Pure and Applied Chemistry

Abstract: This article briefly reviews the interplay of weak noncovalent interactions involved in the formation of self-assembled monolayers of organic molecules and the strong chemical binding in directed-assembly of organic molecules on solid surfaces. For a self-assembled monolayer, each molecule involves at least three categories of weak interactions, including molecule-substrate interactions, molecule-molecule interactions in a lamella, and molecule-molecule interactions between two adjacent lamellae. Basically, molecule-substrate interactions play a major role in determining molecular configuration. Molecule-molecule interactions, particularly the interactions of molecular ending functional groups between two adjacent lamellae, such as hydrogen bonds, play a dominant role in determining the molecular packing pattern in a monolayer. These weak interactions may induce or influence molecular chirality. This understanding at the atomic scale allows us to design 2D nanostructured organic materials via precisely manipulating these weak noncovalent interactions. Compared to the self-assembled monolayer formed via weak noncovalent interactions, the structure of directed-assembled monolayer/multilayers formed through strong chemical bonds is significantly dependent on the geometric arrangement and reactivity of active sites on the solid surface. In contrast to the significant role of weak intermolecular interactions in determining molecular packing in a self-assembled monolayer, strong chemical binding between molecules and reactive sites of a substrate plays a major role in determining the molecular packing pattern in a directed-assembly monolayer. Controllable chemical attachment between organic functional groups and reactive sites of the solid surface is crucial for the formation of a highly oriented organic monolayer and the following multilayer.