Poly(3,4-ethylenedioxythiophene):poly(styrene sulfonate), PEDOT:PSS, has been widely used as an effective hole transporting material in many different organic semiconductor devices for well over a decade.

The field of synthetic metals is, and remains, highly influential for the development of organic semiconductor materials. Yet, with the passing of time and the rapid development of conjugated materials in recent years, the link between synthetic metals and organic semiconductors is at risk of being forgotten. This review reflects on one of the key concepts developed in synthetic metals – heteroatom interactions. The application of this strategy in recent organic semiconductor materials, small molecules and polymers, is highlighted, with analysis of X‐ray crystal structures and comparisons with model systems used to determine the influence of these non‐covalent short contacts. The case is made that the wide range of effective heteroatom interactions and the high performance that has been achieved in devices from organic solar cells to transistors is testament to the seeds sown by the synthetic metals research community.

Design strategy of polyaromatic esters.