Determining local magnetic susceptibility tensors in paramagnetic lanthanide crystalline powders from solid-state NMR chemical shift anisotropies - Archive ouverte HAL Accéder directement au contenu
Article Dans Une Revue The Journal of physical chemistry Année : 2023

Determining local magnetic susceptibility tensors in paramagnetic lanthanide crystalline powders from solid-state NMR chemical shift anisotropies

Détermination d'un tenseur de susceptibilité magnétique local dans une poudre microcristalline de complexes paramagnétiques de lanthanides par analyse des anisotropies de déplacement chimique en RMN des solides.

Résumé

Exploring magnetic properties at the molecular level is a challenge that have been met by developing many experimental and theoretical solutions such as polarized neutron diffraction (PND), muon-spin rotation (µ-SR), electron paramagnetic resonance (EPR), SQUID-based magnetometry measurements and advanced modelling on openshell systems and relativistic calculations. These methods are powerful tools that shed light on the local magnetic response in specifically designed magnetic materials such as contrast agents, for MRI, molecular magnets, magnetic tags for biological NMR etc. All of these methods have their advantages and disadvantages. In order to complement the possibilities offered by these methods, we propose a new tool that implements a new approach combining simulation and fitting for high-resolution solid-state NMR spectra of lanthanide-based paramagnetic species. This method relies on a rigorous acquisition thanks to Short Highpower Adiabatic Pulses (SHAP) of high-resolution solid-state NMR isotropic and anisotropic data on a powdered magnetic material. It is also based on an efficient modelling of this data thanks to a semi-empirical model based on a parametrization of the local magnetism and the crystal structure provided by diffraction methods. The efficiency of the calculation relies on a thorough simplification of the electron-nucleus interactions (point-dipole interaction, no Fermi-contact) which is validated by experimental analysis. By taking advantage of the efficient calculation possibilities offered by our method, we can compare a great number of simulated spectra to experimental data and find the best-matching local magnetic susceptibility tensor. This method was applied to a series of isostructural lanthanide oxalates which are used as a benchmark system for many analytical methods. We present the results of thorough solid-state NMR and extensive modelling of the hyperfine interaction (including up to 400 paramagnetic centers) that yields local magnetic susceptibility tensors measurements that are self-consistent as well as consistent with bulk susceptibility measurements.

Domaines

Chimie
Fichier principal
Vignette du fichier
Ln2Oxa_3Susceptibility.pdf (1.67 Mo) Télécharger le fichier
Ln2Oxa_3Susceptibility_SI.pdf (21.22 Mo) Télécharger le fichier
Origine : Fichiers produits par l'(les) auteur(s)

Dates et versions

hal-03988452 , version 1 (14-02-2023)

Identifiants

Citer

Ridvan Ince, Abdelatif Doudouh, Nicolas Claiser, Eric Furet, Thierry Guizouarn, et al.. Determining local magnetic susceptibility tensors in paramagnetic lanthanide crystalline powders from solid-state NMR chemical shift anisotropies. The Journal of physical chemistry, 2023, 127 (6), pp.1547-1554. ⟨10.1021/acs.jpca.2c06955⟩. ⟨hal-03988452⟩
22 Consultations
20 Téléchargements

Altmetric

Partager

Gmail Facebook X LinkedIn More