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Updated: Oct 8, 2025

Syntheses, Crystallization, and Spectroscopic Characterization of 3,5-Lutidine N-Oxide Dehydrate
Published on: April 24, 2018
Pyridine-Containing Donor-Acceptor Diarylnitroxides: Noncovalent Stabilization of the Redox States
Oleg A Levitskiy1, Alexey V Bogdanov1, Ivan A Klimchuk1
1Department of Chemistry, Lomonosov Moscow State University, Leninskie Gory 1/3, 119991, Moscow, Russian Federation.
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.
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