Template-Directed Assembly of Polyoxothiometalate Scaffolds into Nanomolecular Architectures†

A new family of nanomolecular clusters was obtained by using the squarate anion as a template for the self-assembly of [Mo2O2S2(H2O)6]2+ (A) with the structure-directing anion [Mo5O18]6− (B) whose geometry dictates the formation of the polyoxothiometalate building blocks [(Mo2O2S2)3(OH)4(C4O4)] and [(Mo2O2S2)2(OH)2(C4O4)]. A gradual evolution in both symmetry and structural completeness is observed upon traversing the generations of the POMcycle family.