Optimizing the self‐assembly of conjugated polymers and small molecules through structurally programmed non‐covalent control

Organic conjugated polymers and oligomers are key electronic materials for applications such as transistors, photovoltaics, and light emitting devices due to their potential for solution processability, mechanical flexibility, and precise structure‐based tuning compared to inorganic materials. In dilute environments, the optoelectronic properties of conjugated polymers are largely governed by their constitutional structure and, to a lesser degree, their solution‐state intramolecular configuration. In the solid state, intramolecular conformation and intermolecular electronic coupling impact these properties substantially, especially in relation to device performance. Therefore, an increasingly important area of research concerning conjugated materials is developing design strategies aimed at optimizing the solid‐state packing for electronic applications. Programming solid‐state packing arrangements through discrete non‐covalent interactions is an emerging strategy within the context of conjugated polymers. This review focuses on the use of the two most prevalent discrete and directional interactions used to dictate the self‐assembly of conjugated polymers and oligomers—hydrogen bonds and chalcogen bonds. We also discuss how these design motifs can imbue conjugated materials with appealing physical properties while simultaneously retaining or improving electronic capabilities.