Polymers with charged or redox-active pendant side groups have recently found applications ranging from redox flow batteries to biomolecular complexation agents for imaging and drug delivery. These versatile materials rely on solubilized polymer chains whose conformations must allow fast solvent access for charge transfer at discrete sites, yet retain a measure of volumetric charge storage capacity. To understand the local environment where charge transfer takes place, we study a model system where small molecular dopants (e.g., 1,2,4,5-tetracyanobenzene) form neutral complexes with aromatic side chains of a nonpolar polymer (e.g., polystyrene) and undergo efficient photolysis with UV light. Irradiation of solid films of these neutral complexes in contact with simple aqueous electrolyte solutions results in substantial macromolecular phase transfer mediated by photogenerated ions. Importantly, photolysis of a fraction of the charge transfer complexes is enough to solubilize entire chains along with the remaining neutral complexes. Time-resolved fluorescence experiments of these phase-transferred polymer-dopant complexes reveal fluorescence decay time scales similar to those in a solid film, while transient anisotropy measurements display a molecular rotation diffusion time scale comparable to that of a fully-solubilized chain. Such hybrid photophysics suggest a locally-flexible yet stable molecular environment, with interesting implications for polymeric redox shuttles and polyelectrolyte complexes.

Local environment of polymer: Dopant charge transfer complexes after photoinduced phase-transfer

Macromolecular Chemistry: The Second Century

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ACS Spring 2020 National Meeting & Expo

The official archive and repository for all ACS Meetings & Expositions abstracts and select posters or presentations.