Validation of Ab-Initio-Predicted Magnetic Anisotropies and Magneto-structural Correlations in Linear Hetero-trinuclear DyIII-NiII2 Compounds

Reported are single crystal SQUID and single crystal high-frequency/high-field EPR data of a trinuclear complex with a rare six-coordinate coordination sphere of a Dy-III center coupled to two terminal six-coordinate Ni-II ions. The analysis of the single crystal spectroscopic parameters allows for an accurate description of the ground state wavefunction. The experimental analysis is supplemented by the analysis of the paramagnetic NMR spectra, allowing for a thorough description of the Dy-III center. The experimental data are interpreted on the basis of an ab initio ligand field analysis, and the computed parameters are in good agreement with the experimental observations. This supports the quality of the theoretical approach based on a pseudo-spin Hamiltonian for the electronic ground state. Further support emerges from the ab initio ligand field theory based analysis of a structurally very similar system that, in contrast to the complex reported here, shows single molecule magnetic properties, and this is in agreement with the quantum-chemical prediction and analysis.

Automated summary

The study presents single crystal data of a trinuclear complex and analyzes the ground state wavefunction accurately based on spectroscopic parameters. The experimental analysis also provides a detailed description of the Dy-III center through paramagnetic NMR spectra. The theoretical approach, supported by ab initio ligand field analysis, shows good agreement with the experimental observations, confirming the quality of the theoretical method based on a pseudo-spin Hamiltonian for the electronic ground state.