Series of Organic鈥揑norganic Hybrid Rare Earth Derivatives Based on [MnV13O38]7鈥?/sup> Polyoxoanion: Syntheses, Structures, and Magnetic and Electrochemical Properties

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• 作者：Ding Liu ; Ying Lu ; Hua-Qiao Tan ; Ting-Ting Wang ; En-Bo Wang
• 刊名：Crystal Growth & Design
• 出版年：2015
• 出版时间：January 7, 2015
• 年：2015
• 卷：15
• 期：1
• 页码：103-114
• 全文大小：1082K
• ISSN：1528-7505

文摘

A family of polyoxometalate compounds based on 1:13 polyoxoanions [MnV₁₃O₃₈]^{7鈥?/sup>, organic molecules, and lanthanide cations, H[{La₂(DMF)₅(H₂O)₄}{MnV₁₃O₃₈}]路DMF路5H₂O (1), H[{Ce₂(DMF)₂(H₂O)₇}{MnV₁₃O₃₈}]路0.5DMF路5.5H₂O (2), H₂[{K(H₂O)₂}₂{Nd(DMF)(H₂O)₃}{MnV₁₃O₃₈}]路5H₂O (3), H[{Ln₂(C₆H₅NO₂)₃(H₂O)₆}{[MnV₁₃O₃₈}]路C₆H₅NO₂路10H₂O (Ln = La 4, Ce 5), and H_2.5[{Pr(C₆H₅NO₂)(H₂O)_3.5}{Pr_0.5(H₂O)₂}{MnV₁₃O₃₈}]路0.5C₆H₅NO₂路10H₂O (6) (DMF = N,N-dimethylformamide; C₆H₅NO₂ = isonicotinic acid), have been obtained utilizing a conventional method of aqueous solution and further characterized by elemental analysis, IR spectrum, UV spectrum, thermogravimetric analysis, and single-crystal X-ray diffraction. Compounds 1 and 2 exhibit a one-dimensional extended chain structure constructed by [MnV₁₃O₃₈]7鈥?/sup> and lanthanide-organic coordination linkage, while compound 3 reveals three-dimensional (3D) open framework formed by polyoxoanion-lanthanide chains and potassium cations. Compounds 4鈥?b>6 exhibit 3D supramolecular framework architectures based on [MnV₁₃O₃₈]7鈥?/sup> polyoxoanions and lanthanide-organic coordination units. These compounds represent the first examples of extended organic鈥搃norganic hybrids built up by [MnV₁₃O₃₈]7鈥?/sup> building blocks and rare earth cations. The influences of the lanthanide contraction effect on the structural alterations from 1 to 3 and from 4 to 6 have been disscussed. The electrochemical and electrocatalytic properties for compounds 1鈥?b>6 have been studied. Magnetic studies indicate that antiferromagnetic interactions exist in compounds 1鈥?b>6.}