How do high nuclearity inorganic and supramolecular assemblies form? Is there a general route to explore the mechanism and how can one given compound dominate from a combinatorial explosion of possibilities? Take the example of a recent molecule discovered in our laboratory: A palladium oxometalate {Pd84}-ring cluster 3.3 nm in diameter; [Pd84O42(OAc)28(PO4)42]70- ({Pd84} = {Pd12}7) which is formed in water just by mixing two reagents at room temperature and can be observed in solution within a few days of mixing and crystallised a few days later, see Figure. Yet in terms of probability if, one just considers the Pd ions alone of which there are three types in this structure, then the probability of formation of the is extremely small. It is therefore perhaps safe to assume that the structure therefore did not 'spontaneously' form by random chance, but a series of templating events, combined with the correct kinetics, allowed this cluster to be selected from the vast envelope of possible structures available in solution under the conditions under study. In this lecture I will outline a new theory that I believe could underpin the formation of almost all large inorganic architectures and lead to new design approaches and understanding never been possible before. 

Exploring the roles of catalysis, templating and probability in the self assembly of giganatic inorganic clusters

247th National Meeting (2014)

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