Three-Dimensional Architectures Based on Lanthanide-Substituted Double-Keggin-Type Polyoxometalates and Lanthanide Cations or Lanthanide-Organic Complexes

A family of three-dimensional (3D) architectures based on lanthanide-substituted polyoxometaloborate building blocks, [LnK(H(2)O)(12)][Ln(H(2)O)(6)](2)[(H(2)O)(4)LnBW(11)O(39)H](2)·20H(2)O (Ln = Ce 1, Nd 2), H(2)K(2)(H(2)O)(n)[(C(6)NO(2)H(5))Ln(H(2)O)(5)](2)[(H(2)O)(4)LnBW(11)O(39)H](2)·18H(2)O (Ln = Ce n = 8 3, Nd n = 9 4, C(6)NO(2)H(5) = 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 [{(H(2)O)(4)Ln(BW(11)O(39)H)}(2)](10-) linked by Ln(3+) cations to form a 3D open framework with one-dimensional (1D) channels. The polyoxoanion [{(H(2)O)(4)Ln(BW(11)O(39)H)}(2)](10-) consists of two α(1)-type mono-Ln-substituted Keggin anions, constituted by two [BW(11)O(39)H](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 [{(H(2)O)(4)Ln(BW(11)O(39)H)}(2)](10-) linked by the [Ln(C(6)NO(2)H(5))](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.