Magnetic interactions in a series of paramagnetic Ln(III) complexes with a chelated imino nitroxide radical

Abstract: The magnetic interactions in a new series of isostructural imino nitroxide radical lanthanide(III) complexes, [Ln(hfac)3(IM2py)] (Ln=Gd–Yb: IM2py=2-(2′-pyridyl)-4,5-dihydro-4,4,5,5-tetramethyl-1H-imidazoline-1-oxy; hfac=1,1,1,5,5,5-hexafluoro-2,4-pentanedione), are examined by considering the intrinsic paramagnetic contribution of the Ln(III) ion from the corresponding [Ln(hfac)3(pybzim)] with a diamagnetic pybzim(2-(2-pyridyl)benzimidazole) ligand; the Ln(III)–IM2py interaction being antiferromagnetic for the 4f7 to 4f13 Ln(III) complexes and negligibly small for the other complexes. This series is the first example reverse to the previous cases for the series of Ln–Cu or Ln–aminoxyl(NIT) radical (4,5-dihydro-4,4,5,5-tetramethyl-1H-imidazoline-3-oxide-1-oxy) complexes, other than only a few examples of semiquinone Ln complexes. This reverse nature of the magnetic interaction, as compared with the NIT complexes, validates the empirical approach by O. Kahn et al. [Inorg. Chem. 38 (1999) 3692; J. Am. Chem. Soc. 122 (2000) 3413] in the spin-coupled systems for a series of Ln(III) complexes. [Copyright &y& Elsevier]