| Project/Area Number |
17350063
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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 |
Functional materials chemistry
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| Research Institution | Tohoku University |
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Principal Investigator |
KOBAYASHI Nagao Tohoku University, Graduate School of Science, Professor, 大学院理学研究科, 教授 (60124575)
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| Co-Investigator(Kenkyū-buntansha) |
MURANAKA Atsuya Tohoku University, Graduate School of Science, Research assistant, 大学院理学研究科, 助手 (20374902)
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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 |
¥13,100,000 (Direct Cost: ¥13,100,000)
Fiscal Year 2006: ¥4,600,000 (Direct Cost: ¥4,600,000)
Fiscal Year 2005: ¥8,500,000 (Direct Cost: ¥8,500,000)
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| Keywords | phthalocyanines / porphyrins / circular dichroism spectra / chirality / ポルフィリン |
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| Research Abstract |
In this research, nano-sized, chiral assemblies of phthalocyanines (Pcs) and their analogues have been constructed, and their spectroscopic properties analyzed. Syntheses and analyses of the building blocks have also been carried out.
Chiral complexes formed between naturally occurring procyanidins and phthalocyanines were studied. All the complexes studied exhibited intense CD signals in the region where Pc chromophores absorb photons. It was found that the CD intensity and sign are correlated with the number of catechin (or epicatechin) and their three-dimensional structure of the procyanidins.
Helical conformation of the nickel complex of a fused porphyrin dimers was assigned using time-dependent density functional theory (TDDFT).
Silicon μ-oxo Pc oligomers, up to trimer, with optically active alkoxy substituents at the periphery were prepared. In the CD spectra of these oligomers, the (R)-and (S)-isomers exhibited mirror-image signals. The result indicates that these isomers take mirror-imaged helical structures. Computational studies were performed using the TDDFT method, in order to assign the helical geometry.
Construction of rare-earth sandwich double-and triple-decker compounds with optical activity were attempted using Pcs and naphthalocyanines. The desired racemic complexes were successfully synthesized, but the optical resolution was unsuccessful.
Synthetic studies of a tretraazaporphyrin trimer with screwed geometry were performed. Chiral tris(phenanthroline)-ruthenium complexes and unsymmetrical tetraazaporphyrins with amino gourps were synthesized.
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