Two New 2p–3d Metal Complexes with a Nitronyl-Nitroxide Ligand Derived from o-Vanillin: Synthesis, Crystals Structures and Magnetic Properties

Two new 2p–3d complexes, (Et₃NH)[ML(hfac)₂], have been obtained using the nitronyl-nitroxide radical (HL) derived from 2-hydroxy-3-methoxy-5-nitrobenzaldehyde (M = Mn 1; Co 2). The two compounds are isomorphous and their structures consist of anionic mononuclear species, [M(hfac)₂L]⁻, M = Mn 1; Co 2, and triethylammonium cations, Et₃NH⁺. The metal ions adopt an octahedral geometry, being coordinated by phenoxido and aminoxyl oxygen atoms from the ligand and four oxygen atoms from the hexafluoroacetylacetonato (hfac⁻) ligand. The cryomagnetic behaviors of the two compounds reveal relatively strong antiferromagnetic M(II)-Rad interactions (J_MnRad = −191 cm⁻¹, J_CoRad = −166 cm⁻¹ with H = −JS_MS_Rad). The EPR spectra (X- and Q-band) of compound 1 below 70 K show the characteristical features of a S = 2 spin system with zero field splitting terms of D = 0.26 cm⁻¹ and E = 0.031 cm⁻¹.