Supramolecular architectures built of triangular molybdenum(IV) heterometallic clusters encapsulating novel water clusters

The hydrothermal reaction of the dimolybdenum(V) Na2[Mo2O3S(HNTA)2] · 6H2O (1) and the lanthanide(III) ion yield the neutral trimolybdenum(IV) heterometalic cluster, [(H2O)8NdMo3O3S(HNTA)2(NTA)] · 7H2O (2) (NTA = nitrilotriacetato ligand). The addition reaction of Ag+ and [Mo3O4(C2O4)3(H2O)3]2− affords the anionic heterometallic cluster in N(C2H5)4[Ag(H2O)3Mo3O4(C2O4)3(H2O)3] · 5H2O (3). The H-bonded self-assemblies of the resulting asymmetric and larger heterometallic clusters form the 2D layered structure and 3D supramolecular open framework in 2 and 3, respectively, with larger pores to be stabilized by water clusters. These water clusters appear as (H2O)4 and (H2O)18 in 2 and (H2O)22 in 3.

Graphical abstractThe addition of the M(H2O)x moiety to the polycarboxylated [Mo3X4]4+ cluster has been observed in 2 and 3. The complementary H-bonded self-assemblies of the resulting asymmetric and larger heterometallic cluster yield 2D double layer and 3D supramolecular open framework of 2 and 3, respectively, with larger pores to be stabilized by water clusters.Figure optionsDownload full-size imageDownload as PowerPoint slide