| Project/Area Number |
02044011
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| Research Category |
Grant-in-Aid for international Scientific Research
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| Allocation Type | Single-year Grants |
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| Section | Joint Research |
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| Research Institution | Tohoku University |
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Principal Investigator |
AZUMI Tohru Tohoku University, Professor, 理学部, 教授 (90013490)
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| Co-Investigator(Kenkyū-buntansha) |
GLENN A. GRO ワシトン州立大学, 化学科, 教授
IKEYAMA Takeshi Miyagi University of Education, Associate Professor, 助教授 (50159646)
MAEDA kiminori Tohoku University, Assistant Professor, 理学部, 助手 (70229300)
CROSBY Glenn A. Washington State University, Professor
池田 滋 東北大学, 大学院・理学研究科, 博士課程後期1年
CROSBY Glenn ワシントン州立大学, 化学科, 教授
寺嶋 正秀 京都大学, 理学部, 講師 (00188674)
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| Project Period (FY) |
1990 – 1992
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| Project Status |
Completed (Fiscal Year 1992)
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| Budget Amount *help |
¥7,900,000 (Direct Cost: ¥7,900,000)
Fiscal Year 1992: ¥2,700,000 (Direct Cost: ¥2,700,000)
Fiscal Year 1991: ¥2,700,000 (Direct Cost: ¥2,700,000)
Fiscal Year 1990: ¥2,500,000 (Direct Cost: ¥2,500,000)
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| Keywords | Zn / Cd / Rh / Closed shell electron configuration / Triplet sublevel / Phenanthroline / Zero field magnetic resonance / Phosphorescence / 混合配位子錯体 / 閉殻金属イオン / 三重項励起状態 / 光検出磁気共鳴 / ゼロ磁場分裂 / Zn錯体 / フェナントレン錯体 / チオフェノ-ル錯体 / ゼロ磁場分裂定数 / フェナントレン / チオフェノ-ル |
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| Research Abstract |
Spectroscopic and magnetic properties have been investigated for complexes of d^<10> closed shell metal ions, and the results of significance are summarized as follows.
(1) Mixed ligand complexes of the type Zn(X-PhS)_2(phen)
The triplet sublevels associated with the lowest ligand charge transfer (LLCT) triplet excited state have been investigated for a series of the complexes of the type Zn(X-PhS)_2(phen), where X is a substituent on the benzenthiol ligand and phen is 1,10-phenanthroline. The zero field splitting parameters D* are significantly larger than the values calculated quantum mechanically based on a model of pure charge transfer state. This discrepany suggests that the phen localized pipi* states mixes with the LLCT state. The degree of mixing is obtained based on this mixing mechanism from the results of both the lifetime and the zero field splitting. The mixing coefficients determined show a good and expected correlation with the electron donating ability of the substituent X on benzenethiol. Thus, the participation of LLCT to phen localized pipi* state is well substantiated.
(2) Complexes of the type MX_2(phen)
Fluorescence and the triplet sublevel properties have been investigated for a series of complexes of the type MX_2(phen), where M is Zn(II) or Cs(II) and X is C1, Br, or I. The fluorescence lifetime, zero field splittings,and the radiative rate constants for sublevels are all interpreted satisfactorily by a theoretical model in which the phen localized pipi* state mixes with charge transfer state arising from the electron promotion from p orbital of halogen to pi* orbital phen.
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