Intra- and Inter-Self-Assembly of Identical Supramolecules on Silver Surfaces.

Self-assembly of identical organometallic supramolecules into ordered superstructures is of great interest in both chemical science and nanotechnology due to its potential to generate neoteric properties through collective effects. In this work, we demonstrate that large-scale self-organization of atomically precise organometallic supramolecules can be achieved through cascaded on-surface chemical reactions, by the combination of intra- and inter-supramolecular interactions. Supramolecules with defined size and shape are first built through intramolecular reaction and intermolecular metal coordination, followed by the formation of well-ordered two-dimensional arrays with the assistance of Br atoms by -C-H···Br interactions. The mechanism of this process has been investigated from the perspectives of thermodynamics and kinetics.