Anisotropy of 4f states in 3d-4f single-molecule magnets

We have measured angular-dependent fluorescence-yield x-ray magnetic circular dichroism spectra on single crystals of the heterometallic 3d-4f 12-metallacrown-4 TbMn4 and DyMn4 complexes. Simulated spectra using crystal-field multiplet calculations reproduce the experimentally observed spectra. The orientation of the molecules causes linear dichroism spectra of the 4f absorption spectra. This natural linear dichroism shows the anisotropic charge distribution of the rare-earth 4f state in the tetragonal crystal field despite the small 4f crystal-field splitting. The magnetic moment of the molecule is dominated by the rare-earth moment revealing a considerably large contribution of orbital moment. From a sum-rule analysis of experimental and simulated x-ray magnetic circular dichroism, we determined corrected spin and orbital Dy moments at low temperature (14 K) within a magnetic field of 7 T. We find a significant angular dependence of the Dy magnetic moments, indicating the presence of fourth-order magnetic anisotropy

Solvent-induced high-spin transition in double-decker 3d–4f metallacrowns

Element-specific magnetic spin and orbital magnetic moments of 3d-4f double-decker metallacrown molecules have been investigated using x-ray magnetic circular dichroism. The double-decker metallacrowns comprise one rare-earth Gd(III) or Tb(III) ion embedded between two squared scaffolds of four Ni(II) ions. We observe a strong increase of the Ni(II) moments if the molecules are dissolved in methanol, indicating a spin crossover from a low-spin to a high-spin state. In contrast, dichloromethane does not change the spin state. This result is explained by a change of the coordination environment of nickel. The comparison of charge-transfer multiplet calculations with the experimental absorption spectra confirm the different ligand fields

Anisotropy of 4f states in 3d 4f single molecule magnets

We have measured angular dependent fluorescence yield x ray magnetic circular dichroism spectra on single crystals of the heterometallic 3d amp; 8722;4f 12 metallacrown 4 TbMn4 and DyMn4 complexes. Simulated spectra using crystal field multiplet calculations reproduce the experimentally observed spectra. The orientation of the molecules causes linear dichroism spectra of the 4f absorption spectra. This natural linear dichroism shows the anisotropic charge distribution of the rare earth 4f state in the tetragonal crystal field despite the small 4f crystal field splitting. The magnetic moment of the molecule is dominated by the rare earth moment revealing a considerably large contribution of orbital moment. From a sum rule analysis of experimental and simulated x ray magnetic circular dichroism, we determined corrected spin and orbital Dy moments at low temperature 14 K within a magnetic field of 7 T. We find a significant angular dependence of the Dy magnetic moments, indicating the presence of fourth order magnetic anisotrop

Element-specific magnetic properties of mixed 3d−4f metallacrowns

Single molecule magnets comprising rare earth metals are of high interest due to the unquenched orbital moments of the rare earth ions that result in a large energy barrier for magnetization reversal. We investigate the magnetic properties of polynuclear 3d-4f 15-MC-5 metallacrowns using x-ray magnetic circular dichroism of powder samples at a temperature of 7 K in a magnetic field of 7 T. The sum rule analysis reveals element-specific spin and orbital moments. The magnetic moments of the 3d transition metal Ni(II) ions are coupled antiferromagnetically to each other and contribute only little to the total molecular moment. The spin and orbital moments of the rare earth ions are unexpectedly smaller than the ionic values resulting from Hund's rules. We explain the reduction of the orbital magnetic moment by a finite magnetic anisotropy. Considering an energy functional including magnetic anisotropy and Zeeman energy the powder average reveals a magnetic anisotropy of 28 meV (340 K) in the case of Dy(III) and 7 meV (85 K) in the case of Tb(III). The spin moments agree with the ionic value, too, when the expectation values of the dipole operator are considered

Anisotropy of 4f states in 3d-4f single-molecule magnets

We have measured angular-dependent fluorescence-yield x-ray magnetic circular dichroism spectra on single crystals of the heterometallic 3d-4f 12-metallacrown-4 TbMn4 and DyMn4 complexes. Simulated spectra using crystal-field multiplet calculations reproduce the experimentally observed spectra. The orientation of the molecules causes linear dichroism spectra of the 4f absorption spectra. This natural linear dichroism shows the anisotropic charge distribution of the rare-earth 4f state in the tetragonal crystal field despite the small 4f crystal-field splitting. The magnetic moment of the molecule is dominated by the rare-earth moment revealing a considerably large contribution of orbital moment. From a sum-rule analysis of experimental and simulated x-ray magnetic circular dichroism, we determined corrected spin and orbital Dy moments at low temperature (14 K) within a magnetic field of 7 T. We find a significant angular dependence of the Dy magnetic moments, indicating the presence of fourth-order magnetic anisotropy