Studies of the Temperature Dependence of the Structure and Magnetism of a Hexagonal-Bipyramidal Dysprosium(III) Single-Molecule Magnet

Abstract

The hexagonal-bipyramidal lanthanide(III) complex [Dy(O ^tBu)Cl(18-C-6)][BPh ₄] ( 1; 18-C-6 = 1,4,7,10,13,16-hexaoxacyclooctadecane ether) displays an energy barrier for magnetization reversal ( U _eff) of ca. 1000 K in a zero direct-current field. Temperature-dependent X-ray diffraction studies of 1 down to 30 K reveal bending of the Cl–Ln–O ^tBu angle at low temperature. Using ab initio calculations, we show that significant bending of the O–Dy–Cl angle upon cooling from 273 to 100 K leads to a ca. 10% decrease in the energy of the excited electronic states. A thorough exploration of the temperature and field dependencies of the magnetic relaxation rate reveals that magnetic relaxation is dictated by five mechanisms in different regimes: Orbach, Raman-I, quantum tunnelling of magnetization, and Raman-II, in addition to the observation of a phonon bottleneck effect.

Abstract

The temperature-dependent crystallography down to 30 K and field-dependent magnetic relaxation rate using both alternating- and direct-current magnetic measurements of a hexagonal-bipyramidal dysprosium(III) compound, [Dy(O ^tBu)Cl(18-C-6)][BPh ₄], were studied. Temperature-dependent bending of the Cl−Ln−O angle results in an approximate 10% decrease in the energy of the excited electronic states. Magnetic studies reveal that magnetic relaxation is dictated by five mechanisms in different regimes: Orbach, Raman-I, quantum tunnelling of magnetization, and Raman-II, in addition to the observation of a phonon bottleneck effect.