High-spin polyarylmethyl polyradical: Fragment of a macrocyclic 2-strand based upon calix[4]arene rings

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Abstract

Annelated triple-calix[4]arene-based tetradecaether 1-(OMe) 14 is synthesized. Its three isomers, 1X-(OMe) 14, 1Y-(OMe) 14, 1Z-(OMe) 14, are isolated and characterized. The corresponding triarylmethyl carbopolyanion is prepared and oxidized to polyradical 1. SQUID magnetometry for 1 in THF-d 8/2-MeTHF gives S = 6.2, below the theoretical value of 7 expected for strong ferromagnetic coupling between 14 'unpaired' electrons. Chemical quenching studies suggest that approximately one deuterium from the deuterated solvent is incorporated in 1, thus accounting in part for S < 7. Study of the temperature dependence of magnetization indicates that ferromagnetic coupling between 'unpaired' electrons is not very strong in 1; i.e., the thermal population of low-spin excited states is detected in the cryogenic temperature range. Upon exposure of 1 in THF-d 8/2-MeTHF to ambient temperature for 30 min, a narrow distribution of spin systems with an 'average' S = 2.5 is obtained; upon a longer exposure time of 24 h, an 'average' S = 1 is produced.

Original languageEnglish (US)
Pages (from-to)10335-10345
Number of pages11
JournalJournal of the American Chemical Society
Volume119
Issue number43
DOIs
StatePublished - Nov 25 1997

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ASJC Scopus subject areas

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

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