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 language | English (US) |
|---|---|
| Pages (from-to) | 2350-2356 |
| Number of pages | 7 |
| Journal | Journal of the American Chemical Society |
| Volume | 135 |
| Issue number | 6 |
| DOIs | |
| State | Published - Feb 13 2013 |
| Externally published | Yes |
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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 journal › Article
}
TY - JOUR
T1 - Structural factors controlling the spin-spin exchange coupling
T2 - EPR spectroscopic studies of highly asymmetric trityl-nitroxide biradicals
AU - Liu, Yangping
AU - Villamena, Frederick A.
AU - Rockenbauer, Antal
AU - Song, Yuguang
AU - Zweier, Jay L.
PY - 2013/2/13
Y1 - 2013/2/13
N2 - 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.
AB - 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.
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U2 - 10.1021/ja311571v
DO - 10.1021/ja311571v
M3 - Article
VL - 135
SP - 2350
EP - 2356
JO - Journal of the American Chemical Society
JF - Journal of the American Chemical Society
SN - 0002-7863
IS - 6
ER -