Taking the Third Route for Construction of POMOFs: The First Use of Carboxylate-Functionalized MnIII Anderson–Evans POM-Hybrid Linkers and Lanthanide Nodes

The purpose of the present contribution is to illustrate how to design and grow crystals of POMOFs based on POM-hybrid linkers with lanthanide ions as nodes. Thus, the MnIII-centered Anderson–Evans polyoxometalate (Mn-A-E-POM) was functionalized with 4-(((1,3-dihydroxy-2-(hydroxymethyl)­propan-2-yl)­amino)­methyl)­benzoic acid (H4L) to afford the hybrid inorganic–organic POM [N­(n-C4H9)4]4[(MnMo6O18)­(HL)­(L)] (1), which in turn reacts with lanthanide salts and yields two three-dimensional frameworks with the general formulas Ln­(DMF)6­Ln­(DMF)5­Ln3(DMF)10­[(MnMo6O18)­(L)2]3·xDMF (2; Ln = La–Nd) and [Ln­(DMF)4­(H2O)]2­[Ln3(DMF)6]­[(MnMo6O18)­(L)2]3·xDMF (3; Ln = Y, Sm–Lu). The differentiation in these two families results from the lanthanide contraction. The crystallization process is crucial for obtaining these two families in a bulk pure phase. Family 2 can be obtained by stirring, while for family 3 the less energy demanding layering method proved to be the most efficient pathway. Notably, the change in the ionic radii causes a change in space group (from P21 (family 2) to P21/c (family 3); however, the topology of the frameworks is unaffected.