Growth induced reordering of fullerene clusters trapped in a two-dimensional supramolecular network

We have investigated the growth of molecular clusters in confined geometries defined by a bimolecular supramolecular network. This framework provides a regular array of identical nanoscale traps in which further deposited molecules nucleate cluster growth. For the higher fullerene, C-84, molecules aggregate into close packed assemblies with an orientation which switches when the cluster size increases by one molecule. This change is controlled by the interactions between the molecules and the confining boundaries of the network pore. We show that, following nucleation of small clusters, further growth requires a reconfiguration of previously captured molecules resulting in a transition between nanoscale phases with different ordering.