Supramolecular Crystal Engineering at the Solid-Liquid interface from First Principles: Toward Unraveling the Thermodynamics of 2D Self-Assembly

The formation of highly ordered 2D supramolecular architect assembled at the solid-solution interfaces is subject to complex interactions between the analytes, the solvent, and the substrate. These for 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.