Impact of open-shell loading on mass transport and doping in conjugated radical polymers,Journal of Polymer Science

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Impact of open-shell loading on mass transport and doping in conjugated radical polymers
Journal of Polymer Science ( IF 3.9 ) Pub Date : 2021-08-28 , DOI: 10.1002/pol.20210512
Kangying Liu ₁ , Kuluni Perera ₁ , Zhiyang Wang ₁ , Jianguo Mei ₁ , Bryan W. Boudouris _{1,

2}

Affiliation

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.

中文翻译：

开壳负载对共轭自由基聚合物中传质和掺杂的影响

含自由基聚合物是一类不断发展的氧化还原活性大分子，受到了极大的关注。然而，大多数关于自由基聚合物的报告都集中在具有非共轭骨架的材料上，因为它们的应用驱动程序不需要这种共轭。相反，用于下一代应用的自由基聚合物的开发最近有所增加，其中赋予自由基聚合物的主链共轭可能具有显着益处。为此，我们设计并合成了一系列基于 3,4-丙烯二氧噻吩 (ProDOT) 的聚合物，这些聚合物通过直接芳基化聚合带有硝基氧自由基侧基。具体而言，我们提出了四种自由基聚合物，其开壳负载范围为每个聚合物链重复单元总数的 24% 至 82%。然后使用循环伏安法、光谱电化学分析和具有耗散监测的电化学石英晶体微天平确定开壳负载对这些聚合物在不同电解质中的电化学行为的影响。我们证明在基于 ProDOT 的聚合物中加入开壳部分会降低共轭骨架的氧化起始电位，并显着增加溶剂和离子的吸收。因此，这项工作为基于 ProDOT 的自由基聚合物的传质和掺杂机制提供了清晰的画面，以帮助指导其未来的设计。和具有耗散监测的电化学石英晶体微量天平。我们证明在基于 ProDOT 的聚合物中加入开壳部分会降低共轭骨架的氧化起始电位，并显着增加溶剂和离子的吸收。因此，这项工作为基于 ProDOT 的自由基聚合物的传质和掺杂机制提供了清晰的画面，以帮助指导其未来的设计。和具有耗散监测的电化学石英晶体微量天平。我们证明在基于 ProDOT 的聚合物中加入开壳部分会降低共轭骨架的氧化起始电位，并显着增加溶剂和离子的吸收。因此，这项工作为基于 ProDOT 的自由基聚合物的传质和掺杂机制提供了清晰的画面，以帮助指导其未来的设计。

更新日期：2021-08-28

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