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.

Controllable self-assembly of organic-inorganic amphiphiles containing Dawson polyoxometalate clusters.

An organic-inorganic molecular hybrid containing the Dawson polyoxometalate, ((C(4)H(9))(4)N)(5)H[P(2)V(3)W(15)O(59)(OCH(2))(3)CNHCOC(15)H(31)], was synthesized and its surfactant-like amphiphilic properties, represented by the formation of bilayer vesicles, were studied in polar solvents. The vesicle size decreases with both decreasing hybrid concentration and with increasing polarity of the solvent, independently. The self-assembly behavior of this hybrid can be controlled by introducing different counterions into the acetonitrile solutions.