2001 Fiscal Year Final Research Report Summary
Construction of Molecular Chain Reaction Synstem Based on Porphyrin Arreys and Chain Protochemical Reactions
| Project/Area Number |
11223205
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| Research Category |
Grant-in-Aid for Scientific Research on Priority Areas (B)
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| Allocation Type | Single-year Grants |
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| Review Section |
Science and Engineering
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| Research Institution | KYOTO UNIVERSITY |
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Principal Investigator |
OSUKA Atsuhiro Kyoto University, Graduate School of Science, Professor, 大学院・理学研究科, 教授 (80127886)
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| Co-Investigator(Kenkyū-buntansha) |
SHINMORI Hideyuki Kyoto University, Graduate School of Science, Inst., 大学院・理学研究科, 助手 (40311740)
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| Project Period (FY) |
1999 – 2001
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| Keywords | porphyrin array / meso-meso linked porphyrin arrays / monodisperse giant molecule / molecular wire / porphyrin sheet / ポルフィリンシート |
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| Research Abstract |
1) We have prepared a series of meso-meso linked diporphyrins strapped with variable length dioxymethylene group. These diporphyrins exhibit systematic spectral changes upon the decrease in the dihendral angle. Two-bands shape Soret band in non-strapped diporphyrins changes into four-bands shape Soret band.
2) Discrete 1024-mer of meso-meso linked porphyrin arrays has been prepared and charactrized, which is by far the longest man-made dicrete molecule. It is to be noted that even 1-240mer is certainly soluble in organic solvents and can be manipulated.
3) Oxidation with Sc(OTf)_3 and DDQ realized very efficient transformation of end-phenyl capped meso-meso linked porphyrin arrays to triply-linked conjugated porphyrin arrays. The absorption spectra of these conjugated 6-mer, 8-mer and 12-mer display the electronic absorption band deep into infrared region up to 1500 cm^<-1>.
Starting from 5,10-diaryl metalloporphyrin, conjugated rectangular-shaped porphyrin sheets have been prepared in 10-15% yields, which have 2-dimensionally expanded π-network.
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[Publications] A. Nakano, Y. Yasuda, T. Yamazaki, S. Akimoto, I. Yamazaki, H. Miyasaka, A. Itaya, M. Murakami, and H. Miyasaka: "Modified Windmill Porphyrin Arrays: Coupled Light-Harvesting and Charge Separation, Conformational Relaxation, and S_<2->S_2 Energy Transfer"Chem. Eur. J.. 7. 3134-3151 (2001)
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