| Project/Area Number |
15K05424
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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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| Research Field |
Organic chemistry
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| Research Institution | Kobe University |
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Principal Investigator |
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| Research Collaborator |
Chaolu Eerdun
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| Project Period (FY) |
2015-04-01 – 2019-03-31
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| Project Status |
Completed (Fiscal Year 2018)
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| Budget Amount *help |
¥4,940,000 (Direct Cost: ¥3,800,000、Indirect Cost: ¥1,140,000)
Fiscal Year 2017: ¥780,000 (Direct Cost: ¥600,000、Indirect Cost: ¥180,000)
Fiscal Year 2016: ¥910,000 (Direct Cost: ¥700,000、Indirect Cost: ¥210,000)
Fiscal Year 2015: ¥3,250,000 (Direct Cost: ¥2,500,000、Indirect Cost: ¥750,000)
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| Keywords | オリゴピロール / キロプティカル分子スイッチ / らせん方向制御 / 酸化還元 / らせん不斉 / ヘリケート / 円偏光 / キロプティカル特性 / 溶媒応答性 |
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| Outline of Final Research Achievements |
Bimetallic complexes of hexapyrrole-α,ω-dicarbaldimines with stereogenic centers at both ends and an aromatic spacer in the center were prepared. Some complexes were found to adopt a one-handed helical form with showing a strong CD 1st Cotton effect in the Vis/NIR region. Since they underwent reversible one-electron redox leading to drastic changes in their chiroptical properties, they were investigated by spectroelectrochemistry. The bisNi helicate of a 2,5-hydroquinone spacer enabled on-off switching at 681 nm in the redox cycle between 0.2 V and -0.2 V (vs. Ag/AgNO3 reference) with the maximum CD intensity (Δε = -200 M-1.cm-1) at 681 nm in the oxidized state decreased to zero intensity in the reduced state. The bisNi helicate of a 3,5-pyridinium spacer also showed remarkable UV/Vis and CD spectral changes that are dependent on the solvent polarity and hydride redox state.
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| Academic Significance and Societal Importance of the Research Achievements |
鎖状オリゴピロールは環状のポルフィリンと比べて研究例が少なく、特に、長鎖誘導体の研究は非常に限られている。本研究では種々のオリゴピロール複核錯体を開発し、それらの不斉立体構造の完全制御、酸化還元活性とスペクトル特性の構造依存性について明らかにした。本研究では酸化還元や溶媒などの外部刺激に応じてCDスペクトルの変化が起こるキロプティカル分子スイッチを開発した。これらのらせん化合物は構造有機化学の分野で新規性が高い。また、円偏光による光通信では大容量のデータ通信が可能となると言われており、近未来テクノロジーに使用できる機能材料として応用が期待される
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