2001 Fiscal Year Final Research Report Summary
Construction of 3D structure of porphyrin polymer complexes and control of their electronic transition
| Project/Area Number |
11650903
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| Research Category |
Grant-in-Aid for Scientific Research (C)
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| Allocation Type | Single-year Grants |
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| Section | 一般 |
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| Research Field |
高分子合成
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| Research Institution | The University of Tokyo |
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Principal Investigator |
SEGAWA Hiroshi The University of Tokyo, Graduate School of Arts and Sciences, Associate Professor, 大学院・総合文化研究科, 助教授 (50216511)
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| Project Period (FY) |
1999 – 2001
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| Keywords | porphyrin / polymer compley / elecfron transfer / Tc-radical / triplet state / photpinduced electron transfer / cheinical oxidation / photo-oxidation |
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| Research Abstract |
The electronic transition of 3D porphyrin arrays are important not only for elucidation of the functions of the natural systems but also for application of the functions to molecular architecture. In this study, a novel systematic synthesis of various types of porphyrin arrays were investigated.
Among them, the excited state properties of phosphorus(V) porphyrin dimers were investigated on the contribution of a charge transfer (CT) state. The lifetime of the symmetry-disturbed "center-to-edge" dimer was remarkably shortened through the CT state. The photo-induced Electron Transfer through the CT state was observed in the triad molecular systems of the phosphorus(V) porphyrins. On the other hand, zinc meso-(1-pyrenyl)triphenylporphyrin derivatives were synthesized and investigated on their photophysical properties. While the S1 fluorescence of the porphyrin derivatives was not quenched by the pyrenyl group at all, the S2 fluorescence was remarkably quenched through intramolecular CT state.
On the other hand, poly-π-radical cations of directly meso-linked Zn(II)porphyrin arrays (dimer ZnP2, trimer ZnP3, and tetramer ZnP4) were synthesized and investigated for spin alignment. The high-spin states based on the exchange interaction between adjacent porphyrin π-radicals were observed. The temperature dependence indicated a temperature-dependent singlet-triplet crossover at the relatively high temperature.
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