Pyridine-Containing Donor-Acceptor Diarylnitroxides: Noncovalent Stabilization of the Redox States

Oleg A. Levitskiy, Alexey V. Bogdanov, Ivan A. Klimchuk, Tatiana V. Magdesieva*

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

6 Citations (Scopus)

Abstract

A series of new pyridyl- or 2-pyridyloxide-containing donor-acceptor diarylnitroxides was obtained and characterized; high stability of the ortho-2-pyridyl-containing diarylnitroxides was determined by kinetic measurements (τ1/2=1733 h in benzene). Comparative voltammetric study of new nitroxides and their analog in which the Py replaces the Ph group revealed both through-bond and through-space stabilization of the NO redox states with the pyridyl/ 2-pyridyloxide moiety, providing reversibility of both oxidation and reduction processes. Adaptive conformational behavior of new pyridyl/pyridyloxide containing nitroxides upon one-electron oxidation and reduction was confirmed by DFT calculations. Stimuli-responsive conformational changes allow switching on/off dispersion and electrostatic interactions within the molecule and increase stability of the redox states. Spectroelectrochemical measurements provided experimental evidence for reversibility of the through-space stabilization of the oxidized state of the nitroxides with the neighboring pyridine lone pair.

Original languageEnglish
Article numbere202100508
JournalChemPlusChem
Volume87
Issue number3
DOIs
Publication statusPublished - Mar 2022
Externally publishedYes

All Science Journal Classification (ASJC) codes

  • General Chemistry

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