Supramolecular Crystal Engineering at the Solid–Liquid Interface from First Principles: Toward Unraveling the Thermodynamics of 2D Self‐Assembly

Abstract

Abstract 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.