Development of Chemistry of Expanded Porphyrins
| Project/Area Number |
15350022
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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 | 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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| Project Period (FY) |
2003 – 2004
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| Project Status |
Completed (Fiscal Year 2004)
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| Budget Amount *help |
¥14,600,000 (Direct Cost: ¥14,600,000)
Fiscal Year 2004: ¥4,100,000 (Direct Cost: ¥4,100,000)
Fiscal Year 2003: ¥10,500,000 (Direct Cost: ¥10,500,000)
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| Keywords | porphyrins / expanded porphyrins / aromaticity / metal complexes / size-selective synthesis / hexaphyrins / octaphyrins |
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| Research Abstract |
The large ring size of expanded porphyrins encourages the possibility of the formation of related multi-metal complexes. Along this line, we examined the Cu(II) metalation of an octaphyrin, which led to the formation of bis-Cu(II) octaphyrin quantitatively. Interestingly, the heating of this bis-Cu(II) octaphyrin resulted in the splitting into two Cu(II) porphyrins. We named this interesting reaction as a molecular mitosis. This reaction is accompanied by a large spectral change, which may be used in memory devices We thus made a film composed of bis0Cu(II) octaphyrin that was found to be more robust against the thermal splitting than in solution.
We also examined the Cu(II)-metalation of a decaphyrin, which led to the isolation of two tris-Cu(II) decaphyrins that were found to show very unique structures, in which the edged two Cu(II) ions are coordinated within a hemi-porphyrin-like tetrapyrrolic ligand, while the central Cu(II) ion is coordinated with only pyrrolic nitrogen atoms, constituting a very rare case.
We also examined the size-selective synthesis of expanded porphyrins with a tripyrrane as a starting substrate. From this reaction, we isolated rubyrin, nonaphyrin, dodecaphyrin, some of which were found to be useful as an anion sensing agent.
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Report
(3 results)
Research Products
(90 results)
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[Journal Article] Directly meso-meso Linked Porphyrin Rings : Synthesis, Characterization, and Efficient Excitation Energy Hopping2005
Author(s)
Y.Nakamura, I.-W.Hwang, N.Aratani, T.K.Ahn, D.M.Ko, A.Takagi, T.Kawai, T.Matsumoto, D.Kim, A.Osuka
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Journal Title
J.Am.Chem.Soc. 127
Pages: 236-246
Description
「研究成果報告書概要(和文)」より
Related Report
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[Journal Article] Directly meso-meso-Linked Porphyrin Rings : Synthesis, Characterization, and Efficient Excitation Energy Hopping2005
Author(s)
Y.Nakamura, I.-W.Hwang, N.Aratani, T.K.Ahn, D.M.Ko, A.Takagi, T.Kawai, T.Matsumoto, D.Kim, A.Osuka
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Journal Title
J.Am.Chem.Soc. 127
Pages: 236-246
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[Journal Article] Synthesis of Directly Linked Zinc^<[II]> Porphyrin-Imide Dyads and Energy Gap Dependence of Intramolecular Electron Transfer Reactions2003
Author(s)
N.Yoshida, T.Ishizuka, K.Youfu, M.Murakami, H.Miyasaka, T.Okada, Y.Nagata, A.Itaya, H.S.Cho, D.Kim, A.Osuka
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Journal Title
Chem.Eur.J. 9
Pages: 2854-2866
Description
「研究成果報告書概要(和文)」より
Related Report
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[Publications] N.Yoshida, T.Ishizuka, K.Youfu, M.Murakami, H.Miyasaka, T.Okada, Y.Nagata, A.Itaya, H.S.cho, D.Kim, A.Osuka: "Synthesis of Directly Linked Zinc[II] Porphyrin-Imide Dyads and Energy Gap Dependence of Intramolecular Electron Transfer Reactions"Chem.Eur.J.. 9. 2854-2866 (2003)
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