Bicomponent H‑Bonded Porous Molecular Networks at the Liquid–Solid Interface: What Is the Influence of Preorganization in Solution?

Tailoring the architecture of porous two-dimensional networks formed by molecules is essential for developing functional materials with low dimensionality. Here we present bicomponent porous networks with tunable pore-sizes that were formed by self-assembly of hydrogen-bonding molecules at the liquid/graphite interface. Scanning tunneling microscopy investigations demonstrate the formation and coexistence of three polymorphs. It is found that the occurrence of these polymorphs depends critically on the surface coverage. Further on, atomic force microscopy measurements, spectroscopic studies, and dynamic light scattering investigations show the propensity of one of the two molecular components to form aggregates beyond the monolayer. We discuss how these preorganized aggregates in solution may affect the self-assembly at the interface.