are built from novel hexadecahedral {Ln 6 W 8 O 28 } heterometallic cage-shaped clusters. Intriguingly, every tetrameric {[Ln 3 (H 2 O) 3 (α-SiW 11 O 39 ) 2 ] 2 } 14− cage-cluster is linked with another eight tetrameric cage-clusters by Ln 3+ 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.

The assembly of heterometallic cluster substituted polyoxometalates (POMs) remains a great challenge for inorganic synthetic chemistry up to now. Herein, a series of 5p–4f heterometallic cluster substituted POMs were successfully isolated by a facile one-step hydrothermal reaction method, namely H17(H2en)3[SbIII 9SbVLn3O14(H2O)3]­[(SbW9O33)3(PW9O34)]·28H2O­(1-Ln, Ln = Ce, Sm, Eu, Gd, Tb, Dy) (en = ethylenediamine). Interestingly, by replacing en with imidazole, another series of 5p–4f heterometallic cluster substituted POMs H13(HIm)4K2Na4(H2O)9[SbIII 9SbVLn3O14(H2O)3]­[(SbW9O33)3(PW9O34)]·26H2O (2-Ln, Ln = Sm, Eu, Gd, Tb, Dy, Im = imidazole) were obtained. Structural analyses indicate that both 1-Ln and 2-Ln are made up of an unprecedented 5p–4f heterometallic {Sb10Ln3O14(H2O)3} cluster stabilized simultaneously by mixed trilacunary heteropolyanions including {A-α-PW9O34} and {B-α-SbW9O33}. Impedance measurements indicate that both compounds exhibit different proton conduction properties, and the conductivity of 2 can reach up to 1.64 × 10–2 S cm–1 at 85 °C under 98% relative humidity. Moreover, the fluorescence emission behaviors of both compounds have been studied.

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Two novel inorganic-organic hybrid 3-D TM-Ln incorporated POM-based frameworks, H2[Cu2OL3(H2O)2][Ce(L)(H2O)3(PW11O39)]·17H2O (1) and H4[CuL3]2[Ln(H2O)3(PW11O39)]2·28H2O (2), (L = 4,4'-bipyridine) were hydrothermally synthesized at different temperatures. Structural analysis reveals that both compounds are...

This study reported a series of cube-shaped polyoxoniobates, {MCu12O8)(Cu12XmOn)(Nb7(OH)O21)8} [M = Nb(1, 2), Ln3+(3), X = I(1, m = 3, n = 3; 2, m = 5, n = 1), Br(3, m = 5, n = 1)]. As the first octahedral Cu12XmOn cluster incorporated polyoxoniobate, the cube-shaped three-shell structure of {MCu12O8)(Cu12XmOn)(Nb7(OH)O21)8} polyanion contains a {MCu12O8} body-centered cuboctahedron, a {Cu12XmOn} octahedron and a {Cu12(Nb7(OH)O21)8} cube. Compounds 1, 2, 3 show effective catalytic activities for the hydrolytic decomposition of chemical warefare agent simulants.