Electronic Structure of Persistent Radicals: Nitroxides

Igor Novak, Leslie J. Harrison, Branka Kovac, Lawrence M. Pratt

Research output: Contribution to journalArticlepeer-review

52 Citations (Scopus)


The molecular and electronic structures of 10 free nitroxide radicals have been investigated by HeI/HeII photoelectron spectroscopy (UPS), DFT calculations, and comparison with the spectra of related compounds. We observe that the electronic structure of the nitroxide group is unaffected by substitution except in a carbonyl derivative where nitroxide group orbitals are noticeably stabilized. Also, we have detected small variations in the photoionization cross-sections for singlet and triplet states of cation, the states belonging to the same electron configuration. The relationship between electronic structure and radical reactivity is discussed, and an experimentally based estimate of delocalization energy of the unpaired electron is given. Some conflicting kinetic data on radical reactivity have been analyzed in view of the UPS results.
Original languageEnglish
Pages (from-to)7628-7634
Number of pages7
JournalJournal of Organic Chemistry
Issue number22
Publication statusPublished - 2004


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