A variety of metal-based clusters can be incorporated inside carbon cages that vary in size, shape and electronic properties. The most abundant compounds include trimetallic nitrides, with general formula M3N@C2n (n starting at 34), but dimetallic sulfides have also been prepared and characterized in our research group, M2S@C2n. In the latter series we have fully characterized the compounds with C82 cages (two isomers), C72 and C70, mainly with rare earth metals inside. The compound with the C72 cage elegantly exemplifies the principle of shape complementarity between the cluster and the cage and these results will be presented and discussed. The interplay between size and electronic complementarity will be illustrated with the trimetallic nitride series, changing the metal size going from Sc to La. One of the unusual observations in this series, especially for cages smaller than C86, is the existence of pentalene units on the surface of the cages, resulting in violations of the Isolated Pentagon Rule (IPR). Electronic factors are involved in these IPR violations. Using sulfides, we recently succeeded in preparing and characterizing a compound containing transition metals only inside, Ti?2?S@C78, which exhibits very interesting electrochemical properties, see figure.

Endohedral clusterfullerenes: Size, shape, and electronic complementarity between the carbon cages and the metal-containing clusters

248th National Meeting (2014)

The official archive and repository for all ACS Meetings & Expositions abstracts and select posters or presentations.