| Project/Area Number |
14540526
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| Research Category |
Grant-in-Aid for Scientific Research (C)
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| Allocation Type | Single-year Grants |
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| Section | 一般 |
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| Research Field |
機能・物性・材料
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| Research Institution | Utsunomiya University |
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Principal Investigator |
HIRATANI Kazuhisa Utsunomiya University, Department of Applied Chemistry, Professor, 工学部, 教授 (40343082)
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| Co-Investigator(Kenkyū-buntansha) |
KARIKOMI Micninari Utsunomiya University, Department of Applied Chemistry, Associate Professor, 工学部, 助教授 (00224709)
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| Project Period (FY) |
2002 – 2004
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| Project Status |
Completed (Fiscal Year 2004)
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| Budget Amount *help |
¥3,500,000 (Direct Cost: ¥3,500,000)
Fiscal Year 2004: ¥800,000 (Direct Cost: ¥800,000)
Fiscal Year 2003: ¥900,000 (Direct Cost: ¥900,000)
Fiscal Year 2002: ¥1,800,000 (Direct Cost: ¥1,800,000)
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| Keywords | Tandem Claisen Rearrangement / Crownophanes / Rotaxanes / Molecular Recognition / Lithium ion Selectivity / Fluorescence Spectrum / Energy Transfer / Supramolecular System / タンデムクライゼン転位 / 大環状化合物 / イオン選択性 / 光学不斉ロタキサン / チリウム選択性 |
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| Research Abstract |
A new route for rotaxane synthesis via covatent bond formation was developed from macrocyclic compounds (crownophanes) prepared by tandem Claisen rearrangement. The construction of [2]rotaxanes by this method and their functions such as sensing based on the energy transfer phenomenon between molecules were investigated. It was found that these rotaxanes can exhibit the selective complexation with lithium ion, where the roter and axle molecules work cooperatively to catch the ion, and the specific increase of fluorescent intensity was observed only in the presence of lithium ion accompanying with energy transfer phenomenon.
In addition, [1]and [3]rotaxanes were successfully synthesized by our method, while their synthesi has not been reported by a synthetic method via covalent bond formation so far. [1]Rotaxanes prepared were confirmed to make complex with lithium ion specifically among alkali metal ions in the NMR and Mass spectra and observed the energy transfer phenomenon. It is concluded that the macrocyclic part and axle part form three dimensional structure (supercryptand structure) to result in the incorporation of lithium ion with high selectivity into the cavity. By our method, [3]rotaxanes were also prepared, and one of them forms 1:1 complex with cesium ion in the manner of sandwich-like structure.
Thus, in this project, a novel synthetic method for rotaxanes has been developed and and the functions have been elucidated. That is, our synthetic method can be applied to the synthesis not only of [2]rotaxanes but also of [1]and [3]rotaxanes, and the specific energy transfer behaviors toward cations were observed in the fluorescence spectrum.
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