Building blocks containing $5d$ spin centres are promising for constructing single molecule magnets due to their large spin-orbit interaction, but experimental and computational results obtained so far indicate that this might not be the case for Re$^\textrm{IV}$ centres in an octahedral environment. Density functional results obtained in this work for [ReCl$_4$(CN)$_2$]$^{2-}$ and trinuclear complexes formed by attaching Mn$^\textrm{II}$ centres to the cyano ligands indicate that zero field splitting in such complexes exhibits large rhombicity (which leads to fast relaxation of the magnetisation) even if there are only small distortions from an ideal geometry with a four-fold symmetry axis. This is already apparent if second-order spin-orbit perturbation theory is applied but even more pronounced if higher-order spin-orbit effects are included as well, as demonstrated by wavefunction based calculations. Computational results are cast into a ligand field model and these simulations show that especially a distortion which is not along the $C_4/C_2$ axeshas a large effect on the rhombicity. Quantum simulations on these complexes are difficult because the zero field splitting strongly depends on the energetic position of the low-lying doublets from the $t_{2g}^3$ configuration.
Electronic effect and geometry distortion of low-symmetry ligand-field on anisotropy barrier (Ueff) of spin reversal have been compared in three Dy(III) single-ion magnets through simultaneous binding of chelating ligands. The...
Abstract
As a model molecule of actinide chemistry, UO molecule plays an important role in understanding the electronic structure and chemical bonding of actinide-containing species. We report a study of the laser-induced fluorescence spectra of the U16O and U18O using two-dimensional spectroscopy. Several rotationally resolved excitation spectra were investigated. Accurate molecular rotational constants and equilibrium internuclear distances were reported. Low-lying electronic states information was extracted from high resolution dispersed fluorescence spectra and analyzed by the ligand field theory model. The configuration of the ground state was determined as U2+(5f37s)O2-. The branching ratios, and the vibrational harmonic and anharmonic parameters were also obtained. Radiative lifetimes were determined by recording the time-resolved fluorescence spectroscopy. Transition dipole moments were calculated using the branching ratios and the radiative lifetimes. These findings were elucidated by using quantum-chemical calculations, and the chemical bonding was also analyzed. The findings presented in this work will enrich our understanding of actinide-containing molecules.
Is [ReCl4(CN)2]2− a good Building Block for Single Molecule Magnets? A Theoretical Investigation.