Syntheses, structure, magnetic and thermodynamics property of novel lanthanide complexes with nitronyl nitroxide radical

Four new nitronyl nitroxide radical-Ln(III) complexes, Ln(hfac)3(NITPhSCF3)2 (Ln(III) = Sm(1), Gd(2), Tb(3), Dy(4); NITPhSCF3 = 2-(4-trifluoromethylthiophenyl)-4,4,5,5-tetramethylimidazoline-1-oxyl- 3-oxide; hfac = hexafluoroacetylacetonate), have been synthesized and characterized. They are isostructural, which show mononuclear tri-spin structures. The central Ln(III) ion is eight-coordinated by three hfac anions and two NITPhSCF3 molecules. Direct-current magnetic study shows that there exist ferromagnetic interactions between Gd(III) ion and radicals (NITPhSCF3) with JGd-Rad = 1.61 cm−1, and antiferromagnetic interactions between radicals with JRad-Rad = −2.83 cm−1 in complex 2. The magnetic analysis with the rough approximate model show that a ferromagnetic coupling exists between Tb(III) and radical in 3, while a antiferromagnetic coupling between Dy(III) and radical in 4. The thermodynamics properties of four complexes were studied with differential scanning calorimetry (DSC), such as heat capacity, thermodynamic functions (HT-H298.15K), (ST-S298.15K), and (GT-G298.15K).