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    Impact of open-shell loading on mass transport and doping in conjugated radical polymers

    Year: 2021

    Journal: J. Polym. Sci., Volume 59, NOV 15, page 2771–2782

    Authors: Liu, Kangying; Perera, Kuluni; Wang, Zhiyang; Mei, Jianguo; Boudouris, Bryan W.

    Organizations: Ambilight, Inc. [40001872]; Air Force Office of Scientific Research (AFOSR) [FA9550-19-1-0271]

    Keywords: coupled transport; direct arylation polymerization (DArP); electrochromic behavior; open-shell macromolecules; ProDOT-based radical polymers

    Radical-containing polymers are an evolving class of redox-active macromolecules that have received great interest; however, most reports regarding radical polymers have focused on materials with nonconjugated backbones because their application drivers did not require this conjugation. Conversely, there has been a recent rise in the development of radical polymers for next-generation applications where imparting conjugation to the backbone of the radical polymer could be of significant benefit. To this end, we designed and synthesized a series of 3,4-propylenedioxythiophene (ProDOT)-based polymers bearing nitroxide radical pendent groups via direct arylation polymerization. Specifically, we present four radical polymers with open-shell loadings ranging from 24% to 82% of the total number of repeat units per polymer chain. The impact of open-shell loading on the electrochemical behaviors of these polymers in different electrolytes was then established using cyclic voltammetry, spectroelectrochemical analyses, and electrochemical quartz-crystal microbalance with dissipation monitoring. We demonstrate that incorporating the open-shell moieties in the ProDOT-based polymers lowers the oxidation onset potential of the conjugated backbone and increases the solvent and ion uptake significantly. Thus, this effort provides a clear picture of the mass transfer and doping mechanism of the ProDOT-based radical polymers to aid in guiding their future design.
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