Bottom-up construction of POM-based macrostructures: coordination assembled paddle-wheel macroclusters and their vesicle-like supramolecular aggregation in solution.

A bottom-up approach to obtain nanoclusters and large, uniform vesicle-like structures containing organic functionalized hexamolybdates in solution state were developed. Hexamolybdate functionalized carboxylic acid coordinated with two copper ions to form paddle-wheel tetrapolyoxometalate clusters with the features of macro-ions, which can spontaneously assemble into large, stable blackberry-type structures in suitable solvents, completing a hierarchical organization from small POM molecules to nanoscale complexes and then to supramolecular structures.