Two Heterometallic Aggregates Constructed from the {P₂W₁₂}-Based Trimeric Polyoxotungstates and 3d-4f Heterometals

Reactions of hexavacant polyoxotungstate [H2P2W12O48]12− ({P2W12}) with transition-metal and lanthanide-metal cations assisted with organic molecules (tartrate or dimethylammonium chloride) lead to the isolation of two polyoxotungstates: K3Na8[K3⊂{GdMn(H2O)10}{HMnGd2(Tart)O2(H2O)15}{P6W42O151(H2O)7}]·44H2O (1) and K3Na10[K3⊂{GdCo(H2O)11}2{P6W41O148(H2O)7}]·43H2O (2). Single-crystal X-ray diffraction analyses reveal that both 1 and 2 contain a crown-type polyoxoanion shell [{WO(H2O)}3(P2W12O48)3]30− ({P6W39}), which consists of three {P2W12} units connected by three {WO(H2O)} linkers. Compound 1 has a two-dimensional porous framework constructed from 3d-4f cluster-containing {P6W39} aggregates and mixed 3d and 4f linkers. Compound 2 exhibits a one-dimensional chain-like structure composed of di-Co-containing {P6W39} aggregates and {Gd(H2O)7}3+ bridging units. Magnetic studies of compounds 1 and 2 indicate that antiferromagnetic interactions exist in these two compounds.