Do high-spin topology rules apply to charged polyradicals? Theoretical and experimental evaluation of pyridiniums as magnetic coupling units

A. P. West, S. K. Silverman, D. A. Dougherty

Research output: Contribution to journalArticle

Abstract

Ab initio calculations on pyridine and pyridinium analogues of m-xylylene indicate that the neutral heterocycle is essentially equivalent to benzene as a ferromagnetic coupling unit, while the cationic pyridiniums behave much differently. Depending on the substitution pattern, a protonated pyridine can serve as a ferromagnetic coupling unit or an antiferromagnetic coupling unit. Both valence bond and molecular orbital arguments provide qualitative rationalizations of these results. In an effort to test the theoretical predictions, bis(trimethylenemethane) analogues of the pyridine and pyridinium biradicals were synthesized and analyzed by electron paramagnetic resonance spectroscopy. General support for the theoretical predictions is obtained.

Original languageEnglish (US)
Pages (from-to)1452-1463
Number of pages12
JournalJournal of the American Chemical Society
Volume118
Issue number6
DOIs
StatePublished - Jan 1 1996
Externally publishedYes

ASJC Scopus subject areas

  • Catalysis
  • Chemistry(all)
  • Biochemistry
  • Colloid and Surface Chemistry

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