Supramolecular Tessellations at Surfaces by Vertex Design.

Assembly and tessellation of organic species at surfaces are important for the design of advanced materials, particularly for the development of spontaneous self-assemblies of supramolecular systems of increasing complexity. However, there are few examples where the ability to steer the system between supramolecular tessellations has been achieved. Here, we demonstrate a series of steps to reduce and then restore molecular symmetry; those variations impact vertex symmetry and thus generate a series of tessellations that reflect the molecular symmetry. We deposit 4,4'-dihydroxybiphenyl on the Ag(111) surface, then anneal at specific temperatures to achieve stepwise dehydrogenation of the terminal hydroxyls. The symmetry of tessellation vertices in the self-assembled structure also changes, as characterized by scanning tunneling microscopy and synchrotron radiation photoemission spectroscopy. This control over vertex geometry and spontaneous tessellation structure extends our understanding of supramolecular design control and advances architectural complexity for the development of functional surfaces.