Studies on Photo-excited State valence Tautomerism of Multinuclear Metal Complexes by X-ray Crystallographic Analyses
| 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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Report
(3 results)
Research Products
(19 results)
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[Journal Article] A High-Conductivity Crystal Containing a Copper(I)Coordination Polymer Bridged by the Organic Acceptor TANG2006
Author(s)
Tadokoro, M., S. Yasuzuka, M. Nakamura, a. Shinoda, T. Tatenuma, M. Mitsumi, Y. Ozawa, K. Toriumi, H. Yoshino, D. Shiomi, K. Sato, T, Takui, T, Mori, K. Murata
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Journal Title
Angewandte Chemie, International Edition 45(31)
Pages: 5144-5147
Description
「研究成果報告書概要(和文)」より
Related Report
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[Journal Article] Direct Observation of Photochromic Dynamics in the Crystalline State of an Organorhodium Dithionite Complex2006
Author(s)
Nakai, H., M. Mizuno, T. Nishioka, N. Koga, K. Shiomi, Y. Miyano, M. Irie, B.K. Breedlove, I. Kinoshita, Y. Hayashi, Y. Ozawa, T. Yonezawa, K. Toriumi, K. Isobe
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Journal Title
Angewandte Chemie, International Edition 45(39)
Pages: 6473-6476
Description
「研究成果報告書概要(和文)」より
Related Report
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[Journal Article] A High-Conductivity Crystal Containing a Copper(l) Coordination Polymer Bridged by the Organic Acceptor TANC.2006
Author(s)
Tadokoro, M., S. Yasuzuka, M. Nakamura, a. Shinoda, T. Tatenuma, M. Mitsumi, Y. Ozawa, K. Toriumi, H. Yoshino, D. Shiomi, K. Sato, T. Takui, T. Mon, K. Murata
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Journal Title
ingewandte Chemie, International Edition 45(31)
Pages: 5144-5147
Description
「研究成果報告書概要(欧文)」より
Related Report
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[Journal Article] Isobe, Direct Observation of Photochromic Dynamics in the Crystalline State of al Organorhodium Dithionite Complex2006
Author(s)
Nakai, H., M. Mizuno, T. Nishioka, N. Koga, K.Shiomi, Y. Miyano, M. Irie, B. K. Breedlove, I. Kinoshita, Y. Hayashi, Y. Ozawa, T. Yonezawa, K. Toriumi, K.
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Journal Title
Angewandte Chemie, International Edition 45(39)
Pages: 6473-6476
Description
「研究成果報告書概要(欧文)」より
Related Report
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[Journal Article] Direct Observation of Photochromic Dynamics in the Crystalline State of an Organorhodium Dithionite Complex.2006
Author(s)
H.Nakai, M.Mizuno, T.Nishioka, N.Koga, K.Shiomi, Y.Miyano, M.Irie, B.K.Breedlove, I.Kinoshita, Y.Hayashi, Y.Ozawa, T.Yonezawa, K.Toriumi, K.Isobe
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Journal Title
Angewandte Chemie, International Edition 45・39
Pages: 6473-6476
Related Report
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