| Project/Area Number |
15205020
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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 |
Functional materials chemistry
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| Research Institution | Nara Institute of Science and Technology |
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Principal Investigator |
KOBUKE Yoshiaki Nara Institute of Science and Technology, Graduate School of Materials Science, Professor, 物質創成科学研究科, 教授 (80026195)
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| Co-Investigator(Kenkyū-buntansha) |
SATAKE Akiharu Nara Institute of Science and Technology, Graduate School of Materials Science, Assistant Professor, 物質創成科学研究科, 助手 (00277831)
OGAWA Kazuya Nara Institute of Science and Technology, Graduate School of Materials Science, Assistant Professor, 物質創成科学研究科, 助手 (50335486)
釘宮 愼一 奈良先端科学技術大学院大学, 物質創成科学研究科, 助教授 (60183795)
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| Project Period (FY) |
2003 – 2006
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| Project Status |
Completed (Fiscal Year 2006)
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| Budget Amount *help |
¥50,310,000 (Direct Cost: ¥38,700,000、Indirect Cost: ¥11,610,000)
Fiscal Year 2006: ¥11,570,000 (Direct Cost: ¥8,900,000、Indirect Cost: ¥2,670,000)
Fiscal Year 2005: ¥12,610,000 (Direct Cost: ¥9,700,000、Indirect Cost: ¥2,910,000)
Fiscal Year 2004: ¥12,610,000 (Direct Cost: ¥9,700,000、Indirect Cost: ¥2,910,000)
Fiscal Year 2003: ¥13,520,000 (Direct Cost: ¥10,400,000、Indirect Cost: ¥3,120,000)
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| Keywords | porphyrin / phthalocyanine / supramolecular science / artificial photosynthesis / two photon absorption / photo-dynamic therapy / molecular electronics / 光補集アンテナ系 / 自己配位組織化 / 電荷分離系 / 過渡吸収測定 / 光増感 / 光捕集アンテナ系 / 自己組織化 / 反応中心 / エネルギー移動 / 光電流効率 |
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| Research Abstract |
Light-harvesting antenna, photo-induced electron transfer, photo-voltaic cell, and two-photon absorption systems by use of coordination-organized special pair of porphyrins were investigated. To construct stable macrocyclic porphyrin systems, supramolecular methodology and following metathesis linking was developed. Excited energy hopping (EEH) rates of the porphyrin macrorings were estimated as 1/(tens ps) by ultra fast time-resolved spectroscopic techniques. The much shorter EEH time constants compared with fluorescence lifetime indicate that the excited energy can be stored in the macroring for a long period. Photo-induced electron transfer of special pair having electron acceptors and/or donors was also investigated by ultra fast laser photolysis. The special pair moiety is important for acceleration of charge separation and deceleration of charge recombination due to its small reorganization energy. Photo-voltaic cell was constructed on ITO electrode modified by TiO2 and special pairs, and arylphosphonic acid moiety attached to the special pair showed good performance. A supramolecular composite of macrocyclic porphyrin ring and tripyridyl ligand were constructed as a mimic of light-harvesting complex I-reaction center composite. Instead of porphyrin, a special pair composed of two imidazolylphthalocyanines was synthesized. Split of the Q-band in absorption spectrum and charge delocalization of one-electron oxidation state were observed. Acetylene-linked porphyrins having extremely strong two-photon absorption were synthesized. These can be useful for photodynamic therapy anti-cancer agents working at deep part and 3-dimetional optical data storage.
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