Experimental evidence for long-range stabilizing and destabilizing interactions between charge and radical sites in distonic ions

David L. Marshall, Ganna Gryn'ova, Berwyck L.J. Poad, Steven E. Bottle, Adam J. Trevitt, Michelle L. Coote, Stephen J. Blanksby

Research output: Contribution to journalArticlepeer-review

4 Citations (Scopus)


Polarizable radical sites in distonic radical anions are stabilized by ostensibly remote negative charges. Computational evidence suggests bond dissociation energies of closed-shell precursors are significantly lowered by through-space interactions with a proximate negative charge, however direct experimental confirmation has proved challenging. Herein, we exploit two complementary tandem mass spectrometry strategies to probe the influence of a remote charge on the stability of nitroxyl radicals, and vice versa. Dissociation of negatively charge-tagged alkoxyamines reveals that the energetic onset of radical formation is dependent on the proximity and basicity of the charged group, thus providing direct evidence for a charge-induced stabilization of the nitroxyl radical. Complementary kinetic method experiments on a series of proton-bound dimers demonstrate that the presence of a nitroxyl radical decreases the proton affinity for a selection of proximate ionic groups. These data show excellent agreement with quantum-chemical calculations and provide a general framework to explore the magnitude and direction of charge-radical interactions through systematic exploration of the identity, polarity and the proximity of the ion to the radical site. These findings expand our fundamental understanding of radical ion energetics that underpin the application of distonic ions as models for neutral radical reactivity, and open new avenues for exploiting these interactions as chemical switches.

Original languageEnglish
Pages (from-to)195-203
Number of pages9
JournalInternational Journal of Mass Spectrometry
Publication statusPublished - Jan 2019
Externally publishedYes


  • Distonic ion
  • Free radicals
  • Gas-phase ion chemistry
  • Kinetic method
  • Tandem mass spectrometry


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