Polyoxometalates are clusters of metal-oxide units, comprising a large diversity of nanoscale structures, and have many common building blocks; in fact polyoxometalate clusters are perhaps the largest non-biologically derived molecules structurally characterised. Not only can polyoxometalates have gigantic nanoscale molecular structures, but they also a have a vast array of physical properties, many of which can be specifically ‘engineered-in’. Here we describe how building block libraries of polyoxometalates can be used to construct systems with important catalytic, electronic, and structural properties. We also show that it is possible to construct complex chemical systems based upon polyoxometalates, manipulating the templating/self templating rules to exhibit emergent processes from the molecular to the macroscopic scale.

Polyoxometalate-based open frameworks (POM-OFs) are extended architectures incorporating metal-oxide cluster units and comprise an emergent family of materials with a large diversity of topologies, structural flexibility and functionality at the nanoscale.

A Hidden Template: The entropic challenge inherent in forming a ring-shaped molecule generally increases considerably with the size of the ring. Assuming that a linear precursor must bind its ends together, extending its length diminishes the likelihood of the opposite ends approaching one another. In the absence of an external force, how then can a family of molybdenum oxide rings, several nanometers in diameter (quite large at the molecular scale), self-assemble? Miras et al. (p. 72 , see the cover; see the Perspective by Whitmire ) have now uncovered an internal template guiding the process. By carefully controlling conditions in a flow reactor, they were able to halt the assembly process partway through and characterize a smaller molybdenum oxide core cluster, around which the larger ring was forming. Ejection of this template then yielded the hollow finished product.