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

Abstract

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.

State-of-the-art advances in the syntheses, structures, and applications of polyoxometalate-based metal–organic frameworks

“…Anderson-type POM-MOFs have also attracted increasing interest. [112][113][114][115][116][117][118][119] In 2016, Wang et al 19a). 116 Furthermore, this material can serve as an electrocatalyst and used for electrocatalytic reduction of NO2 -, Cr(VI) and BrO3as well as the electrocatalytic oxidation of ascorbic acid.…”

“…18g). Apart from the most commonly used copper ions, Powell et al launched the study on the reactivity of RE cations with carboxylate-functionalized Anderson-type precursor [N(n-C4H9)4]4[(MnMo6O18)(HL)(L)] (H4L = 4-(((1,3-dihydroxy-2-(hydroxymethyl)-propan-2-yl)amino)methyl)benzoic acid) and discovered two families of 3-D POM-MOFs [RE(DMF)6RE(DMF)5RE3(DMF)10[(MnMo6O18)(L)2]3•xDMF (RE = La 3+ -Nd 3+ ) and [RE(DMF)4(H2O)]2[RE3(DMF)6][(MnMo6O18)(L)2]3•xDMF (RE = Y 3+ , Sm 3+ -Lu 3+) 119. The difference of these two kinds of Anderson-type POM-MOFs mainly stems from the lanthanide contraction.…”

“…113 (e) 3-D framework of [(CH3)2NH2]3[Co5(µ3-O)2(L b )6][MnMo6O18(L a )2]•5DMF highlighting tetragonal channels. 113 (f) 2-D sheet of (TBA)n{[Cu(PPh3)2]2[MnMo6O18((OCH2)3CN=CH-3-Py)2]}n•(2DMF)n. 114 (g) 2-D sheet of {[Cu(PPh3)2]3[MnMo6O18 ((OCH2)3CN=CH-3-Py)2]•(CH3CN)}n•(5CH3CN)n. 114 (h) Coordination of a {RE3(DMF)10/6} 9+ cluster and six {MnMo6O18}BBs 119.…”

Latest progress in covalently modified polyoxometalates-based molecular assemblies and advanced materials

“…Covalently modified POMs can further form hybrid functional materials containing frameworks [31][32][33][34] , polymers and other nanostructures [35][36][37][38][39] by coordination assembling with metal ions or metal clusters. Metal-organic frameworks (MOFs) were a kind of porous crystalline materials, which were formed by self-assembly of metal ions/clusters with organic ligands via coordination bonds.…”

“…Forgan et al reported the coordination assembly of pyridine-appended Mn-Anderson clusters with Zn 2+ and Cu 2+ into two-and three-dimensional network solids with connectivity and topology [31] . The covalently modified POMs can also be coordinated with Cu + , Ag + , Fe 2+ , lanthanide ions and metal clusters [32][33][34]40] . Discrete supramolecular coordination complexes were prone to form multilevel self-assembled structures through non-covalent interactions.…”