| Project/Area Number |
20K20367
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| Project/Area Number (Other) |
18H05355 (2018-2019)
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| Research Category |
Grant-in-Aid for Challenging Research (Pioneering)
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| Allocation Type | Multi-year Fund (2020)
Single-year Grants (2018-2019) |
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| Review Section |
Medium-sized Section 34:Inorganic/coordination chemistry, analytical chemistry, and related fields
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| Research Institution | Tokyo Institute of Technology |
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Principal Investigator |
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| Co-Investigator(Kenkyū-buntansha) |
玉置 悠祐 東京工業大学, 理学院, 助教 (10752389)
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| Project Period (FY) |
2018-06-29 – 2022-03-31
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| Project Status |
Completed (Fiscal Year 2021)
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| Budget Amount *help |
¥26,000,000 (Direct Cost: ¥20,000,000、Indirect Cost: ¥6,000,000)
Fiscal Year 2021: ¥6,500,000 (Direct Cost: ¥5,000,000、Indirect Cost: ¥1,500,000)
Fiscal Year 2020: ¥6,500,000 (Direct Cost: ¥5,000,000、Indirect Cost: ¥1,500,000)
Fiscal Year 2019: ¥6,500,000 (Direct Cost: ¥5,000,000、Indirect Cost: ¥1,500,000)
Fiscal Year 2018: ¥6,500,000 (Direct Cost: ¥5,000,000、Indirect Cost: ¥1,500,000)
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| Keywords | 光反応化学 / レドックス光増感錯体 / S-T吸収 / 光触媒反応 |
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| Outline of Research at the Start |
本来は禁制遷移である光増感錯体の一重項－三重項遷移（S-T遷移：基底状態から3MLCT励起状態への直接遷移）の遷移確率を飛躍的に向上させる新手法の開発を目指す。S-T吸収帯を強く発現できれば、反応に必要な性質を維持したまま、吸収できる光の波長領域をはるかに長波長側に拡大することができる。
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| Outline of Final Research Achievements |
In order to utilize solar light efficiently, absorption of longer-wavelength visible-light is highly important. In this study, therefore, we have focused on developing the redox photosensitizer expressing S-T absorption, that is originally forbidden direct transitions from ground state to the triplet excited states.
We have found that the heteroleptic ruthenium complexes having two different tridentate ligands function as a redox photosensitizer exhibiting S-T absorption. Based on the results using ligands with various electronic and steric characters, the ruthenium complexes having push-pull type configuration of tridentate ligands expressed strong S-T absorption and absorbed light shorter than 720 nm. The osmium complex with similar ligands absorbed entire wavelength range of visible light up to 800 nm and functioned as a redox photosensitizer.
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| Academic Significance and Societal Importance of the Research Achievements |
太陽光を有効に利用するには、長波長の光を活用することが不可欠である。従来の方法で光増感剤の吸収を長波長化すると、光増感剤に深刻な機能低下を引き起こしてしまう。本研究では、S-T吸収により光増感剤の機能を維持したまま、長波長の可視光を利用することに成功した。S-T吸収を発現できるルテニウム錯体の分子設計を明らかにできたことは、光化学の学術面で非常に意義深いものである。また可視光の全波長領域を利用できる光増感剤は、様々な光反応を可視光全域で駆動できる可能性がある。
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