| 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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| Project Status |
Completed (Fiscal Year 2001)
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| Budget Amount *help |
¥31,700,000 (Direct Cost: ¥30,800,000、Indirect Cost: ¥900,000)
Fiscal Year 2001: ¥3,900,000 (Direct Cost: ¥3,000,000、Indirect Cost: ¥900,000)
Fiscal Year 2000: ¥3,400,000 (Direct Cost: ¥3,400,000)
Fiscal Year 1999: ¥11,800,000 (Direct Cost: ¥11,800,000)
Fiscal Year 1998: ¥12,600,000 (Direct Cost: ¥12,600,000)
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| Keywords | radical complex / magnetic interaction / electronic spectrum / circular dichroism / stereospecific assembly / magnetic circular dichroism / hetero dinuclear complex / ランタニド-遷移金属錯体 / エネルギー移動 / クロム(III)錯体 / ニッケル(II)錯体 / ランタニド遷移金属多核錯体 / ランタニド-遷移金属多核錯体 |
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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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