2001 Fiscal Year Final Research Report Summary
Stereospecific assembly of chiral heterometallic dinuclear (3d - 4f) complexes
| Project/Area Number |
10304056
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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 |
Inorganic chemistry
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| Research Institution | Osaka University |
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Principal Investigator |
KAIZAKI Sumio Osaka University, Graduate School of Science, Professor, 大学院・理学研究科, 教授 (20089874)
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| Co-Investigator(Kenkyū-buntansha) |
SUZUKI Takayoshi Osaka University, Graduate School of Science, Research Associate, 大学院・理学研究科, 助手 (80249953)
FUYUHIRO Akira Osaka University, Graduate School of Science, Research Associate, 大学院・理学研究科, 助手 (90156951)
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| Project Period (FY) |
1998 – 2001
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| Keywords | radical complex / magnetic interaction / electronic spectrum / circular dichroism / stereospecific assembly / magnetic circular dichroism / hetero dinuclear complex |
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| Research Abstract |
The treatment of [Ln(hfac)3(H2O)2] (Ln(III) = Y, Nd - Lu) and IM-2py (2-(2-pyridyl)-4,4,5,5-tetramethyl-4,5-dihydro-1H-imidazolyl-1-oxyl) readily gave a series of the novel rare earth or lanthanide radical complexes [Ln(hfac)3(IM-2py)]. The molecular structures of the Sm, Gd, Dy, Er and Yb complexes have been determined to be bis capped trigonal pyrism(TPRS) by the X-ray diffraction. The magnetic susceptibility data for [Gd(hfac)3(IM-2py)] show that the Gd-IM-2py interaction is weakly antiferromagnetic with an exchange coupling constant J = -3.00 cm-1 in contrast to the ferromagnetic interaction in the Gd(III)-nitronyl nitroxide complexes. The n-π* transition of the IM-2py is found to shift to the lower frequency associated with intensity enhancement and vibronic structure. The luminescence measurement of the Eu(III) and Tb(III) demonstrated the energy transfers for the IM-2py(SOMO π*) → Ln(III)(4f) as a result of the emission quenching which depends on the energy gap of the excited levels in Ln(III) centers and IM-2py. These results reveal that the metal-radical interactions are very weak in the magnetic interaction but are relatively strong in the energy transfer.
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