| Project/Area Number |
17350015
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| Research Category |
Grant-in-Aid for Scientific Research (B)
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| Allocation Type | Single-year Grants |
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| Section | 一般 |
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| Research Field |
Organic chemistry
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| Research Institution | Tokyo Institute of Technology (2006)
The University of Tokyo (2005) |
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Principal Investigator |
GOTO Kei Tokyo Institute of Technology, Graduate School of Science and Engineering, Associate Professor, 大学院・理工学研究科, 助教授 (70262144)
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| Project Period (FY) |
2005 – 2006
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| Project Status |
Completed (Fiscal Year 2006)
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| Budget Amount *help |
¥11,400,000 (Direct Cost: ¥11,400,000)
Fiscal Year 2006: ¥3,500,000 (Direct Cost: ¥3,500,000)
Fiscal Year 2005: ¥7,900,000 (Direct Cost: ¥7,900,000)
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| Keywords | highly coordinated main-group elements / silicon compounds / macrocyclic compounds / nano-size molecules / cage-type molecules / hypervalent bonding / X-ray crystallographic analysis / thermodynamic control / ナノスケール分子 / 分子スクエア / 分子プリズム / 動的共有結合 |
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| Research Abstract |
The design and construction of nano-size macrocyclic compounds has been attracting increasing attention. The hypervalent bonding interaction of highly coordinated main-group elements is considered to be versatile for the construction of such type of nano-size architecture because it has moderate strength and well-defined geometric characters. In this study, the construction of nano-size macrocycles by utilizing the characteristics of highly coordinated silicon was investigated. A biphenyl derivative containing highly coordinated hydrosilane units at both ends was allowed to react with various diols such as 1,4-butanediol and 4,4'-biphenol, and the corresponding square-shaped macrocycles were obtained by just heating without addition of any other reagents or catalysts. In the reaction of a 1,3,5-triarylbenzene containing highly coordinated hydrosilane units at three ends with 4,4'-biphenol, the corresponding prism-type molecular capsule was obtained in 87% yield. The structures of these macrocycles were established by X-ray crystallographic analysis. Monitoring of the reactions by ^1H NMR and GPC indicated that polymeric intermediates were formed at the early stage of the reaction, which were converted to the macrocycles by prolonged heating under thermodynamic control.
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