Impact of Backbone Tether Length and Structure on the Electrochemical Performance of Viologen RAPs

Generalized schematic that explains how we used a systematic molecular design approach to investigate the impact of linker and redox-pendant electronic interactions on the performance of viologen RAPs.

Scientific Achievement

Fundamental inter-valence interactions are used as starting point for improving the electrochemical properties of redox active polymers and explore structure/activity relationships.

Significance and Impact

The modulation of RAP inter-pendant interactions decisively impacts charge transfer. While polymers with optimized macroscopic reversibility were obtained, the microscopic trends describing small molecule electrochemistry did not hold for polymers, showing anti-Marcus effects that require further investigation.

Research Details

  • The information garnered from the electrochemical and spectroscopic measurements offer a diverse experimental approach to reliably study the RAPs charge transfer kinetics and charge propagation in solution and as a film.
  • Tailored inter-pendant interactions help us probe concepts aimed at facilitating the size-scaling of materials for size-exclusion flow batteries.
  • Correlating electronic structure and rate effects on RAPs with well-controlled architectures lead to unprecedented understanding of how electrochemical properties in monomers translate to their polymer equivalents.

DOI: 10.1021/acs.chemmater.6b02825

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