Post-polymerisation approaches for the rapid modification of conjugated polymer properties

Abstract

Post-polymerisation functionalisation provides a facile and efficient way for the introduction of functional groups on the backbone of conjugated polymers. Using post-polymerisation functionalisation approaches, the polymer chain length is usually not affected, meaning that the resulting polymers only differ in their attached functional groups or side chains, which makes them particularly interesting for investigating the influence of the different groups on the polymer properties. For such functionalisations, highly efficient and selective reactions are needed to avoid the formation of complex mixtures or permanent defects in the polymer backbone. A variety of suitable synthetic approaches and reactions that fulfil these criteria have been identified and reported. In this review, a thorough overview is given of the post-polymerisation functionalisations reported to date, with the methods grouped based on the type of reaction used: cycloaddition, oxidation/reduction, nucleophilic aromatic substitution, or halogenation and subsequent cross-coupling reaction. Instead of modifications on the aliphatic side chains of the conjugated polymers, we focus on modifications directly on the conjugated backbones, as these have the most pronounced effect on the optical and electronic properties. Some of the discussed materials have been used in applications, ranging from solar cells to bioelectronics. By providing an overview of this versatile and expanding field for the first time, we showcase post-polymerisation functionalisation as an exciting pathway for the creation of new conjugated materials for a range of applications.