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Development of space- and time-resolved absorption spectra of organic radical ions

Research Project

Project/Area Number 18K05176
Research Category

Grant-in-Aid for Scientific Research (C)

Allocation TypeMulti-year Fund
Section一般
Review Section Basic Section 34020:Analytical chemistry-related
Research InstitutionKyushu University

Principal Investigator

ISHIMATSU Ryoichi  九州大学, 工学研究院, 助教 (90512781)

Co-Investigator(Kenkyū-buntansha) 水野 潤  早稲田大学, ナノ・ライフ創新研究機構, 上級研究員(研究院教授) (60386737)
Project Period (FY) 2018-04-01 – 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: ¥650,000 (Direct Cost: ¥500,000、Indirect Cost: ¥150,000)
Fiscal Year 2019: ¥650,000 (Direct Cost: ¥500,000、Indirect Cost: ¥150,000)
Fiscal Year 2018: ¥2,990,000 (Direct Cost: ¥2,300,000、Indirect Cost: ¥690,000)
Keywordsラジカルイオン / 分光電気化学 / 分子間ダイマー / 電気化学発光 / エキシマー / 速度論 / イオン対 / ラジカルアニオン / 電子移動速度 / 共反応体 / マーカス理論 / 電気化学 / 寿命 / 高速検出
Outline of Final Research Achievements

A spectroelectrochemical measurement system using a conventional three-electrode system was developed. This system was used for the radical anion of pyrene, and it was found that the radical anion forms an intermolecular dimer. Furthermore, when the measurement system was applied to measure time-resolved electrogenerated chemiluminescence (ECL) for pyrene and its derivative, it was found the first that the emission originated from monomer pyrene was observed in the early stage of the emission caused by the ion annihilation between the radical cation and anion. From the result and the kinetics based on the Marcus model, we proposed the mechanism of excimer ECL. We also revealed the mechanism to enhance the ECL efficiency for near-infrared luminescent molecules.

Academic Significance and Societal Importance of the Research Achievements

ラジカルイオン種は様々な反応に関与し、それらを検出することや、その反応性を理解することは非常に重要である。本研究によって、分光電気化学的にラジカルイオン種の光吸収スペクトルを非常に迅速かつ簡便に測定可能な系を構築した。これを使い、ピレンのアニオンが分子間ダイマーを形成することを初めて見出した。さらに、開発した系の高い時間分解能を利用し、これまでほとんどわかっていなかった電気化学発光におけるラジカルの安定性が発光に及ぼす影響について、ピレンやその誘導体を用いて解析を行った。また、近赤外電気化学発光の効率を増加させることが可能な新たな原理を見出した。

Report

(4 results)
  • 2020 Annual Research Report   Final Research Report ( PDF )
  • 2019 Research-status Report
  • 2018 Research-status Report
  • Research Products

    (16 results)

All 2020 2019 2018 Other

All Journal Article (4 results) (of which Peer Reviewed: 3 results) Presentation (11 results) (of which Int'l Joint Research: 2 results,  Invited: 2 results) Remarks (1 results)

  • [Journal Article] Efficient Electrogenerated Chemiluminescence of Pyrrolopyrrole Aza-BODIPYs in the Near-Infrared Region with Tripropylamine: Involving Formation of S2 and T2 StatesEfficient Electrogenerated Chemiluminescence of Pyrrolopyrrole Aza-BODIPYs in the Near-Infrared Region with Tripropylamine: Involving Formation of S2 and T2 States2019

    • Author(s)
      R. Ishimatsu, H. Shintaku, Y. Kage, M. Misaki, S. Shimizu, K. Nakano, H. Furuta, T. Imato
    • Journal Title

      J. Am. Chem. Soc.

      Volume: 141 Issue: 30 Pages: 11791-11795

    • DOI

      10.1021/jacs.9b05245

    • Related Report
      2019 Research-status Report
    • Peer Reviewed
  • [Journal Article] Kinetics of Excimer Electrogenerated Chemiluminescence of Pyrene and 1-Pyrenebutyricacid 2-Ethylhexylester in Acetonitrile and an Ionic Liquid, Triethylpentylphosphonium Bis(trifluoromethanesulfonyl)imide2019

    • Author(s)
      R. Ishimatsu, S. Tashiro, T. Kasahara, J. Oshima, J. Mizuno, K. Nakano, C. Adachi, T. Imato
    • Journal Title

      J. Phys. Chem. B

      Volume: 123 Issue: 50 Pages: 10825-10836

    • DOI

      10.1021/acs.jpcb.9b08813

    • Related Report
      2019 Research-status Report
    • Peer Reviewed
  • [Journal Article] Electrogenerated Chemiluminescence and Electronic States of Several Organometallic Eu(III) and Tb(III) Complexes: Effects of the Ligands2019

    • Author(s)
      R. Ishimatsu, E. Kunisawa, K. Nakano, C. Adachi, T. Imato
    • Journal Title

      ChemistrySelect

      Volume: 4 Issue: 9 Pages: 2815-2831

    • DOI

      10.1002/slct.201900595

    • Related Report
      2018 Research-status Report
    • Peer Reviewed
  • [Journal Article] Electrogenerated Chemiluminescence of Tris(dibenzoylmethane)phenanthroline Europium(III) as a Light Source: an Application for the Detection of PO43- Based on the Ion Associate Formation of Phosphomolybdic Acid and Malachite Green2019

    • Author(s)
      E. Kunisawa, R. Ishimatsu, K. Nakano, T. Imato
    • Journal Title

      Analytical sciences

      Volume: 印刷中

    • NAID

      130007676957

    • Related Report
      2018 Research-status Report
  • [Presentation] ピレンのミリ秒時間分解電気化学発光スペクトル:エキシマー発光の速度論的解析2020

    • Author(s)
      〇石松亮一,中野幸二
    • Organizer
      電気化学会第87回大会
    • Related Report
      2020 Annual Research Report
  • [Presentation] ペリレンの電気化学発光と 3 重項-3 重項消滅に よってアップコンバートされた発光スペクトル についての考察2020

    • Author(s)
      〇石松亮一,中野幸二
    • Organizer
      第 66 回ポーラログラフィーおよび電気分析化学討論会
    • Related Report
      2020 Annual Research Report
  • [Presentation] ピレンのミリ秒時間分解電気化学発光スペクトル:エキシマー発光の速度論的解析2020

    • Author(s)
      石松亮一,中野幸二
    • Organizer
      電気化学会第87回大会
    • Related Report
      2019 Research-status Report
  • [Presentation] Portable Analytical Detection Systems Based on Light Emitting Devices2019

    • Author(s)
      Ryoichi Ishimatsu
    • Organizer
      International Conference on Electronics Packing, ICEP 2019
    • Related Report
      2019 Research-status Report
    • Int'l Joint Research / Invited
  • [Presentation] 電極反応で生成する有機ラジカルイオンのミリ秒時間分解スペクトルの取得による均一電子移動反応速度の評価2019

    • Author(s)
      石松 亮一、 山口 雄輝、中野 幸二
    • Organizer
      第79回分析化学討論会
    • Related Report
      2019 Research-status Report
  • [Presentation] 電気化学発光における高位励起状態形成の可能性2019

    • Author(s)
      石松亮一、中野幸二
    • Organizer
      2019年電気化学会秋季大会
    • Related Report
      2019 Research-status Report
  • [Presentation] Excimer Formation of Pyrene in Electrogenerated Chemiluminescence2019

    • Author(s)
      Ryoichi Ishimatsu, Koji Nakano
    • Organizer
      The International Joint Meeting of the Polarographic Society of Japan (PSJ) and National Taiwan University (NTU)
    • Related Report
      2019 Research-status Report
    • Int'l Joint Research
  • [Presentation] Eu(III)およびTb(III)錯体の電子状態と電気化学発光特性2018

    • Author(s)
      石松亮一,國澤栄里,中野幸二,今任稔彦
    • Organizer
      第64回ポーラログラフィーおよび電気分析化学討論会
    • Related Report
      2018 Research-status Report
  • [Presentation] 電極反応で生成する有機ラジカルイオンのミリ秒時間分解スペクトル2018

    • Author(s)
      石松亮一、古川佳栄、中野幸二、今任稔彦
    • Organizer
      日本分析化学会第67年会
    • Related Report
      2018 Research-status Report
  • [Presentation] 近赤外発光するpyrrolopyrrole aza-BODIPY類の電気化学発光特性2018

    • Author(s)
      石松 亮一、新宅 浩聡、鹿毛 悠冬、清水 宗治、古田 弘幸、中野 幸二、今任 稔彦
    • Organizer
      2018年電気化学秋季大会
    • Related Report
      2018 Research-status Report
  • [Presentation] 電気化学発光フローデバイスの検討2018

    • Author(s)
      石松亮一
    • Organizer
      第78回分析化学討論会
    • Related Report
      2018 Research-status Report
    • Invited
  • [Remarks]

    • URL

      http://www.cstf.kyushu-u.ac.jp/~chemenvironlab/index.html

    • Related Report
      2018 Research-status Report

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Published: 2018-04-23   Modified: 2022-01-27  

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