Single molecule magnetism in a family of mononuclear β-diketonate lanthanide(iii) complexes: Rationalization of magnetic anisotropy in complexes of low symmetry

The use of an amino-pyridyl substituted β-diketone, N-(2-pyridyl)-ketoacetamide (paaH), has allowed for the isolation of two new families of isostructural mononuclear lanthanide complexes with general formulae: [Ln(paaH*)2(H2O)4][Cl]3·2H2O (Ln = Gd (1), Tb (2), Dy (3), Ho (4), Er (5) and Y (6)) and [Ln(paaH*)2(NO3)2(MeOH)][NO3] (Ln = Tb (7), Dy (8), Ho (9) and Er (10)). The dysprosium members of each family (3 and 8) show interesting slow magnetic relaxation features. Compound 3 displays Single Molecule Magnet (SMM) behaviour in zero DC field with an energy barrier to thermal relaxation of Ea= 177(4) K (123(2) cm−1) with τ0= 2.5(8) × 10−7s, while compound 8 shows slow relaxation of the magnetization under an optimum DC field of 0.2 T with an energy barrier to thermal relaxation of Ea= 64 K (44 cm−1) with τ0= 6.2 × 10−7s. Ab initio multiconfigurational calculations of the Complete Active Space type have been employed to elucidate the electronic and magnetic structure of the low-lying energy levels of compounds 2–5 and 8 . The orientation of the anisotropic magnetic moments for compounds 2–5 are rationalized using a clear and succinct, chemically intuitive method based on the electrostatic repulsion of the aspherical electron density distributions of the lanthanides. © 2013 The Royal Society of Chemistry.