Three-Dimensional Architectures Based on Lanthanide-Substituted Double-Keggin-Type Polyoxometalates and Lanthanide Cations or Lanthanide-Organic Complexes
Three-Dimensional Architectures Based on Lanthanide-Substituted Double-Keggin-Type Polyoxometalates and Lanthanide Cations or Lanthanide-Organic Complexes
复制标题
基于稀土取代双Keggin型多金属氧酸盐和稀土阳离子或稀土有机配合物的三维结构
DOI：
10.1021/ic1013335
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发表时间：
2010-12-20
影响因子：
4.6
通讯作者：
Xu, Tieqi
中科院分区：
文献类型：
--
作者：
An, Haiyan;Han, Zhengbo;Xu, Tieqi
基于镧系元素取代的多氧杂硼酸盐构建块的三维（3D）结构族，[LnK（H2O）（12）][Ln（H2O）（6）]（2）[（H2O）（4）LnBW（11）O（39）H]（2）中心点20 H（2）O（Ln = Ce 1，Nd 2），H2K2（H2O）n[（C6NO2H5）Ln（H2O）（5）]（2）[（H2O）（4）LnBW（11）O（39）H]（2）中心点18H（2）O（Ln = Ce n = 8 3，Nd n = 9 4，C6 NO2 H5 =吡啶-4-羧酸）的合成，并通过元素分析、红外光谱、热重分析粉末X射线衍射和单晶X射线衍射。化合物1和2是同结构的，由镧系元素取代的双Keggin型多氧阴离子[{（H2O）（4）Ln（BW 11 O39 H）}（2）]（10-）通过Ln（3+）阳离子连接形成具有一维（1D）通道的3D开放骨架。Th 9多氧阴离子[{（H2O）（4）Ln（BW 11 O 39 H）}（2）]（10-）由两个α（1）型单Ln取代Keggin阴离子组成，由两个[BW 11 O 39 H]（8-）多氧阴离子和两个镧系阳离子组成。在1、2的反应体系中加入吡啶-4-羧酸配体，得到化合物3、4。同结构化合物3和4由镧系元素取代的双Keggin型多氧阴离子[{（H2O）（4）Ln（BW 11 O39 H）}（2）]（10-）通过[Ln（C6 NO2 H5）]（3+）桥连接形成三维通道骨架。从拓扑学的角度来看，化合物1-4的3D网络是具有三个和六个连接节点的双节点的，并且表现出金红石拓扑。化合物1-4代表基于镧系元素取代的聚氧杂环丁烷酸盐的3D结构的实例。通过测量化合物1-4在2-300 K温度范围内的磁化率，研究了化合物1-4的磁性。
A family of three-dimensional (3D) architectures based on lanthanide-substituted polyoxometaloborate building blocks, [LnK(H2O)(12)][Ln(H2O)(6)](2)[(H2O)(4)LnBW(11)O(39)H](2)center dot 20H(2)O (Ln = Ce 1, Nd 2), H2K2(H2O)n[(C6NO2H5)Ln(H2O)(5)](2)[(H2O)(4)LnBW(11)O(39)H](2)center dot 18H(2)O (Ln = Ce n = 8 3, Nd n = 9 4, C6NO2H5 = pyridine-4-carboxylic acid), have been synthesized and characterized by elemental analysis, IR spectroscopy, thermogravimetric (TG) analysis, powder X-ray diffraction and single crystal X-ray diffraction. Compounds 1 and 2 are isostructural, and are built up of lanthanide-substituted double-Keggin-type polyoxoanions [{(H2O)(4)Ln(BW11O39H)}(2)](10-) linked by Ln(3+) cations to form a 3D open framework with one-dimensional (1D) channels. Th9 polyoxoanion [{(H2O)(4)Ln(BW11O39H)}(2)](10-) consists of two alpha(1)-type mono-Ln-substituted Keggin anions, constituted by two [BW11O39H](8-) polyoxoanions and two lanthanide cations. When pyridine-4-carboxylic acid ligand was added to the reaction system of 1, 2, compounds 3, 4 were obtained. Isostructural compounds 3 and 4 are constructed from the lanthanide-substituted double-Keggin-type polyoxoanions [{(H2O)(4)Ln(BW11O39H)}(2)](10-) linked by the [Ln(C6NO2H5)](3+) bridges to form a 3D channel framework. From the topological point of view, the 3D nets of compounds 1-4 are binodal with three- and six-connected nodes and exhibit a rutile topology. Compounds 1-4 represent the examples of 3D architectures based on lanthanide-substituted polyoxometalates. The magnetic properties of compounds 1-4 have been studied by measuring their magnetic susceptibility in the temperature range 2-300 K.