“Switching on” the single-molecule magnet properties within a series of dinuclear cobalt(iii)–dysprosium(iii) 2-pyridyloximate complexes

Abstract

The use of 2-pyridinealdoxime (paoH), methyl 2-pyridyl ketone oxime (mepaoH), phenyl 2-pyridyl ketone oxime (phpaoH) and pyridine-2-amidoxime (NH₂paoH) for the synthesis of dinuclear Co^III/Dy^III complexes is described in the absence or presence of an external base. Complexes [CoDy(pao)₃(NO₃)₃] (1), [CoDy(mepao)₃(NO₃)₃] (2), [CoDy(phpao)₃(NO₃)₃] (3) and [CoDy(NH₂pao)₃(NO₃)₃]·3MeOH (4·3MeOH) have been isolated and their structures have been determined by single-crystal X-ray crystallography. The complexes crystallize in non-centrosymmetric (2, 3) or centrosymmetric (1, 4·3MeOH) trigonal space groups and form a family of triply-oximate bridged dinuclear Co(III)–Dy(III) complexes. The crystals of 1, 3 and 4·3MeOH contain mixtures of Δ and Λ enantiomers, whereas complex 2 is enantiomerically pure (Λ). A 3-fold crystallographic axis (C₃) passes through two metal ions in all complexes. The low-spin Co^III and Dy^III ions are bridged by three oximate groups belonging to the η¹:η¹:η¹:μ 2-pyridyloximate ligands. The Co^III centre is octahedrally coordinated by the six nitrogen atoms of the deprotonated organic ligands in a facial arrangement. The Dy^III centre is bound to an O₉ set of donor atoms, its coordination sphere being completed by three bidentate chelating nitrato groups. The coordination polyhedron around Dy^III in 1 is best described as the Johnson tricapped trigonal prism, while the coordination geometries of the Dy^III centres in 2, 3 and 4·3MeOH are best described as consisting of spherical tricapped trigonal prismatic coordination polyhedra. The spectroscopic data of the complexes are also reported and discussed in the infra-red region in terms of the coordination modes of the ligands involved. The magnetic properties of these complexes were studied between 300 and 1.8 K revealing mainly the depopulation of the Dy^IIIm_j sublevels of the ground ⁶H_15/2 state. The intrinsic magnetic anisotropy of the Dy^III centers is clearly observed by the non-superimposed magnetization (M) versus H/T data, but single-molecule magnet (SMM) properties were detected only for the mepao⁻-containing complex 2. The origin of these properties in 2 is critically discussed and supported by computational studies.