| 二聚结构[(CH3)4N]4[PW11O39H2La(H2O)4]2·3H2O的合成、结构及性质 |
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| 引用本文： | 张少伟,马鹏涛,陈幻妮,王敬平,牛景杨. 二聚结构[(CH3)4N]4[PW11O39H2La(H2O)4]2·3H2O的合成、结构及性质[J]. 科学通报, 2011, 56(9): 652-657. DOI: 10.1360/972010-2056 |
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| 作者姓名： | 张少伟 马鹏涛 陈幻妮 王敬平 牛景杨 |
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| 作者单位： | 河南大学化学化工学院分子与晶体工程研究所; |
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| 基金项目： | 国家自然科学基金(20771034,20773035); 教育部博士点基金(200804750003)资助项目 |
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| 摘 要： | 以α-Na7PW11O39·nH2O, LaCl3·7H2O 和(CH3)4NCl 为原料, 利用常规水溶液方法合成了 2:2 型二聚的单缺位Keggin 结构稀土衍生物[(CH3)4N]4[PW11O39H2La(H2O)4]2·3H2O (1). X 射线 单晶衍射结果表明, 该晶体属三斜晶系, P-1 空间群, 晶胞参数: a = 1.35383(10) nm, b = 1.60687(12) nm, c = 1.86958(13) nm, α = 65.9630(10)°, β = 83.1650(10)°, γ = 83.6780(10)°, Z = 1, R1 = 0.0589, wR2 = 0.1447. 二聚阴离子{[(α-PW11O39H2)La(H2O)4]2}4-由2个[α-PW11O39]7-缺位阴 离子通过2 个[La(H2O)4]3+配离子连接形成, La3+离子占据[α-PW11O39]7-阴离子的缺位位置, 采 用九配位单加冠四方反棱柱构型, 相邻的2 个单取代阴离子[α-PW11LaO39]4-通过2个La –Ot –W 桥连成二聚物. 热重分析结果表明, 化合物1 在25～600℃范围内表现为两步失重; 循环伏安 行为表明, 化合物1 阴离子在pH 4.3 的水溶液中存在两步可逆的单电子还原过程.
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| 关 键 词： | 多金属氧酸盐 单缺位 Keggin 结构 稀土离子 二聚 |
| 收稿时间： | 2010-11-04 |
Syntheses, crystal structure and properties of the dimeric [(CH3)4N]4[PW11O39H2La(H2O)4]2 · 3H2O |
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| ZHANG ShaoWei,MA PengTao,CHEN HuanNi,WANG JingPing , NIU JingYang Institute of Molecular , Crystal Engineering,College of Chemistry , Chemical Engineering,Henan University,Kaifeng ,China. Syntheses, crystal structure and properties of the dimeric [(CH3)4N]4[PW11O39H2La(H2O)4]2 · 3H2O[J]. Chinese Science Bulletin, 2011, 56(9): 652-657. DOI: 10.1360/972010-2056 |
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| Authors: | ZHANG ShaoWei MA PengTao CHEN HuanNi WANG JingPing & NIU JingYang Institute of Molecular Crystal Engineering College of Chemistry Chemical Engineering Henan University Kaifeng China |
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| Affiliation: | ZHANG ShaoWei,MA PengTao,CHEN HuanNi,WANG JingPing & NIU JingYang Institute of Molecular and Crystal Engineering,College of Chemistry and Chemical Engineering,Henan University,Kaifeng 475004,China |
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| Abstract: | 2:2-type dimeric [(CH3)4N]4[PW11O39H2La(H2O)4]2·3H2O was successfully synthesized by reaction of the monovacant Keggin structure α-Na7PW11O39·nH2O with LaCl3·7H2O and (CH3)4NCl in aqueous solution. Single crystals of this compound were analyzed by X-ray crystallography and found to be in the triclinic space group P1 with the following parameters: a = 1.35383(10) nm, b = 1.60687(12) nm, c= 1.86958(13) nm, α= 65.9630(10)°, β = 83.1650(10)°, γ= 83.6780(10)°, Z = 1, R1 = 0.0589, wR2 = 0.1447. The dimeric polyoxoanion [{(α-PW11O39H2)La(H2O)4}2]4– consisted of two [α-PW11O39]7- subunits linked together by two [La(H2O)4]3+ cations. The nine-coordinate La3+ cation was incorporated in the vacant site of the [α-PW11O39]7- subunit, which adopted monocapped square antiprismatic coordination geometry. Thermogravimetric analysis exhibited two weight loss steps between 25 and 600°C; cyclic voltammetry indicated that two reversible single-electron reductions of the synthesized compound occurred in aqueous solution at pH 4.3. |
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| Keywords: | polyoxometalates monovacant keggin lanthanide cations dimeric |
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