⁸⁹Y chemical shift anisotropy: a sensitive structural probe of layered yttrium hydroxides revealed by solid-state NMR...

Anion-exchangeable Y₂(OH)₅X·nH₂O (LYH-X, X = monovalent anions, n ≈ 1.5) materials are an ideal platform for incorporating the unique properties of layered metal hydroxides and rare-earth (RE) ions, and thus have exhibited promising prospects for various applications. To further improve the performance of LYH-X and related functional materials, their structure-property relationships must be explored. However, due to the intrinsic felxibility, extracting the local structural details of these materials is particularly challenging. In this work, we utilized a combined approach of ⁸⁹Y solid-state NMR (ssNMR) spectroscopy and density functional theory (DFT) calculations to reveal the response of ⁸⁹Y chemical shift anisotropy (CSA) in LYH-X to the structural changes including a small displacement of cationic yttrium hydroxide layers and intercalated anions. Such subtle structural changes are often associated with dehydration/rehydration, anion-exchange, exfoliation, and the self-assembly process of LYH-X and related functional materials, which are exceedingly difficult to detect using other techniques. The principal components of ⁸⁹Y CSA show a larger variation range than isotropic chemical shifts, making CSA a more sensitive probe. In addition, it is found that the response of ⁸⁹Y CSA to structural changes is distinct for Y sites with different local coordination environments, opening great opportunities to analyze each Y site within these materials. All these observations suggest that the strategy involving both experimental (⁸⁹Y ssNMR) and theoretical (DFT) approaches can be utilized to extract previously unavailable ultrafine structural information of LYH-X and related materials, and provide fruitful insights into their thorough structure-property relationships.