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Organic Polyradicals as Redox Mediators: Effect of Intramolecular Radical Interactions on Their Efficiency
16 February 2021

The spin–spin interactions between unpaired electrons in organic (poly)radicals, especially nitroxides, are largely investigated and are of crucial importance for their applications in areas such as organic magnetism, molecular charge transfer, or multiple spin labeling in structural biology. Recently, 2,2,6,6-tetramethylpiperidinyloxyl and polymers functionalized with nitroxides have been described as successful redox mediators in several electrochemical applications; however, the study of spin–spin interaction effect in such an area is absent.

This communication reports the preparation of a novel family of discrete polynitroxide molecules, with the same number of radical units but different arrangements to study the effect of intramolecular spin–spin interactions on their electrochemical potential and their use as oxidation redox mediators in a Li–oxygen battery. We find that the intensity of interactions, as measured by the d1/d electron paramagnetic resonance parameter, progressively lowers the reduction potential. This allows us to tune the charging potential of the battery, optimizing its energy efficiency.

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Organic Polyradicals as Redox Mediators: Effect of Intramolecular Radical Interactions on Their Efficiency


Elena Badetti*, Vega Lloveras, Emanuele Amadio, Rosalia Di Lorenzo, Mara Olivares-Marín, Alvaro Y. Tesio, Songbai Zhang, Fangfang Pan, Kari Rissanen, Jaume Veciana, Dino Tonti*, Jose Vidal-Gancedo*, Cristiano Zonta, and Giulia Licini*

ACS Appl. Mater. Interfaces 2020, 12, 41, 45968–45975
Publication Date:September 15, 2020
DOI:https://pubs.acs.org/doi/10.1021/acsami.0c09386