Transient methods for understanding the properties of strongly oxidizing radicals

Polyansky, Dmitry E.

doi:10.1039/d4cc06158f

Transient methods for understanding the properties of strongly oxidizing radicals

Journal Article · Thu Jan 30 00:00:00 EST 2025 · ChemComm

DOI:https://doi.org/10.1039/d4cc06158f· OSTI ID:2525829

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Brookhaven National Laboratory (BNL), Upton, NY (United States)

This review discusses the properties of strongly oxidizing radicals in organic and aqueous media and highlights the challenges in obtaining accurate values of their reduction potentials. Transient redox equilibrium methods based on the use of strong photooxidants or initiated by pulse radiolysis are shown to provide versatile approaches for decoupling electron transfer reactions from follow-up reactivity of unstable radical species, resulting in accurate values of reduction potentials of very positive couples, including some solvent radical cations. Here, we also show that correlations of reduction potentials with Hammett Σσ⁺_p parameters, as well as gas phase ionization potentials, can be used to estimate the redox properties of unknown couples within a homologous series of compounds. The effects of ion pairing and hemicolligation on redox properties of organic and inorganic radicals are also discussed.

View Accepted Manuscript (DOE)

Research Organization:: Brookhaven National Laboratory (BNL), Upton, NY (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division (CSGB)

Grant/Contract Number:: SC0012704

OSTI ID:: 2525829

Alternate ID(s):: OSTI ID: 2507491

Report Number(s):: BNL--227629-2025-JAAM

Journal Information:: ChemComm, Journal Name: ChemComm Journal Issue: 17 Vol. 61; ISSN 1359-7345

Publisher:: Royal Society of ChemistryCopyright Statement

Country of Publication:: United States

Language:: English

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14 SOLAR ENERGY
biphenyl radical cation
hemicolligation
ion pairing
pulse radiolysis

Transient methods for understanding the properties of strongly oxidizing radicals

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