Oligo(phenyleneethynylene)s: Shape‐Tunable Building Blocks for Supramolecular Self‐Assembly

Oligo(phenyleneethynylene)s (OPEs) have attracted widespread attention due to their remarkable (opto)electronic and photophysical properties, which have enabled numerous applications. The versatile functionalization possibilities of OPEs make them unique candidates to form various shape‐persistent geometries, including linear, triangular, rectangular, hexagonal and macrocyclic. However, as a result of this structural variety, it is oftentimes challenging to correlate molecular design with self‐assembly properties. In this minireview, we have classified OPEs based on their molecular shapes and correlated them with their self‐assembly behavior in solution. Particularly, we provide important insights into the aggregation propensity of the different molecular shapes and how to tune the association strength using various non‐covalent interactions. Our classification will enable a better understanding of the structure‐property correlation in OPEs, which is key to develop supramolecular functional materials