Self-templating 2D supramolecular networks: a new avenue to reach control over a bilayer formation

One of the greatest challenges in 2D self-assembly at interfaces is the ability to grow spatially controlled supramolecular motifs in the third dimension, exploiting the surface as a template. In this manuscript a concentration-dependent study by scanning tunneling microscopy at the solid–liquid interface, corroborated by Molecular Dynamics (MD) simulations, reveals the controlled generation of mono- or bilayer self-assembled Kagomé networks based on a fully planar tetracarboxylic acid derivative. By programming the backbone of the molecular building blocks, we present a strategy to gain spatial control over the adlayer structure by conferring self-templating capacity to the 2D self-assembled network.