Nuclear Quadrupolar Resonance Structural Characterization of Halide Perovskites and Perovskitoids: A Roadmap from Electronic Structure Calculations for Lead–Iodide-Based Compounds

Metal halide perovskites, including some of their related perovskitoid structures, form a semiconductor class of their own, which is arousing ever-growing interest from the scientific community. With halides being involved in the various structural arrangements, namely, pure corner-sharing MX6 (M is metal and X is halide) octahedra, for perovskite networks, or alternatively a combination of corner-, edge-, and/or face-sharing for related perovskitoids, they represent the ideal probe for characterizing the way octahedra are linked together. Well known for their inherently large quadrupolar constants, which is detrimental to the resolution of nuclear magnetic resonance spectroscopy, most abundant halide isotopes (35/37Cl, 79/81Br, 127I) are in turn attractive for magnetic field-free nuclear quadrupolar resonance (NQR) spectroscopy. Here, we investigate the possibility of exploiting NQR spectroscopy of halides to distinctively characterize the various metal halide structural arrangements, using density functional theory simulations. Our calculations nicely match the available experimental results. Furthermore, they demonstrate that compounds with different connectivities of their MX6 building blocks, including lower dimensionalities such as 2D networks, show distinct NQR signals in a broad spectral window. They finally provide a roadmap of the characteristic NQR frequency ranges for each octahedral connectivity, which may be a useful guide to experimentalists, considering the long acquisition procedures typical of NQR. We hope this work will encourage the incorporation of NQR spectroscopy to further our knowledge of the structural diversity of metal halides.