A new family of Ln–radical chains (Ln = Nd, Sm, Gd, Tb and Dy): synthesis, structure, and magnetic properties

Abstract

Five new one-dimensional rare earth–nitronyl nitroxide radical complexes [Ln(hfac)₃(NIT-3BrPhOMe)]_n (Ln = Nd (1), Sm (2), Gd (3), Tb (4), Dy (5); hfac = hexafluoroacetylacetonate; NIT-3BrPhOMe = 2-(3′-bromo-4′-methoxyl)-4,4,5,5-tetramethyl-imidazolyl-1-oxyl-3-oxide) have been successfully prepared and structurally characterized. Five complexes possess linear chain structure in which the NIT-3BrPhOMe radical ligands link Ln(hfac)₃ units through the oxygen atoms of nitronyl nitroxide groups. DC magnetic studies show that Nd, Sm and Gd complexes are paramagnetic above 2.0 K, whereas Tb and Dy complexes show antiferromagnetic ordering with T_N = 19.9 K and 6.4 K, respectively. Moreover, Tb and Dy complexes exhibit frequency-dependence of ac magnetic susceptibilities, suggesting the presence of slow magnetic relaxation. This work demonstrated that the substituents of the nitronyl nitroxide radical and the lanthanide ion can play a crucial role in modulating the magnetic behavior for one-dimensional lanthanide–radical systems.