Exchange Coupling Mediated Through-Bonds and Through-Space in Conformationally-Constrained Polyradical Scaffolds: Calix4arene Nitroxide Tetraradicals And Diradical

摘要

Calix[4]arenes constrained to 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 Kelvin.