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

Pyridine‐Containing Donor‐Acceptor Diarylnitroxides: Noncovalent Stabilization of the Redox States 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. http://www.deepdyve.com/assets/images/DeepDyve-Logo-lg.png ChemPlusChem Wiley

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

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References (2)

Publisher
Wiley
Copyright
© 2022 Wiley‐VCH GmbH
eISSN
2192-6506
DOI
10.1002/cplu.202100508
Publisher site
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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.

Journal

ChemPlusChem – Wiley

Published: Mar 1, 2022

Keywords: donor-acceptor compounds; nitroxides; noncovalent interactions; radicals; redox behaviour

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