Key Laboratory of Polyoxometalate Science of Ministry of Education, Department of Chemistry, Northeast Normal University, Changchun, Jilin 130024, PR China.
Dalton Trans. 2013 Apr 28;42(16):5839-47. doi: 10.1039/c3dt32658f.
Four heteropoly blue complexes constructed from Keggin-type heteropoly blue molybdenum-tungsten clusters and Cu(II) ions as linkers, H2[α-SiW10Mo(V)2O40][Cu(PDA)2·H2O]2 (1), H2[α-SiW10Mo(V)2O40][Cu(DEF)3·H2O][Cu(DEF)2·2H2O]·6H2O (2), H2[α-SiW10Mo(V)2O40][Cu(DMF)3H2O]2·6H2O (3), and H4[α-SiW10Mo(V)2O40]2[CuK2(DMF)6][Na0.75K3.25(DMF)6] (4) [PDA = propanediamide, DEF = N,N-diethylformamide and DMF = N,N-dimethylformamide], have been synthesized by conventional reactions and characterized by single-crystal X-ray diffraction, elemental analysis, IR spectroscopy, thermogravimetry, X-ray powder diffraction (XRD) and UV spectra. The amount of Cu(II) and the nature of the ligand (DMF, DEF and PDA) can control both the linkage pattern of Cu(II) ions and the dimensionality of the frameworks; this demonstrates for the first time the possibility to assemble heteropoly blue architectures in different dimensionality ranging from zero-dimensional (0D) to one-dimensional (1D), two-dimensional (2D) and three-dimensional (3D). The magnetic investigation showed that the positive magnetic moment could be observed at room temperature, which should be unusual results in magnetochemistry of the two-electron reduced heteropoly blue. The stability and formation conditions of the four compounds are also discussed.
四个杂多蓝配合物由 Keggin 型杂多钼钨簇和 Cu(II)离子作为连接物构建而成，H2[α-SiW10Mo(V)2O40][Cu(PDA)2·H2O]2（1）、H2[α-SiW10Mo(V)2O40][Cu(DEF)3·H2O][Cu(DEF)2·2H2O]·6H2O（2）、H2[α-SiW10Mo(V)2O40][Cu(DMF)3H2O]2·6H2O（3）和 H4[α-SiW10Mo(V)2O40]2[CuK2(DMF)6][Na0.75K3.25(DMF)6]（4）[PDA = 丙二酰胺，DEF = N，N-二乙基甲酰胺和 DMF = N，N-二甲基甲酰胺]，通过常规反应合成并通过单晶 X 射线衍射、元素分析、IR 光谱、热重分析、X 射线粉末衍射（XRD）和 UV 光谱进行了表征。Cu(II)的量和配体（DMF、DEF 和 PDA）的性质可以控制 Cu(II)离子的连接方式和框架的维度；这首次证明了在不同维度上组装杂多蓝结构的可能性，从零维（0D）到一维（1D）、二维（2D）和三维（3D）。磁性研究表明，在室温下可以观察到正磁矩，这在两电子还原杂多蓝的磁化学中应该是不寻常的结果。还讨论了四个化合物的稳定性和形成条件。
