Single-Ion Anisotropy and Intramolecular Interactions in CeIII and NdIII Dimers

This article reports the syntheses, characterization, structural description, together with magnetic and spectroscopic properties of two isostructural molecular magnets based on the chiral ligand N,N'-bis((1,2-diphenyl-(pyridine-2-yl)methylene)-(R,R/ S, S)-ethane-1,2-diamine), L1, of general formula [Ln(2)(RR-L1)(2)(Cl-6)]center dot MeOH center dot 1.5H(2)O, (Ln = Ce (1) or Nd (2)). Multifrequency electron paramagnetic resonance (EPR), cantilever torque magnetometry (CTM) measurements, and ab initio calculations allowed us to determine single-ion magnetic anisotropy and intramolecular magnetic interactions in both compounds, evidencing a more important role of the anisotropic exchange for the Nd-III derivative. The comparison of experimental and theoretical data indicates that, in the case of largely rhombic lanthanide ions, ab initio calculations can fail in determining the orientation of the weakest components, while being reliable in determining their principal values. However, they remain of paramount importance to set the analysis of EPR and CTM on sound basis, thus obtaining a very precise picture of the magnetic interactions in these systems. Finally, the electronic structure of the two complexes, as obtained by this approach, is consistent with the absence of zero-field slow relaxation observed in ac susceptibility.

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This study reports the synthesis, characterization, structural description, and magnetic and spectroscopic properties of two isostructural molecular magnets based on a chiral ligand. Experimental and theoretical data comparison shows that ab initio calculations are reliable in determining principal values and are crucial for establishing the analysis of EPR and CTM.