| Project/Area Number |
09640608
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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 |
Physical chemistry
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| Research Institution | Osaka University |
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Principal Investigator |
YOSHIMURA Akio Osaka University, Graduate School of Science, Research Associate, 大学院・理学研究科, 助手 (00029737)
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| Project Period (FY) |
1997 – 1998
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| Project Status |
Completed (Fiscal Year 1998)
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| Budget Amount *help |
¥3,200,000 (Direct Cost: ¥3,200,000)
Fiscal Year 1998: ¥800,000 (Direct Cost: ¥800,000)
Fiscal Year 1997: ¥2,400,000 (Direct Cost: ¥2,400,000)
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| Keywords | Supramolecule / Electron Transfer / Reorganization Energy / Intramolecular Reorganization / Solid State Reaction / Laser Photochemistry |
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| Research Abstract |
Purpose of this work is to clarify the intramolecular reorganization energy of the photo-induced electron transfer (ET) reaction from the laser-trabsient absorption spectroscopy of supramolecules in the crystal state where outer sphere reorganization of solvents is excluded and the atomic arrangement is fixed. To attain the uniform excitation, microcrystals of supramolecules are ground together with KCl crystal and pressed under more than 7 ton/cm^2. The thermal conductivity of KCl is higher than that of KBr, so KCl is better to avoid the thermal decomposition of the sample. The isolated solid state was also examined for the supramolecule adsorbed on the silica gel in a low coverage prepared using sol-gel method. In these measurements under the uniform excitation condition, it was possible to determine the concentration of the excited state formed. This means the quantitave analysis is also possible in the investigation of emission change. By the excitation of Ru(bpy)_3^<2+> in the microcrystal, the T-T annilation between the excited compounds at the closest distance occurred in a couple of ten picosecond. The second order component due to T-T rection was also observed in the highly concentrated solution in a thin cell. These T-T reactions were examined and the FT products (Ru^<3+> and Ru^<1+>) were detected in the reaction. The supramolecules with Ru(II) and Co(III) were examined mainly, where the back FT (normal- region) was slow due to the high inner reorganization for the process of Co(II) to Co(III). If the ET in the supramolecule is faster, then T-T contribution is less. So the donor-a ceeptor compounds of Ru(II) and Co(III) connected by a ligand composed of conjugated pi-el ectron system, with the strong interaction and ligid structure were synthesized and examined.
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