Abstract
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) × 10−7 s, 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 × 10−7 s. 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.
Original language | English |
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Pages (from-to) | 1719-1730 |
Number of pages | 12 |
Journal | Chemical Science |
Volume | 4 |
Issue number | 4 |
DOIs | |
Publication status | Published - 31 Jan 2013 |