| Project/Area Number |
17550065
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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 |
Inorganic chemistry
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| Research Institution | University of Hyogo |
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Principal Investigator |
OZAWA Yoshiki University of Hyogo, Department of Material Science, Associate Professor (40204200)
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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 |
¥3,200,000 (Direct Cost: ¥3,200,000)
Fiscal Year 2006: ¥700,000 (Direct Cost: ¥700,000)
Fiscal Year 2005: ¥2,500,000 (Direct Cost: ¥2,500,000)
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| Keywords | X-ray structure analysis / photo-excited states / multinuclear metal complex / Copper compound / luminescent Properties / synchrotron radiation / metal-organic framework / 金属錯体 / 結晶構造 / 単結晶X線構造解析 / 放射光 / 多核銅錯体 / 原子価互変異性 / X線構造解析 / 光物性 / 物性実験 |
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| Research Abstract |
Although syntheses and crystallization of iodo-bridged platinum(II),(IV) bis-diamine complex have been performed, no good crystal sample for photo-excited crystallographic studies was successfully obtained. Instead, photo-excited state X-ray diffraction studied for luminescent halogen-bridged copper(I) polymer complexes have been progressed. Luminescent dicopper(I) complexes [Cu_2X_2(PPh_3)_2L]∞(X=I, Br, Cl; L=bipyridine or pyradine) consist of {Cu_2X_2} rhombic units, which are bridged by diimine ligands constructing an infinite chain structure. The origin of emission bands are assigned mainly to a Cu(I) to ligand charge transfer (MLCT) and a halogen to ligand (XLCT) excited states. Single crystal X-ray diffraction experiments under photo-illumination for the iodine-complex [Cu_2I_2(PPh_3)_2(bpy)]∞ have shown that two iodine atoms are moved toward close to each other within the {Cu_2I_2} plane. The same manner in the motion of the metal and halogen atoms have found in [Cu_2I_2(PPh_3)_2(pyz)]∞. While in the case of a related discrete complex [Cu_2I_2(PPh_3)(pyz)_2] which has the same {Cu_2I_2} indicate that a very small portion of {Cu_2I_2} core in the crystal is rotated with little bond enlarge or shrinkage. There are no significant geometrical distortion has found in another discrete complex [Cu_2I_2(PPh_3)(Ph-py)_2] which shows intense luminescence which is assigned to a different nature as a ligand π-π* transition state. Some significant correlations have been revealed between excited-state structure changes and ground state geometries in the {Cu2I2} framework, which are also related with their luminescent properties.
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