| Project/Area Number |
14205127
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| Research Category |
Grant-in-Aid for Scientific Research (A)
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| Allocation Type | Single-year Grants |
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| Section | 一般 |
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| Research Field |
Synthetic chemistry
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| Research Institution | OSAKA UNIVERSITY |
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Principal Investigator |
TAKAHASHI Shigetoshi OSAKA UNIVERSITY, ISIR (SANKEN), PROFESSOR, 産業科学研究所, 教授 (70029875)
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| Co-Investigator(Kenkyū-buntansha) |
TAKEI Fumie OSAKA UNIVERSITY, ISIR (SANKEN), TECHNICAL STAFF, 産業科学研究所, 教務職員 (30252711)
ZHOU Da-yang OSAKA UNIVERSITY, ISIR (SANKEN), RESEARCH ASSOCIATE, 産業科学研究所, 助手 (00324848)
ONITSUKA Kiyotaka OSAKA UNIVERSITY, ISIR (SANKEN), ASSOCIATE PROFESSOR, 産業科学研究所, 助教授 (10244633)
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| Project Period (FY) |
2002 – 2003
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| Project Status |
Completed (Fiscal Year 2003)
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| Budget Amount *help |
¥27,820,000 (Direct Cost: ¥21,400,000、Indirect Cost: ¥6,420,000)
Fiscal Year 2003: ¥9,620,000 (Direct Cost: ¥7,400,000、Indirect Cost: ¥2,220,000)
Fiscal Year 2002: ¥18,200,000 (Direct Cost: ¥14,000,000、Indirect Cost: ¥4,200,000)
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| Keywords | organometallic compounds / giant molecule / helix / dendrimer / polyisocyanide / precise polymerization / 白金アセチリド / ポルフィリン / エネルギー異動 / 有機金属高分子 / キラル高分子 / らせんキラリティ |
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| Research Abstract |
In this research project, we have worked on the synthesis of giant organometallic molecules with definite and characteristic three-dimensional structures by utilizing structural flexibility and specific reactivities of organometallic compounds, and on the development of new molecular functionalities. Our research has been focused on dendritic and helical chiral macromolecules, and we have obtained the following results:
(1) Platinum-acetylide dendrimers having porphyrin at the core were prepared by a convergent method up to the third generation, and the intramolecular energy-transfer from platinum-acetylide moieties to the porphyrin core was observed.
(2) Efficient synthetic route for platinum-acetylide dendrimers was developed, and the sixth dendrimer that is the largest organometallic dendrimer so far was precisely prepared by a divergent method.
(3) Ruthenium-acetylide dendrimers having bridging ligands derived from triarylamine were prepared, and the relatively large interaction among metal moieties was observed.
(4) Helical chiral polyisocyanides having ferrocenyl groups, which showed a good redox property, as pendants were precisely synthesized. The polyisocyanides showed reversible conformational change responding to an electrochemical stimulus against the ferrocenyl pendants.
(5) Intramolecular energy transfer was observed in the helical chiral polyisocyanides with porphyrin pendants. We found that the helical structure enhanced the efficiency of the energy transfer, and that the functional group binding the porphyrin pendants to the main chain of the polyisocyanides affected the efficiency of the energy transfer.
(6) One handed helical poly(aryl isocyanide)s with bulky substituents at ortho-position of the aryl groups were predominantly prepared by using organorhodium complexes as initiators.
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