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

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