11931

    • DOI

      10.1039/c9tc04176a

    • Related Report
      2019 Research-status Report
    • Peer Reviewed
  • [Presentation] Unexpected dynamic rectification behavior in single-molecule junction of symmetrical stilbenes2021

    • Author(s)
      〇Yosuke Tani, Hiroki Taniguchi, Takanori Morikawa, Makusu Tsutsui, Masateru Taniguchi, Takuji Ogawa
    • Organizer
      Joint Symposium of JSPS-DST Bilateral Research Project "Charge- and Spin-Blockade in Ultrathin-Layers of Single Molecule Magnets"
    • Related Report
      2020 Annual Research Report
    • Int'l Joint Research
  • [Presentation] Synthesis and Single Molecule Conductance Measurement of NHeterocyclic Carbene Metal Complexes2021

    • Author(s)
      ○Yosephin Dewiani Rahmayanti, Yosuke Tani, Zhijin Chen, Tatsuhiko Ohto, Ryo Yamada, Hirokazu Tada, Takuji Ogawa
    • Organizer
      Joint Symposium of JSPS-DST Bilateral Research Project "Charge- and Spin-Blockade in Ultrathin-Layers of Single Molecule Magnets"
    • Related Report
      2020 Annual Research Report
    • Int'l Joint Research / Invited
  • [Presentation] 熱および機械刺激応答型ターンオンりん光を示すチエニルジケトン結晶2021

    • Author(s)
      〇谷洋介、小川琢治
    • Organizer
      日本化学会第101春季年会
    • Related Report
      2020 Annual Research Report
  • [Presentation] 無溶媒液体状態におけるヘテロ芳香族ジケトンの室温りん光とりん光サーモクロミズム2021

    • Author(s)
      〇小村真央、谷洋介、小川琢治
    • Organizer
      日本化学会第101春季年会
    • Related Report
      2020 Annual Research Report
  • [Presentation] 脱離基を利用した単分子架橋形成の促進及び抑制2020

    • Author(s)
      ○島崎 周磨,谷 洋介,Zhijin Chen,山田 亮,夛田 博一,小川 琢治
    • Organizer
      第11回分子アーキテクトニクス研究会
    • Related Report
      2020 Annual Research Report
  • [Presentation] Metal-dependent Conductance of N-Heterocyclic Carbene Complexes in Single-Molecule Junctions2020

    • Author(s)
      ○Yosephin Dewiani Rahmayanti, Yosuke Tani, Zhijin Chen, Ryo Yamada, Hirokazu Tada, Takuji Ogawa
    • Organizer
      第11回分子アーキテクトニクス研究会
    • Related Report
      2020 Annual Research Report
  • [Presentation] チエニルジケトン誘導体をドープしたポリマーフィルムが示す室温大気下での高効率なりん光2020

    • Author(s)
      ○王瑛梨樺、谷洋介、小川琢治
    • Organizer
      2020年Web光化学討論会
    • Related Report
      2020 Annual Research Report
  • [Presentation] 無溶媒液体状態で室温りん光を示すチエニルジケトン誘導体2020

    • Author(s)
      ○大島祐也、谷洋介、小川琢治
    • Organizer
      2020年Web光化学討論会
    • Related Report
      2020 Annual Research Report
  • [Presentation] 機械刺激応答性 Turn-on りん光:非対称化を鍵とする分子振動の積極利用2020

    • Author(s)
      〇谷洋介、小村真央、小川琢治
    • Organizer
      2020年Web光化学討論会
    • Related Report
      2020 Annual Research Report
  • [Presentation] 機械刺激応答性Turn-Onりん光における分子間相互作用の影響2020

    • Author(s)
      〇谷洋介、小村真央、寺崎守永、小川琢治
    • Organizer
      基礎有機化学会 若手オンラインシンポジウム
    • Related Report
      2020 Annual Research Report
  • [Presentation] 柔軟な有機分子の室温りん光と配座変化に基づく機械刺激応答機能2020

    • Author(s)
      ○谷洋介
    • Organizer
      第11回 "光"機到来!Qコロキウム
    • Related Report
      2020 Annual Research Report
    • Invited
  • [Presentation] ポリオキソメタレート/金属ポルフィリン錯体の合成と単分子電気伝導度測定2020

    • Author(s)
      青山 智哉、小川 琢治、谷 洋介
    • Organizer
      日本化学会第100春季年会
    • Related Report
      2019 Research-status Report
  • [Presentation] Mechanoresponsive Turn-On of Organic Room-Temperature Phosphorescence2020

    • Author(s)
      Yosuke Tani, Mao Komura, Takuji Ogawa
    • Organizer
      日本化学会第100春季年会
    • Related Report
      2019 Research-status Report
  • [Presentation] Single molecule conductance measurement of anthrone under acidic condition2020

    • Author(s)
      Yuki Miyoshi, Yosuke Tani, Makusu Tsutsui, Masateru Taniguti, Takuji Ogawa
    • Organizer
      The 67th JSAP Spring Meeting 2020
    • Related Report
      2019 Research-status Report
  • [Presentation] Large Stochastic Binary Fluctuation of Single Molecule Conductance of POM dithiols2020

    • Author(s)
      Nunik Nurhayati, Zhijin Chen, Yosuke Tani, Ken-ichi Yamashita, Takuji Ogawa
    • Organizer
      The 67th JSAP Spring Meeting 2020
    • Related Report
      2019 Research-status Report
  • [Presentation] Study toward controllable random signal generation based on chemical reactions2019

    • Author(s)
      Yosuke Tani, Takuji Ogawa
    • Organizer
      International Symposium for Neuromorphic Hardware Research
    • Related Report
      2019 Research-status Report
    • Int'l Joint Research
  • [Presentation] 室温りん光メカノクロミズムを示す1,2-ジケトンの非対称化と物性制御2019

    • Author(s)
      谷 洋介、小村真央、小川琢治
    • Organizer
      第28回有機結晶シンポジウム
    • Related Report
      2019 Research-status Report
  • [Presentation] イミダゾール誘導体における量子干渉効果の観測2019

    • Author(s)
      辻田 貴大 , 谷 洋介 , Zhijin Chen , 山田 亮 , 夛田 博一 , 小川 琢治
    • Organizer
      第10回分子アーキテクトニクス研究会
    • Related Report
      2019 Research-status Report
  • [Presentation] チエニルジケトン誘導体の室温りん光メカノクロミズム2019

    • Author(s)
      谷 洋介、寺崎守永、小村真央、小川琢治
    • Organizer
      第30回基礎有機化学討論会
    • Related Report
      2019 Research-status Report
  • [Presentation] ブリンク法を用いた直交型ポルフィリン・イミドの単分子整流特性測定 と機械学習によるデータ解析2019

    • Author(s)
      Chen Zhijin, Albert C. Aragones, Ismael Diez-Perez, 谷 洋介, 山下 健一, 山田 亮, 夛田 博一, 小川 琢治
    • Organizer
      応用物理学会秋季学術講演会2019
    • Related Report
      2019 Research-status Report
  • [Presentation] Effect of desymmetrization on the room-temperature phosphorescence of 1,2-diketone derivatives2019

    • Author(s)
      小村真央, 谷 洋介, 小川 琢治
    • Organizer
      2019年光化学討論会
    • Related Report
      2019 Research-status Report
  • [Presentation] ジ(2-チエニル)ジケトン誘導体のりん光メカノクロミズム2019

    • Author(s)
      小村真央, 谷 洋介, 小川 琢治
    • Organizer
      第40回光化学若手の会
    • Related Report
      2019 Research-status Report
  • [Presentation] 金属を含まない有機分子のりん光メカノクロミズム2019

    • Author(s)
      谷 洋介
    • Organizer
      触媒有機化学セミナー
    • Related Report
      2019 Research-status Report
  • [Remarks]

    • URL

      http://www.chem.sci.osaka-u.ac.jp/lab/ogawa/

    • Related Report
      2019 Research-status Report

URL: 

Published: 2019-04-18   Modified: 2022-01-27  

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