Synthesis of a rotaxane possessing of Janus-type macrocycle: new type of switching and multi-state switching
| Project/Area Number |
16K05691
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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 | University of Fukui |
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Principal Investigator |
Tokunaga Yuji 福井大学, 学術研究院工学系部門, 教授 (80250801)
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| Project Period (FY) |
2016-04-01 – 2019-03-31
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| Project Status |
Completed (Fiscal Year 2018)
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| Budget Amount *help |
¥4,810,000 (Direct Cost: ¥3,700,000、Indirect Cost: ¥1,110,000)
Fiscal Year 2018: ¥1,430,000 (Direct Cost: ¥1,100,000、Indirect Cost: ¥330,000)
Fiscal Year 2017: ¥1,430,000 (Direct Cost: ¥1,100,000、Indirect Cost: ¥330,000)
Fiscal Year 2016: ¥1,950,000 (Direct Cost: ¥1,500,000、Indirect Cost: ¥450,000)
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| Keywords | 分子スイッチ / 刺激応答 / 水素結合 / アミド / ロタキサン / 超分子化学 / 分子機械 / 分子認識 / 分子応答 |
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| Outline of Final Research Achievements |
We synthesized the macrocyclic tetraamide, possessing four tertiary amide units, as hosts for mono- and bis-ammonium ions, forming corresponding [2]pseudorotaxanes stabilized through hydrogen bonding between the components. In a nonpolar solvent, only one conformational isomer existed for each [2]rotaxane. On the other hand, in a polar solvent, the rotaxane possessing a mono-ammonium ion in the axle was partially isomerized; only a single rotational isomer existed for the rotaxane featuring a bis-ammonium ion in the axle, because of a complete set of hydrogen bonds.
Conformational isomerization of the macrocycle in the bis-ammonium-rotaxane was completed in response to base and acid: (1) under neutral conditions, the macrocycle exists as a single rotarmer; (2) in the presence of 1 eq of base, a small amount of rotarmer exists; (3) in the presence of excess base, non-selective isomerization was observed. These motions of the macrocyclic component proceeded reversibly.
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| Academic Significance and Societal Importance of the Research Achievements |
分子スイッチの一つとして知られているロタキサンは、数多くの化合物が合成されているものの、多用されている軸と環の組み合わせは数種に過ぎない。まず本研究では、環状アミドとアンモニウムイオンからロタキサンが形成することを見出した。次に本ロタキサンを用い、溶媒の極性や液性に応答しアミドのロータマー異性のコントロールに成功した。本刺激応答はこれまでとは異なる新しいスイッチ様式であり、またスイッチングは多段階で進行することも確認している。化合物の新規性、スイッチ様式の新規性、並びに多段階でスイッチすることは、学術的に大きな意義を持つ。
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Report
(4 results)
Research Products
(13 results)
