Nitrogen-14 and oxygen-17 hyperfine interactions in perturbed nitroxides

Allan H. Cohen, Brian M Hoffman*

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

35 Scopus citations

Abstract

We have measured the isotropic and anisotropic hyperfine splittings for di-tert-butyl nitroxide (DTBN) and 2,2,6,6-tetramethylpiperidine N-oxyl (TMPN) perturbed by molecular complex formation, by hydrogen bonding, and by solvent effects in aprotic solvents. We use these measurements to obtain the σ-π interaction parameters for a Karplus-Fraenkel equation (a1 = Q11 iρiπ + Qjj iρj π) which relates the 14N and 17O isotropic hyperfine splittings to the spin density in the nitroxide N-O π-electron system; QNN N = 23.9 ± 1.0 G, QOO N = 3.6 ± 0.4 G, QOO O = 31.7 ± 0.7 G, and QNN O = 4.7 ± 0.5 G. In addition for protonated nitroxides QOO N = 13.2 ± 0.3 G. The values of QNN N for TMPN and DTBN are identical and discussion of the angle dependence of the parameter suggests that the radicals in solution do not differ with respect to planarity at nitrogen.

Original languageEnglish (US)
Pages (from-to)1313-1321
Number of pages9
JournalJournal of Physical Chemistry
Volume78
Issue number13
DOIs
StatePublished - Jan 1 1974

ASJC Scopus subject areas

  • Engineering(all)
  • Physical and Theoretical Chemistry

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