Exchange coupling mediated through-bonds and through-space in conformationally constrained polyradical scaffolds: Calix[4]arene nitroxide tetraradicals and diradical

Andrzej Rajca, Sumit Mukherjee, Maren Pink, Suchada Rajca

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62 Citations (Scopus)

Abstract

Calix[4]arenes constrained to the 1,3-alternate conformation and functionalized at the upper rim with four and two tert-butylnitroxides have been synthesized and characterized by X-ray crystallography, magnetic resonance (EPR and 1H NMR) spectroscopy, and magnetic studies. The 1,3-alternate nitroxide tetraradical and diradical provide unique polyradical scaffolds for dissection of the through-bond and through-space intramolecular exchange couplings. In addition, detailed magnetic studies of the previously reported calix[4]arene nitroxide tetraradical, which possesses cone conformation in solution, reveal conformational dependence of exchange coupling. Through-bond coupling between the adjacent nitroxide radicals is mediated by the nitroxide-m-phenylene-CH2-m-phenylene-nitroxide coupling pathway, and through-space coupling is found between the diagonal nitroxide radicals at the conformationally constrained N⋯N distance of 5-6 Å. Magnetic studies of the calix[4]arene polyradical scaffolds in frozen solutions show that the through-bond exchange coupling in the 1,3-alternate calix[4]arene tetraradical is antiferromagnetic, while that in cone calix[4]arene tetraradical is ferromagnetic. The through-space exchange couplings are antiferromagnetic in both cone and 1,3-alternate calix[4]arene tetraradical, as well as in the 1,3-alternate calix[4]arene diradical. The exchange coupling constants (|J/k|) are of the order of 1 K.

Original languageEnglish (US)
Pages (from-to)13497-13507
Number of pages11
JournalJournal of the American Chemical Society
Volume128
Issue number41
DOIs
StatePublished - Oct 18 2006

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Exchange coupling
Scaffolds
Cones
Conformations
Magnetic Resonance Spectroscopy
Dissection
X ray crystallography
Magnetic resonance
X Ray Crystallography
Nuclear magnetic resonance spectroscopy
Paramagnetic resonance
calix(4)arene

ASJC Scopus subject areas

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

Cite this

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title = "Exchange coupling mediated through-bonds and through-space in conformationally constrained polyradical scaffolds: Calix[4]arene nitroxide tetraradicals and diradical",
abstract = "Calix[4]arenes constrained to the 1,3-alternate conformation and functionalized at the upper rim with four and two tert-butylnitroxides have been synthesized and characterized by X-ray crystallography, magnetic resonance (EPR and 1H NMR) spectroscopy, and magnetic studies. The 1,3-alternate nitroxide tetraradical and diradical provide unique polyradical scaffolds for dissection of the through-bond and through-space intramolecular exchange couplings. In addition, detailed magnetic studies of the previously reported calix[4]arene nitroxide tetraradical, which possesses cone conformation in solution, reveal conformational dependence of exchange coupling. Through-bond coupling between the adjacent nitroxide radicals is mediated by the nitroxide-m-phenylene-CH2-m-phenylene-nitroxide coupling pathway, and through-space coupling is found between the diagonal nitroxide radicals at the conformationally constrained N⋯N distance of 5-6 {\AA}. Magnetic studies of the calix[4]arene polyradical scaffolds in frozen solutions show that the through-bond exchange coupling in the 1,3-alternate calix[4]arene tetraradical is antiferromagnetic, while that in cone calix[4]arene tetraradical is ferromagnetic. The through-space exchange couplings are antiferromagnetic in both cone and 1,3-alternate calix[4]arene tetraradical, as well as in the 1,3-alternate calix[4]arene diradical. The exchange coupling constants (|J/k|) are of the order of 1 K.",
author = "Andrzej Rajca and Sumit Mukherjee and Maren Pink and Suchada Rajca",
year = "2006",
month = "10",
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pages = "13497--13507",
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T2 - Calix[4]arene nitroxide tetraradicals and diradical

AU - Rajca, Andrzej

AU - Mukherjee, Sumit

AU - Pink, Maren

AU - Rajca, Suchada

PY - 2006/10/18

Y1 - 2006/10/18

N2 - Calix[4]arenes constrained to the 1,3-alternate conformation and functionalized at the upper rim with four and two tert-butylnitroxides have been synthesized and characterized by X-ray crystallography, magnetic resonance (EPR and 1H NMR) spectroscopy, and magnetic studies. The 1,3-alternate nitroxide tetraradical and diradical provide unique polyradical scaffolds for dissection of the through-bond and through-space intramolecular exchange couplings. In addition, detailed magnetic studies of the previously reported calix[4]arene nitroxide tetraradical, which possesses cone conformation in solution, reveal conformational dependence of exchange coupling. Through-bond coupling between the adjacent nitroxide radicals is mediated by the nitroxide-m-phenylene-CH2-m-phenylene-nitroxide coupling pathway, and through-space coupling is found between the diagonal nitroxide radicals at the conformationally constrained N⋯N distance of 5-6 Å. Magnetic studies of the calix[4]arene polyradical scaffolds in frozen solutions show that the through-bond exchange coupling in the 1,3-alternate calix[4]arene tetraradical is antiferromagnetic, while that in cone calix[4]arene tetraradical is ferromagnetic. The through-space exchange couplings are antiferromagnetic in both cone and 1,3-alternate calix[4]arene tetraradical, as well as in the 1,3-alternate calix[4]arene diradical. The exchange coupling constants (|J/k|) are of the order of 1 K.

AB - Calix[4]arenes constrained to the 1,3-alternate conformation and functionalized at the upper rim with four and two tert-butylnitroxides have been synthesized and characterized by X-ray crystallography, magnetic resonance (EPR and 1H NMR) spectroscopy, and magnetic studies. The 1,3-alternate nitroxide tetraradical and diradical provide unique polyradical scaffolds for dissection of the through-bond and through-space intramolecular exchange couplings. In addition, detailed magnetic studies of the previously reported calix[4]arene nitroxide tetraradical, which possesses cone conformation in solution, reveal conformational dependence of exchange coupling. Through-bond coupling between the adjacent nitroxide radicals is mediated by the nitroxide-m-phenylene-CH2-m-phenylene-nitroxide coupling pathway, and through-space coupling is found between the diagonal nitroxide radicals at the conformationally constrained N⋯N distance of 5-6 Å. Magnetic studies of the calix[4]arene polyradical scaffolds in frozen solutions show that the through-bond exchange coupling in the 1,3-alternate calix[4]arene tetraradical is antiferromagnetic, while that in cone calix[4]arene tetraradical is ferromagnetic. The through-space exchange couplings are antiferromagnetic in both cone and 1,3-alternate calix[4]arene tetraradical, as well as in the 1,3-alternate calix[4]arene diradical. The exchange coupling constants (|J/k|) are of the order of 1 K.

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