Two‐Dimensional Supramolecular Chemistry

Abstract

Abstract Two‐dimensional assembly of molecular assemblies on surfaces represents a significant challenge to chemists, materials scientists, and physicists. Supramolecular chemistry offers many advantageous strategies for the development of such arrays through the use of intermolecular interactions to control the process of molecular organization and self‐assembly. This article reveals how hydrogen bonds, dipole–dipole, van der Waals interactions, and metal–ligand coordination can be used to assemble two‐dimensional arrays on surfaces. Such supramolecular assemblies can be used to trap guest species mimicking host–guest chemistry in the solution phase. By the use of the molecular resolution of scanning‐probe microscopies, particularly scanning tunneling microscopy, the precise arrangement of the supramolecular assemblies can be probed and evaluated including the relative orientation with respect to the surface. The influence of the surface on the self‐assembly process is discussed and it is shown that far from playing a passive role in the self‐assembly process the substrate can strongly influence the supramolecular chemistry observed. Such images provide great insight into the advantages and restrictions of working in two dimensions in comparison to the solution phase or the solid state.