Determining Local Magnetic Susceptibility Tensors in Paramagnetic Lanthanide Crystalline Powders from Solid-State NMR Chemical Shift Anisotropies

Autor: Ridvan Ince, Abdelatif Doudouh, Nicolas Claiser, Éric Furet, Thierry Guizouarn, Laurent Le Pollès, Gwendal Kervern
Přispěvatelé: Cristallographie, Résonance Magnétique et Modélisations (CRM2), Université de Lorraine (UL)-Centre National de la Recherche Scientifique (CNRS), Institut des Sciences Chimiques de Rennes (ISCR), Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)
Rok vydání: 2023
Předmět:
Zdroj: The Journal of physical chemistry
The Journal of physical chemistry, 2023, 127 (6), pp.1547-1554. ⟨10.1021/acs.jpca.2c06955⟩
ISSN: 1520-5215
1089-5639
0022-3654
1541-5740
Popis: International audience; 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 aswell as consistent with bulk susceptibility measurements.
Databáze: OpenAIRE
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