• scanning probe microscopy;
  • self-assembled monolayers;
  • solid–liquid interface;
  • supramolecular materials;
  • thermodynamics


The formation of highly ordered 2D supramolecular architectures self-assembled at the solid–solution interfaces is subject to complex interactions between the analytes, the solvent, and the substrate. These forces have to be mastered in order to regard self-assembly as an effective bottom-up approach for functional-device engineering. At such interfaces, prediction of the thermodynamics governing the formation of spatially ordered 2D arrangements is far from being fully understood, even for the physisorption of a single molecular component on the basal plane of a flat surface. Two recent contributions on controlled polymorphism and nanopattern formation render it possible to gain semi-quantitative insight into the thermodynamics of physisorption at interfaces, paving the way towards 2D supramolecular crystal engineering. Although in these two works different systems have been chosen to tackle such a complex task, authors showed that the chemical design of molecular building blocks is not the only requirement to fulfill when trying to preprogram self-assembled patterns at the solid–liquid interface.