Group 16 conjugated polymers based on furan, thiophene, selenophene, and tellurophene

Five-membered aromatic rings containing Group 16 elements (O, S, Se, and Te), also referred as chalcogenophenes, are ubiquitous building blocks for π-conjugated polymers (CPs). Among these, polythiophenes have been established as a model system to study the interplay between molecular structure, solid-state organization, and electronic performance. The judicious substitution of alternative heteroatoms into polythiophenes is a promising strategy for tuning their properties and improving the performance of derived organic electronic devices, thus leading to the recent abundance of CPs containing furan, selenophene, and tellurophene. In this review, we first discuss the current status of Kumada, Negishi, Murahashi, Suzuki-Miyaura, and direct arylation polymerizations, representing the best routes to access well-defined chalcogenophene-containing homopolymers and copolymers. The self-assembly, optical, solid-state, and electronic properties of these polymers and their influence on device performance are then summarized. In addition, we highlight post-polymerization modifications as effective methods to transform polychalcogenophene backbones or side chains in ways that are unobtainable by direct polymerization. Finally, the major challenges and future outlook in this field are presented.