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Study of excited state chiral dynamics of transition metal complexes by time-resolved circular polarization spectroscopy

Research Project

Project/Area Number 20K05526
Research Category

Grant-in-Aid for Scientific Research (C)

Allocation TypeMulti-year Fund
Section一般
Review Section Basic Section 34010:Inorganic/coordination chemistry-related
Research InstitutionUniversity of Toyama

Principal Investigator

Iwamura Munetaka  富山大学, 学術研究部理学系, 講師 (60372942)

Project Period (FY) 2020-04-01 – 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 2022: ¥390,000 (Direct Cost: ¥300,000、Indirect Cost: ¥90,000)
Fiscal Year 2021: ¥1,560,000 (Direct Cost: ¥1,200,000、Indirect Cost: ¥360,000)
Fiscal Year 2020: ¥2,340,000 (Direct Cost: ¥1,800,000、Indirect Cost: ¥540,000)
Keywords金属錯体 / 希土類 / 円偏光発光 / 時間分解発光 / キラル / 光学選択的反応 / アロステリック効果 / 遭遇イオン対 / 超高速時間分解分光 / 発光分光 / 時間分解円偏光発光 / 光学選択的消光反応 / ユウロピウム / ヤーン・テラー変形
Outline of Research at the Start

CPL分光と、時間分解発光分光の2種の発光分光法を組み合わせ、フェムト秒時間領域まで測定可能なCPL分光システムを開発する。ナノ秒時間分解能を持つシステムを用いて、アミノ酸によってキラリティを誘起された発光性希土類錯体の光学選択的消光反応を観測する。フェムト秒では、円偏光励起した縮重励起状態からの円偏光異方性発光を検出する。

Outline of Final Research Achievements

Time-resolved emission measurements, including time-resolved circularly polarized luminescence (CPL) spectroscopy, have been carried out for photo-excited transition metal complexes. A copper(I) complex exhibiting Jahn-Teller structural change in the excited state was excited by circularly polarized light, and the temporal profiles of the femto-second time-resolved CPL was measured in the femto - pico second time regions. However, no detectable CPL signal was obtained. On the other hand, when we measured the nano - milli second time-resolved CPL of aqueous solutions containing Eu complex and chiral cobalt complexes, we found intense CPL signals in the microsecond time region on the temporal profiles. This is an evidence of that the encounter complex formation between the Eu and Co complexes causes the quenching reaction due to energy transfer and the chiral structural change of the Eu complex by the interactions between the Eu and the Co complexes.

Academic Significance and Societal Importance of the Research Achievements

アキラルな[Eu(pda)2]-がキラルな[Co(en)3]3+により円偏光発光を示すことが明らかとなった。アミノ酸以外のキラル分子で円偏光を[Eu(pda)2]-に誘起するはじめての例である。時間分解CPLを計測することにより、短寿命種がCPLを示すことが分かった。これは時間分解CPLの有効性を示した珍しい例のひとつである。一方、フェムト秒時間分解CPLでは課題を残すことになった。直励起で励起縮重状態を生成する系にて再検討する必要がある。

Report

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

    (9 results)

All 2023 2022 2021 2020

All Journal Article (2 results) (of which Int'l Joint Research: 2 results,  Peer Reviewed: 2 results) Presentation (7 results) (of which Int'l Joint Research: 2 results,  Invited: 1 results)

  • [Journal Article] Spectroscopic mapping of the gold complex oligomers (dimer, trimer, tetramer, and pentamer) by excited-state coherent nuclear wavepacket motion in aqueous solutions2023

    • Author(s)
      M. Iwamura, R. Urayama, A. Fukui, K. Nozaki, L. Liu, H. Kuramochi, S. Takeuchi, T. Tahara
    • Journal Title

      Physical Chemistry Chemical Physics

      Volume: 25 Issue: 2 Pages: 966-974

    • DOI

      10.1039/d2cp04823j

    • Related Report
      2022 Annual Research Report
    • Peer Reviewed / Int'l Joint Research
  • [Journal Article] Coherent Vibration and Femtosecond Dynamics of the Platinum Complex Oligomers upon Intermolecular Bond Formation in the Excited State2020

    • Author(s)
      Iwamura Munetaka、Fukui Airi、Nozaki Koichi、Kuramochi Hikaru、Takeuchi Satoshi、Tahara Tahei
    • Journal Title

      Angewandte Chemie International Edition

      Volume: 59 Issue: 51 Pages: 23154-23161

    • DOI

      10.1002/anie.202011813

    • Related Report
      2020 Research-status Report
    • Peer Reviewed / Int'l Joint Research
  • [Presentation] 発光性分子集合体のコヒーレント振動と構造変形ダイナミクス2023

    • Author(s)
      岩村宗高
    • Organizer
      第103回春季年会
    • Related Report
      2022 Annual Research Report
    • Invited
  • [Presentation] Ultrafast Spectroscopy of Platinum(II) Complex Oligomers in Solutions2022

    • Author(s)
      Munetaka Iwamura, Honoka Watanabe, Koichi Nozaki, Tsukasa Takanashi, Hikaru Kuramochi, and Tahei Tahara
    • Organizer
      ISPPCC 2022
    • Related Report
      2022 Annual Research Report
    • Int'l Joint Research
  • [Presentation] 岩村 宗高・浦山 里奈・福井 愛理・野崎 浩一・Li Liu 倉持 光 竹内 佐年 田原 太平2022

    • Author(s)
      水溶液中におけるジシアノ金(I)錯体の励起2量体から5量体の時間分解吸収・発光および振動スペクトル
    • Organizer
      配位化合物の光化学討論会
    • Related Report
      2022 Annual Research Report
  • [Presentation] 不均一カチオン場をもつ水溶液中における ジシアノ金(I)会合体の発光特性2022

    • Author(s)
      井上 大知・岡田 莉奈  野﨑 浩一・萩原 英久・岩村 宗高
    • Organizer
      配位化合物の光化学討論会
    • Related Report
      2022 Annual Research Report
  • [Presentation] CPL and CD spectra of achiral Eu(III) complex in solution containing amino acids2022

    • Author(s)
      Munetaka Iwamura, Miho Sakai, Yuzuki Nakauchi, Koichi Nozaki
    • Organizer
      第102回日本化学会春季年会
    • Related Report
      2021 Research-status Report
  • [Presentation] Chiral sensing microscopy using circularly polarized luminescence of lanthanide complexes with homo- or hetero-association of chiral amino acids2021

    • Author(s)
      Munetaka Iwamura, Hikaru Koike, Tatsuya Iwashita and Koichi Nozaki
    • Organizer
      Pacifichem 2021
    • Related Report
      2021 Research-status Report
    • Int'l Joint Research
  • [Presentation] 溶液中におけるジピリジル白金(II)錯体会合体の励起状 態ダイナミクス2020

    • Author(s)
      渡邉 ほのか,岩村 宗高, 野﨑 浩一,高梨 司,倉持 光, 田原 太平
    • Organizer
      第70回錯体化学討論会
    • Related Report
      2020 Research-status Report

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Published: 2020-04-28   Modified: 2024-01-30  

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