Cation-Directed Synthetic Strategy Using 4f Tungstoantimonates as Nonlacunary Precursors for the Generation of 3d–4f Clusters

The first synthetic pathway using a series of four nonlacunary 4f-heterometal-substituted polyoxotungstate clusters Na₂₁[(Ln­(H₂O)­(OH)₂(CH₃COO))₃(WO₄)­(SbW₉O₃₃)₃]·nH₂O (NaLnSbW₉; Ln = Tb^III, Dy^III, Ho^III, Er^III, Y^III) as precursors for the directed preparation of nine new 3d–4f heterometallic tungstoantimonates K₅Na₁₂H₃[TM­(H₂O)­Ln₃(H₂O)₅(W₃O₁₁)­(SbW₉O₃₃)₃]·nH₂O (KTMLnSbW₉; TM = Co^II, Ni^II; Ln = Tb^III, Dy^III, Ho^III, Er^III, Y^III) has been developed. Systematic studies revealed an increased K content in the aqueous acidic reaction mixture to be the key step in the cation-directed preparation of 3d–4f compounds; among those, the Co-containing members represent the first examples of KCoLnSbW₉ (Ln = Tb^III, Dy^III, Ho^III, Er^III, Y^III) heterometallic tungstoantimonates exhibiting the SbW₉ building block. All 13 compounds have been characterized thoroughly in the solid state by powder and single-crystal X-ray diffraction (XRD), revealing a cyclic trimeric polyoxometalate architecture with three SbW₉ units encapsulating a planar triangle of Ln^III ions in the case of NaLnSbW₉ and a heterometallic core of one TM^II and three Ln^III for KTMLnSbW₉ (TM = Co^II, Ni^II; Ln = Tb^III, Dy^III, Ho^III, Er^III, Y^III). The results obtained by XRD are supplemented by complementary characterization methods in the solid state such as IR spectroscopy, thermogravimetric analysis, and elemental analysis as well as in solution by UV–vis spectroscopy. Detailed magnetic studies on the representative compounds KTMDySbW₉ (TM = Co^II, Ni^II) and KCoYSbW₉ of the series revealed field-induced slow magnetic relaxation.