Study of excited state chiral dynamics of transition metal complexes by time-resolved circular polarization spectroscopy
| Project/Area Number |
20K05526
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| Research Category |
Grant-in-Aid for Scientific Research (C)
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| Allocation Type | Multi-year Fund |
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| Section | 一般 |
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| Review Section |
Basic Section 34010:Inorganic/coordination chemistry-related
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| Research Institution | University of Toyama |
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Principal Investigator |
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| Project Period (FY) |
2020-04-01 – 2023-03-31
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| Project Status |
Completed (Fiscal Year 2022)
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| 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)
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| 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 |
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| 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。
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| 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.
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| 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。
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Report
(4 results)
Research Products
(9 results)
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[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
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Journal Title
Physical Chemistry Chemical Physics
Volume: 25
Issue: 2
Pages: 966-974
DOI
Related Report
Peer Reviewed / Int'l Joint Research
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