2003 Fiscal Year Final Research Report Summary
A Study on the Synthesis, Structure, Reaction, and Properties of New π-Elecitronic Macrocycles
| Project/Area Number |
14340200
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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 | Kyushu University |
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Principal Investigator |
SHINMYOZU Teruo Kyushu University, Institute for Materials Chemistry and Engineering, Professor, 先導物質化学研究所, 教授 (90037292)
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| Co-Investigator(Kenkyū-buntansha) |
SHIBAHARA Masahiko Oita University, Faculty of Education and Welfare Science, Research Associate, 教育福祉学部, 助手 (60253762)
TAKEMURA Hiroyuki Kyushu University, Faculty of Scieces, Research Associate, 理学部, 助手 (60183456)
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| Project Period (FY) |
2002 – 2003
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| Keywords | prismanes / cage compounds / metallocene / cyclophane / charge transfer complexes / charge transfer interaction / conducting materials / photochemical reaction |
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| Research Abstract |
(1)Synthesis of hexaprismane derivatives via photo-isomerization of multibridged[3_n]cyclophanes(n=3-6)
Our efforts have been made toward the isolation and characterization of hexaprismane derivatives. In order to stabilize the hexaprismane skeleton and deactivate toward chemical reactions, we developed new synthetic methods of fluorinated[3_n]cyclophanes as precursor of the photochemical reactions. We confirmed that the photochemical reactions of these cyclophanes did proceed. The isolation and characterization of the photoproducts are in progress.
As an alternative method for the isolation of hexaprismane derivatives, we found that the[3_3]cyclophane is included in γ-cyelodextrine in 1:1 ratio and the complex is isolated. Irradiation of the complex in the solid state led to the formation of some cage compound(s), and their isolation and characterization are in progress.
2)Synthesis of tube-like molecules as new inclusion host molecules
For the construction of uni-molecular tube-like molecule, we synthesized the new cyclophanes with different cavity sizes as structural units and examined their structural properties. We are now studying connecting methods of these structural units. In connection with this study, we also designed and synthesized several three-dimensional new macrocycles via metal coordination.
(3)Synthesis and properties of metallocenes with cyclophane ligands
We have studied the synthetic route of [3_5]ferrocenophane in which an iron atom is highly compressed. As a new synthetic route, we designed to synthesize the ferrocenophane by the cyclization using olefin-metathesis. According to this route, synthesis is in progress.
We also studied the synthesis of mixed valent Ru(II)Ru(0)-[3_n]cyclophane(n=3,4) complexes as new electron-conducting materials. We found that the Ru(I)Ru(I) complex was formed by the two-electron reduction of the Ru(II)Ru(II)-[3_3]cyclophane complex, and examined its structure and chemical properties.
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