With
their exceptional optoelectronic features, metal halide perovskites
(MHPs) are pushing the next wave of energy-related materials research.
Heretofore, most solid-state nuclear magnetic resonance (NMR) investigations
have focused on readily accessible nuclei. In contrast, the halogen
environments have been avoided due to their challenging quadrupolar
nature. Here, we report a rapid 35/37Cl NMR strategy for
MHPs, halide double perovskites (HDPs), and perovskite-inspired (PI)
materials embracing ultra-wideline acquisition approaches at moderate
and ultrahigh magnetic fields. The observed quadrupolar NMR parameters
(C
Q and η), supported by GIPAW–DFT
computations, provide an analytical fingerprint revealing distinct
features for chemically unique Cl environments sensitive to ion mixing,
dimensionality, cell volume, and Cl coordinating polyhedra. Moreover,
we report resolution between two nearly identical and two distinct
Cl environments of 3D and 2D Cs-based lead halide perovskites, respectively.
These results reveal a strategy for a routine and robust spectroscopic
approach to analyze local Cl chemical environments in metal halide
perovskites that can be extended broadly to other halogen-containing
semiconductors.