Rationalization of the Lanthanide-Ion-Driven Magnetic Properties in a Series of 4f–5d Cyano-Bridged Chains

Abstract

Magnetic properties of new d-f cyanido-bridged 1D assemblies [RE(pzam)(3)(H(2)O)W(CN)(8)]·H(2)O (RE(III) = Gd, 1, Tb, 2, Dy, 3; pzam = pyrazine-2-carboxamide) were studied by temperature- and field-dependent magnetization measurements. No evidence for 3D interchain magnetic ordering is found above 2 K. Multiconfiguration ab initio calculations and subsequent modeling afforded simulation of the weak zero-field splitting effect in 1 and discussion of magnetic anisotropy in the f units of compounds 2 and 3. A semiquantitative corroboration with the experimental magnetic measurements is presented, performing the simulation of magnetic susceptibility vs temperature and magnetization vs field variation. The association into molecular and supramolecular architectures is analyzed by means of energy decomposition subsequent to the DFT calculations on idealized molecular models extracted from the experimental chain structure.

Ligand field density functional theory for the prediction of future domestic lighting

“…While working in the vicinity of our LFDFT developed approach, this methodological update will also help for the reliable determination of the magnetic properties of lanthanide or transition metal complexes being currently popular in theoretical research. [58][59][60][61][62][63][64][65] The formulation of the ligand field interaction, which takes into account the presence of the ligands in the coordination sphere of the lanthanide, is also the subject of intense work. 32,44 Here, the ligand field potential includes two distinct interactions the perturbation of the 4f and 5d orbitals of the lanthanide, respectively, leading to ligand field matrix of 12 by 12 elements.…”

The angular overlap model extended for two-open-shell f and d electrons

“…[6][7][8] We mention also the situation of non-aufbau occupation [9][10][11][12] of the 4f orbitals inasmuch as convergence problems may frequently occur in the self-consistent field (SCF). The calculation of the f-d transitions in lanthanide phosphors is addressed with respect to the ligand field theory 13,14 but not restricted to its classical empirical frame.…”

Realization of the one-dimensional anisotropicXYmodel in a Tb(III)-W(V) chain compound

“…Previously, we reported the synthesis and magnetothermal studies of heterometallic rareearth (RE) -based cyanido-bridged 1D complexes, namely, [RE(pzam) 3 (H 2 O)Mo(CN) 8 ]·H 2 O (RE = Nd, Sm, Gd, Tb, and Er, pzam = pyrazine-2-carboxamide), whose magnetic properties are mainly determined by the particular RE ion involved. [7][8][9][10][11] We found that the Nd(III) and Mo(V) ions are coupled ferromagnetically into magnetic chains by an XY -type (planar) interaction. 10 The interaction between Tb(III) and Mo(V) is likewise ferromagnetic, but with a strong Isingtype anisotropy.…”