Structural factors controlling the spin-spin exchange coupling

EPR spectroscopic studies of highly asymmetric trityl-nitroxide biradicals

Yangping Liu, Frederick A. Villamena, Antal Rockenbauer, Yuguang Song, Jay L. Zweier

Research output: Contribution to journalArticle

Abstract

Highly asymmetric exchange-coupled biradicals, e.g., the trityl-nitroxides (TNs), possess particular magnetic properties that have opened new possibilities for their application in biophysical, physicochemical, and biological studies. In the present work, we investigated the effect of the linker length on the spin-spin coupling interaction (J) in TN biradicals using the newly synthesized biradicals CT02-GT, CT02-AT, CT02-VT, and CT02-PPT as well as the previously reported biradicals TNN14 and TN1. The results show that the magnitude of J can be easily tuned from ∼4 G (conformer 1 in CT02-PPT) to >1200 G (in TNN14) by varying the linker separating the two radical moieties and changing the temperature. Computer simulations of EPR spectra were carried out to estimate J values of the TN biradicals directly. In addition to the spin-spin coupling interaction of TN biradicals, their g, hyperfine-splitting, and zero-field-splitting interactions were explored at low temperature (220 K). Our present study clearly shows that varying the spin-spin interaction as a function of linker distance and temperature provides an effective strategy for the development of new TN biradicals that can find wide applications in relevant fields.

Original languageEnglish (US)
Pages (from-to)2350-2356
Number of pages7
JournalJournal of the American Chemical Society
Volume135
Issue number6
DOIs
StatePublished - Feb 13 2013
Externally publishedYes

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Exchange coupling
Paramagnetic resonance
Temperature
Computer Simulation
Magnetic properties
Computer simulation

ASJC Scopus subject areas

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

Cite this

Structural factors controlling the spin-spin exchange coupling : EPR spectroscopic studies of highly asymmetric trityl-nitroxide biradicals. / Liu, Yangping; Villamena, Frederick A.; Rockenbauer, Antal; Song, Yuguang; Zweier, Jay L.

In: Journal of the American Chemical Society, Vol. 135, No. 6, 13.02.2013, p. 2350-2356.

Research output: Contribution to journalArticle

Liu, Yangping ; Villamena, Frederick A. ; Rockenbauer, Antal ; Song, Yuguang ; Zweier, Jay L. / Structural factors controlling the spin-spin exchange coupling : EPR spectroscopic studies of highly asymmetric trityl-nitroxide biradicals. In: Journal of the American Chemical Society. 2013 ; Vol. 135, No. 6. pp. 2350-2356.
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