Studies on Magneto-Photo Multifunctional System of Polynuclear Complexes Comprised by Discrete Metal Complexes
离散金属配合物多核配合物磁光多功能体系的研究
基本信息
- 批准号:10440196
- 负责人:
- 金额:$ 5.95万
- 依托单位:
- 依托单位国家:日本
- 项目类别:Grant-in-Aid for Scientific Research (B)
- 财政年份:1998
- 资助国家:日本
- 起止时间:1998 至 1999
- 项目状态:已结题
- 来源:
- 关键词:
项目摘要
A tetranuclear manganese(II,III) complex, [MnィイD22ィエD2(O)(PhィイD22ィエD2MeCCOO)(phen)ィイD22ィエD2]ィイD22ィエD2(PFィイD26ィエD2)ィイD22ィエD2 (2), has been assembled from a binuclear manganese(II) complex, [Mn(PhィイD22ィエD2MeCCOO)(phen)ィイD22ィエD2]ィイD22ィエD2(PFィイD26ィエD2)ィイD22ィエD2 (1) by use of a photo-induced oxidation reaction. Tetranuclear core in 2 consists of two μ-oxo-bis(μ-carboxylato)dimanganese units making a dimmer-of-dimers structure. The valence of the central and the terminal manganese atoms are assigned to +3 and +2, respectively. The core structure is stabilized by μィイD23ィエD2-oxo bridgeing and p-p stacking of phen as a terminal ligand. The oxidation reaction of 1 in a methanol/acetonitrile solution has been investigated by means of a photo-irradiation procedure using a super high-pressure mercury lamp. The solution gradually changes from yellow to dark brown, and a new intense absorption band appears at about 20x10ィイD13ィエD1cmィイD1-1ィエD1 with the passage of irradiation.Tetracopper complexes [CuL2H]ィイD24ィエD2 (3), [CuL2Me]ィイD24ィエD2 (4), and [CuL2Cl]ィイD24ィエD2 (5) with a reduced Schiff base type tridentate ligand HィイD22ィエD2L2X (X = H, 4-Me, 4-Cl) were prepared and characterized by elemental analyses and magnetic measurements. The crystal structure of 1 was determined by X-ray crystallography. Tetracopper core is represented as a dimer-of-dimers structure by the stacking of two dicopper nits bridged by alcoholic oxygens. Magnetic behaviors of the complexes are explained by modified equation based on the theoretical Spin Hamiltonian. The exchange integrals (-2J) are evaluated at 292μ 366 cmィイD1-1ィエD1 for SP dicopper cores and 104 - 120 cmィイD1-1ィエD1 for TBP, respectively, indicating the existence of different type of antiferromagnetic interaction-pathways corresponded to each copper geometry.
一种四核锰(II,III)配合物,[Mn D22 D2(O)](Phen D22)(Phen D22)(PF)D26 <$D2)D22 <$D2(2),由双核锰(II)配合物组装而成,[Mn(Phen)D22 MeCCOO)(Phen)D22] Mn D22 MeCCOO)(Phen)D22](Phen)D22 MeCCOO)(Phen)D22 MeCCOO)(Phen)2的四核核心由两个μ-氧代-双(μ-羧基)二锰单元组成,形成二聚体的二聚体结构。中心和末端锰原子的价态分别为+3和+2。其核心结构是通过μ π ι D23 π ι D2-氧桥和phen作为末端配体的p-p堆积来稳定的。用超高压汞灯光辐射法研究了1在甲醇/乙腈溶液中的氧化反应。随着照射时间的延长,溶液由黄色逐渐变为深棕色,在20 × 10 ~(-1)cm ~(合成了[CuL_2Cl]_(24)Cu_(24)Cu_(24)D_2(5)与还原的Schiff碱型三齿配体H_(22)Cu_(24)D_2L_2X(X = H,4-Me,4-Cl)的配合物,并通过元素分析和磁性测量对其进行了表征。通过X射线晶体学测定了化合物1的晶体结构。四铜核心表示为二聚体的二聚体结构,由醇氧桥连的两个二铜单元堆叠而成。基于自旋哈密顿量理论,用修正的方程解释了配合物的磁性行为。在292μ 366 cm λ D_1 -1 λ D_1处计算了SP双铜芯和104 - 120 cm λ D_1 -1 λ D_1处计算了TBP芯的交换积分(-2J),表明存在不同类型的反铁磁相互作用路径,对应于每种铜的几何构型。
项目成果
期刊论文数量(38)
专著数量(0)
科研奖励数量(0)
会议论文数量(0)
专利数量(0)
S.Nishino: "Selective Dioxygenation of Cyclohexane Catalysed by Hydrogen Peroxide and Dinuclear Iron(III) Complexes with μ-Alkoxo Bridges"Journal of Chemical Society,Dalton Transaction. 1509-1513 (1999)
S.Nishino:“过氧化氢和双核铁 (III) 配合物与 μ-Alkoxo Bridges 催化环己烷的选择性二氧化”,《化学学会杂志》,道尔顿汇刊 1509-1513 (1999)。
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S.Tomida, H.Matsushima, M.Koikawa, M.Koikawa and T.Tokii: "Assembly of a Tetetranuclear Mixed-Valence Manganese(II,III) Complex from a Binuclear Manganese(II) Complex by Photo-Irradiation"Chem. Lett.. 437-438 (1999)
S.Tomida、H.Matsushima、M.Koikawa、M.Koikawa 和 T.Tokii:“通过光辐照从双核锰 (II) 配合物组装四核混合价锰 (II,III) 配合物”Chem。
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M.Koikawa, K.B.Jensen, H.Matsushima, T.Tokii and H.Toftlund: "Synthesis and Crystal Structure of Divalent Complexes with a New hexadentate Ligand Derived from 1,4,7-Triazacyclononane"J. Chem. Soc., Dalton Trans.. 1085-1086 (1998)
M.Koikawa、K.B.Jensen、H.Matsushima、T.Tokii 和 H.Toflund:“具有源自 1,4,7-三氮杂环壬烷的新型六齿配体的二价配合物的合成和晶体结构”J。
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M.Kodera, Y.Tachi, T.Kita, H.Kobushi, Y.Sumi, K.Kano, M.Shiro, M.Koikawa, T.Tokii, M.Ohba and H.Okawa: "A Cu(II)-Mediated C-H Oxygenation of Sterically Hindered Tripyridine Ligands To Form Triangular Cu(II)|-D13-|D1 Complexes"Inorg. Chem.. 39. 226-234 (20
M.Kodera、Y.Tachi、T.Kita、H.Kobushi、Y.Sumi、K.Kano、M.Shiro、M.Koikawa、T.Tokii、M.Ohba 和 H.Okawa:“A Cu(II)
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Mohammad Yeamin Reza: "Synthesis and Crystal Structure of a NovelHexanuclear Zr(IV)Complexe with 1,10-Phenanthroline Including Carboxylato,Hydroxo,and Oxo Bridging" Polyhedron. 18. 787-792 (1999)
Mohammad Yeamin Reza:“具有 1,10-菲咯啉的新型六核 Zr(IV) 配合物的合成和晶体结构,包括羧基、羟基和氧桥接”多面体。
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TOKII Tadashi其他文献
TOKII Tadashi的其他文献
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{{ truncateString('TOKII Tadashi', 18)}}的其他基金
Studies on Molecular Building and Characterization of 1-st Dimensional Polynuclear Metal Complexes Comprised by Stacking Binuclear Units
双核单元堆叠组成的一维多核金属配合物的分子构建及表征研究
- 批准号:
08454212 - 财政年份:1996
- 资助金额:
$ 5.95万 - 项目类别:
Grant-in-Aid for Scientific Research (B)
Syntheses and Magnetic Properties of Ni(II) Dimers
Ni(II)二聚体的合成及磁性
- 批准号:
03640523 - 财政年份:1991
- 资助金额:
$ 5.95万 - 项目类别:
Grant-in-Aid for General Scientific Research (C)
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