Insight of the Metal-Ligand Interaction in f-Element Complexes by Paramagnetic NMR Spectroscopy

The magnetic properties of Ln^III and An^III complexes formed with dipicolinate ligands have been studied by NMR spectroscopy. To know precisely the geometries of these complexes, a crystallographic study by single-crystal X-ray diffraction (XRD) and extended X-ray absorption fine structure (EXAFS) in solution was performed. Several methods to separate the paramagnetic shifts observed in the NMR spectra were applied to these complexes. Methods using a number of nuclei of the dipicolinate ligands revealed an abrupt change in the geometries of the complexes and a metal-ligand interaction in the middle of the lanthanide series. A study of the variation of the paramagnetic shifts with temperature demonstrated that higher-order terms of the dipolar and contact contributions are required, especially for the lightest Ln^III and almost all the studied An^III . Bleaney's parameters z >_a and $$ relating to the contact and dipolar terms, respectively, were deduced from experimental data and compared with the results of ab initio calculations. Quite a good agreement was found for the temperature dependencies of z >_a and $$ . However, the $$ values obtained from cation magnetic anisotropy calculations showed some discrepancies with the values derived from Bleaney's equation defined for Ln^III . Other parameters, such as the crystal field parameter and the hyperfine constants F_i obtained from the experimental data of the [An(ethyl-dpa)₃ ]^3- complexes (ethyl-dpa=4-ethyl-2,6-dipicolinic acid), are at odds with the assumptions underlying Bleaney's theory.