Post-Polymerization Click Functionalization of Conjugated Polymers

Abstract

Conjugated polymers attract significant attention due to their interesting optoelectronic and physical properties. Over the past few decades, tremendous effort has been devoted to expanding the structural diversity and applications of this class of macromolecules. The pursuit of structural variability of conjugated polymers has resulted in a broad range of research to understand their structure-property relationships via functionalization. This functionalization is crucial for tailoring performance in any given application. Thus, the ability to synthesize a library of homologous polymers would prove very useful. Efficiency is of utmost importance when creating a library of homologous conjugated polymers, as the faster a library can by synthesized, the sooner said polymers can be screened for any desirable properties. Such an approach requires a post-polymerization functionalization strategy, whereby a progenitor polymer undergoes efficient reactions at each repeat unit of the backbone. The work presented in this thesis involves synthesizing a reactive conjugated polymer scaffold, followed by efficiently post-polymerization functionalization via “click” chemistry. Two elegant click reactions are described in this work; the Strain-Promoted Alkyne-Azide Cycloaddition (SPAAC) and Inverse Electron-Demand Diels-Alder (IEDDA). The SPAAC reaction allowed for rapid functionalization of triazole moieties on a dibenzocyclooctyne-containing polymer backbone, creating a small polymer library with a consistent degree of polymerization (DP). Grafting with polystyrene and polyethylene glycol azide-terminated polymers allowed the efficient syntheses of a series of graft-co-polymers with Mn values up to 800 kDa and varying solubilities. Secondly, The IEDDA reaction was applied to a poly(tetrazine-co-fluorene) conjugated polymer, which resulted in the rapid and quantitative functionalization of the polymer backbone with trans-cyclooctene derivatives. These reactive conjugated polymers were explored in a variety of applications, including supramolecular chemistry and gel formation.