| Project/Area Number |
15550055
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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 | Chiba Institute of Technology |
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Principal Investigator |
TSUCHIMOTO Masanobu Chiba Institute of Technology, Faculty of Engineering, Associate Professor, 工学部, 助教授 (10255599)
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| Project Period (FY) |
2003 – 2005
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| Project Status |
Completed (Fiscal Year 2005)
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| Budget Amount *help |
¥3,200,000 (Direct Cost: ¥3,200,000)
Fiscal Year 2005: ¥900,000 (Direct Cost: ¥900,000)
Fiscal Year 2004: ¥900,000 (Direct Cost: ¥900,000)
Fiscal Year 2003: ¥1,400,000 (Direct Cost: ¥1,400,000)
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| Keywords | lanthanide / vanadium / hetero multinuclear complexes / synthesis / multi-electron redox reaction / fluorescence / ヘテロ多核金属錯体 / 発光 / ランタノイドイオン / バナジウム錯体 / 磁性 |
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| Research Abstract |
A V(V)-Ce(IV)-V(V) trinuclear complex, [{V^VO_2(L)} _2Ce^<IV>] and V(V)-Ln(III)-Ln(III)-V(V) tetranuclear complexes, [{V^vO_2 (L)Ln^<III>(acac)}_2(H_2O)]{Ln=Eu, Gd, Tb ; H_3L : N,N'-bis-3-ethoxysalicylidene-2-hydroxy-1,3-propanediamine ; Hacac:2,4-pentanedione} were prepared. The structures of the complexes were determined by X-ray crystal structure analysis. The basal oxo atoms of the dioxovanadium(V) moieties are coordinated to the central lanthanide ions to form trinuclear or tetranuclear structures. However, the vanadium-basal oxo atom distance of the V(V)-Ce(IV) trinuclear complex (1.711(3)Å) is longer than those of the V(V)-Ln(III) teranuclear complexes (1.664(4)-1.675(4)Å). The basal oxo atoms of the V(V)-Ce(IV) trinuclear complex are coordinated to the Ce(IV) ion more strongly than those of the V(V)-Ln(III) tetranuclear complexes to the Ln(III) ions. The difference between the structures of trinuclear and tetranuclear complexes can be related to the different oxidation states of the lanthanide ions. The cyclic voltammogram of the V(V)-Ce(IV) trinuclear complex shows a quasi-reversible two-electron redox couple with E_<1/2> = -0.60 V vs. Fc/Fc^+. Solvent-dependent fluorescence was observed for the V(V)-Tb(III) tetranuclear complex.
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