A trianionic ligand H3L (2-hydroxy-N-(2-{[(2-hydroxyphenyl)methylene]amino}-2-methylpropyl)benzamide) with an inner N2O2 coordination site and an oxygen atom coming from an amide function not involved in this site yields monoanionic LCu− complexes that react with Ln(hfa)3·2H2O (hfa = hexafluoroacetylacetonato ligand) to give dinuclear Cu–Ln complexes that self-assemble into tetranuclear species, as demonstrated by the structural determination of the [LCuDy(hfa)2(dmf)2]2 complex. High-spin species are then isolated for two ferromagnetic interactions are active in the [Cu–Gd]2 entities, through the double phenoxo bridge (J = 3.2 cm−1) and through the single amide bridge (j = 0.54 cm−1). These interactions are still present in the [Cu–Tb]2 and [Cu–Dy]2 complexes which behave as single molecule magnets (SMMs), due to the introduction of anisotropic Ln ions in place of Gd ions.
The cyanoacetate complexes, {[Ln2(CNCH2COO)6(H2O)4]·2H2O}n, with Ln = Gd, Nd, show field-induced slow relaxation: resonant phonon trapping and Orbach process for Gd, and Orbach and direct processes for Nd.