Investigating trends in actinide covalency and magnetism with ^35/37Cl SSNMR spectroscopy and first-principles...

Solid-state NMR (SSNMR) spectroscopy is a powerful technique for studying actinide chemistry but has been significantly limited due to the complex paramagnetism, and radiological hazards presented by these materials. Lanthanide and actinide salts often feature magnetic ordering and can be paramagnetic, ferromagnetic, or antiferromagnetic depending on temperature and electronic structure. Paramagnetic interactions can manifest in SSNMR both as secular spectral shifts and/or couplings as well as contributions from non-secular relaxation. Both effects can be directly measured with NMR and used to extrapolate rich chemical information such as coordination environments, bonding characteristics, local molecular dynamics, and correlation times. Typically, these studies are carried out on high-γ and highly abundant NMR-active isotopes (e.g., ¹H, ^6/7Li, ¹⁹F, ²³Na, etc.) or on enriched rare isotopes (e.g., ²H and ¹⁷O), which can be expensive. Herein, we present a facile methodology to measure the ^35/37Cl electric-field gradient (EFG) and paramagnetic shift anisotropy (SA) tensor components using static wideline SSNMR measurements of LaCl3, NdCl3, UCl3, and UCl4. The static powder spectra were measured with both ³⁵Cl and ³⁷Cl SSNMR to increase the fidelity of the extracted tensor parameters. Variable temperature NMR of a select case confirms the Curie-Weiss paramagnetism. Relaxation measurements of both nuclei further corroborate observations owing to the paramagnetic relaxation enhancement and reveal simultaneous quadrupolar relaxation mechanisms. Density functional theory (DFT) calculations using Hubbard U corrections to the uranium valence orbitals show excellent agreement with experimental EFG tensor parameters and help describe the bonding characteristics in these lanthanide and actinide systems.