| Project/Area Number |
08454214
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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 |
Inorganic chemistry
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| Research Institution | Kinki University |
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Principal Investigator |
MUNAKATA Megumu KINKI UNIVERSITY,DEPARTMENT OF CHEMISTRY,PROFESSOR, 理工学部, 教授 (80090942)
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| Project Period (FY) |
1996 – 1997
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| Project Status |
Completed (Fiscal Year 1997)
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| Budget Amount *help |
¥8,700,000 (Direct Cost: ¥8,700,000)
Fiscal Year 1997: ¥2,300,000 (Direct Cost: ¥2,300,000)
Fiscal Year 1996: ¥6,400,000 (Direct Cost: ¥6,400,000)
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| Keywords | supramolecular / calixarene / silver / molecular container / crystal engineering / coordination polymer / pi-complex / 三次元錯体 / C_5H_4S_5 / S・・・S接触 / 低次元錯体 |
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| Research Abstract |
Reaction of calix[4]arene and an excess of AgClO_4 in benzene isolated the polymeric complex [Ag2(calix[4]arene(ClO_4)_2]. In this complex, each calix[4]arene is symmetrically bound to four silver atoms with each of the four carbon atoms in the distal phenyl units of the upper rim coordinated to one Ag(I) ion, which in turn bridges two calix[4]arenes. A two-dimensional polymeric framework of calix[4]arene thus resulted from this arrangement is further stabilized by the ClO_4^- anion bridging between two Ag atoms, which partially caps the cavity at the upper rim of the calixarene giving rise to a closed supramolecular container.
The unique two-dimensional framework based on multiple cation-pi interaction of calixarene and metal ions allows the possibility of using pi-metalated calixarenes as building blocks for synthetic supramolecular receptors. In fact, the complex is a rarely observed closed molecular container, in which the four silver atoms attached to the upper rim of a calixarene are bridged in pair by two ClO_4^- ions. The perchlorate ions act as a gate above the upper rim of the calixarene and shuts the path to the bowl cavity. The measured cavity size as an interatomic distance is ca.7.0 * at the upper rim and ca.2.3 * at the lower rim with a depth of ca.4.4 *, taking into consideration of van der Waal's radius. The calix would have a cavity large enough to selectively encapsulate small molecules such as dioxygen and methane. The inclusion of small gaseous molecules and its applications are the subject of ongoing investigations.
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