Selectively Altering the Reactivity of Transient Organic Radical Ions via Their Solvation Environment.
J Phys Chem B
; 126(16): 3107-3115, 2022 04 28.
Article
em En
| MEDLINE
| ID: mdl-35417166
ABSTRACT
Photoexcitation of the charge transfer band of electron donor-acceptor complexes composed of toluene and 1,2,4,5-tetracyanobenzene yields organic radical ion pairs whose ultrafast reactive dynamics are determined by equilibrium solvent properties. A comparative study of ultrafast reaction rates in a series of alkane alcohols identified their dependence on the local polarizability and hydrogen bond donating/accepting character of the solvent. Because of the rapid and efficient equilibration of these radical ion pairs into solvent-separated species, simple modifications to bulk conditions can be used as a means to selectively alter their decay rates. Selectively altering distinct stages in this photochemical cycle via cosolutes or additives is a valuable step toward understanding and controlling the reactivity of organic radical ions in complex environments.
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MEDLINE
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En
Ano de publicação:
2022
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Article