Impact of open‐shell loading on mass transport and doping in conjugated radical polymers
Abstract
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.
Document Details
- Document Type
- Pub Defense Publication
- Publication Date
- Aug 28, 2021
- Source ID
- 10.1002/pol.20210512
Entities
People
- Bryan W Boudouris
- Jianguo Mei
- Kangying Liu
- Kuluni Perera
- Zhiyang Wang
Organizations
- Air Force Office of Scientific Research
- Purdue University