Polyoxometalates (POMs) are a subset of metal oxides with unique physical and chemical properties, which can be reliably modified through various techniques and methods to develop sophisticated materials and devices. In parallel with the large number of new crystal structures reported in the literature, the application of these POMs towards multifunctional materials has attracted considerable attention. This critical review summarizes recent progress on POM-based molecular and composite materials, and particularly highlights the emerging areas that are closely related to surface, electronic, energy, environment, life science, etc. (171 references).

Mn-Anderson-C6 and Mn-Anderson-C16, A type of inorganic-organic hybrid molecules containing a large anionic polyoxometalate (POM) cluster and two C6 and C16 alkyl chains, respectively, demonstrate amphiphilic surfactant behavior in the mixed solvents of acetonitrile and water. The amphiphilic hybrid molecules can slowly assemble into membrane-like vesicles by using the POM clusters as polar head groups, as studied by laser light scattering and TEM techniques. The hollow vesicles have a typical bilayer structure with the hydrophilic Mn-Anderson cluster facing outside and long hydrophobic alkyl chains staying inside to form the solvent-phobic layer. Due to the rigidity of the POM polar heads, the two alkyl tails have to bend significantly for the vesicle formation, which makes the vesicle formation more difficult compared to some conventional surfactants. This is the first example of using hydrophilic POM macroions as polar head groups for a surfactant system.

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