6533b7d4fe1ef96bd1261e82
RESEARCH PRODUCT
Organic Polyradicals as Redox Mediators: Effect of Intramolecular Radical Interactions on Their Efficiency
Jaume VecianaKari RissanenMara Olivares-marínMara Olivares-marínCristiano ZontaRosalia Di LorenzoFangfang PanDino TontiAlvaro Yamil TesioElena BadettiEmanuele AmadioJosé Vidal-gancedoVega LloverasSongbai ZhangGiulia Licinisubject
Materials scienceRedox mediatorsRadical02 engineering and technology010402 general chemistryPhotochemistryElectrochemistry01 natural sciencesRedoxlaw.inventiontitanatraneslawTitanatranesnitroxidesspin−spin interactionsMoleculeSettore CHIM/01 - Chimica AnaliticaGeneral Materials SciencepolymeeritElectron paramagnetic resonanceElectrochemical potentialSpin−spin interactionsNitroxides; Redox mediators; Spin−spin interactions; TEMPO; Titanatranes; μ-oxo complexesNitroxidesSettore CHIM/06 - Chimica Organicapolymeerikemia021001 nanoscience & nanotechnologysähkökemia0104 chemical sciencesredox mediatorsμ-oxo complexesUnpaired electronIntramolecular forceorgaaninen kemiaspin-spin interactionsCondensed Matter::Strongly Correlated Electrons0210 nano-technologyTEMPOResearch Articledescription
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.
| year | journal | country | edition | language |
|---|---|---|---|---|
| 2020-01-01 | ACS Applied Materials & Interfaces |