A series of 3D porous lanthanide-substituted polyoxometalate frameworks, Na2[Ln2(H2O)11]2[Ln3(H2O)3(α-SiW11O39)2]2·69H2O (1-Ln, Ln = Sm, Eu, Gd, Tb, and Dy), are built from novel hexadecahedral {Ln6W8O28} heterometallic cage-shaped clusters. Intriguingly, every tetrameric… Click to show full abstract
A series of 3D porous lanthanide-substituted polyoxometalate frameworks, Na2[Ln2(H2O)11]2[Ln3(H2O)3(α-SiW11O39)2]2·69H2O (1-Ln, Ln = Sm, Eu, Gd, Tb, and Dy), are built from novel hexadecahedral {Ln6W8O28} heterometallic cage-shaped clusters. Intriguingly, every tetrameric {[Ln3(H2O)3(α-SiW11O39)2]2}14- cage-cluster is linked with another eight tetrameric cage-clusters by Ln3+ cations, leading to a novel 3D inorganic porous framework, which exhibits good thermal and chemical stability, excellent water vapor adsorption capacity, and moderate proton conductive properties. Furthermore, the solid state luminescence spectra demonstrate that 1-Sm, 1-Eu, 1-Tb, and 1-Dy display the lanthanide characteristic emission bands. The temperature-dependent magnetic susceptibility indicates that there are antiferromagnetic interactions in 1-Tb and 1-Dy.
               
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