Cs2SnX6 (X = Cl, Br, and I) compounds have emerged as promising lead-free and ambient-stable materials for photovoltaic and optoelectronic applications. To advance these promising materials, it is crucial to determine the correlations between physical properties and their local structure and dynamics. Solid-state NMR spectroscopy of multiple NMR-active nuclei (133Cs, 119Sn, and 35Cl) in these cesium tin­(IV) halides has been used to reveal the atomic structure, which plays a key role in the materials’ optical properties. The 119Sn NMR chemical shifts span approximately 4000 ppm, and the 119Sn spin-lattice relaxation times span 3 orders of magnitude when the halogen goes from chlorine to iodine in these diamagnetic compounds. Moreover, ultrawideline 35Cl NMR spectroscopy of Cs2SnCl6 indicates an axially symmetric chlorine electric field gradient tensor with a large quadrupolar coupling constant of ca. 32 MHz, suggesting the presence of a chlorine moiety that is directly attached to Sn­(IV) ions. Variable-temperature 119Sn spin-lattice relaxation time measurements support the presence of dynamics of octahedral SnI6 units in Cs2SnI6. We further show that complete mixed-halide solid solutions of Cs2SnCl x Br6–x and Cs2SnBr x I6–x (0 ≤ x ≤ 6) form at any halogen compositional ratio. 119Sn and 133Cs NMR spectroscopy resolve the unique local SnCl n Br6–n and SnBr n I6–n (n = 0–6) octahedral and CsBr m I12–m (m = 0–12) cuboctahedral environments in the mixed-halide samples. The experimentally observed 119Sn NMR results are consistent with magnetic shielding parameters obtained by density functional theory computations that were obtained to model the random halogen distribution in mixed-halide analogues. Finally, we demonstrate the difference in the local structures and the optical absorption properties of Cs2SnI6 samples prepared by solvent-assisted and solvent-free synthesis routes.

Vacancy-ordered double perovskites Cs₂SnX₆ (X = Cl, Br, I) have emerged as promising lead-free and ambient-stable materials for photovoltaic and optoelectronic applications. To advance these promising materials, it is crucial to determine the correlations between physical properties and their local structure and dynamics. Solid-state NMR spectroscopy of multiple NMR-active nuclei (¹³³Cs, ¹¹⁹Sn and ³⁵Cl) in these cesium tin(IV) halides has been used to decode the structure, which plays a key role in the materials’ optical properties. The ¹¹⁹Sn NMR chemical shifts span approximately 4000 ppm and the ¹¹⁹Sn spin-lattice relaxation times span three orders of magnitude when the halogen goes from chlorine to iodine in these diamagnetic compounds. Moreover, ultrawideline ³⁵Cl NMR spectroscopy for Cs₂SnCl₆ indicates an axially symmetric chlorine electric field gradient tensor with a large quadrupolar coupling constant of <i>ca.</i> 32 MHz, suggesting a chlorine that is directly attached to Sn(IV) ions. Variable temperature ¹¹⁹Sn spin lattice relaxation time measurements uncover the presence of hidden dynamics of octahedral SnI₆ units in Cs₂SnI₆ with a low activation energy barrier of 12.45 kJ/mol (0.129 eV). We further show that complete mixed-halide solid solutions of Cs₂SnCl_xBr_6−x and Cs₂SnBr_xI_6−x (0 ≤ x ≤ 6) form at any halogen compositional ratio. ¹¹⁹Sn and ¹³³Cs NMR spectroscopy resolve the unique local SnCl<i>_n</i>Br_6−<i>n</i>and SnBr<i>_n</i>I_6−<i>n</i> (<i>n</i> = 0−6) octahedral and CsBr<i>_m</i>I_{12−<i>m</i>} (<i>m</i> = 0−12) cuboctahedral environments in the mixed-halide samples. The experimentally observed ¹¹⁹Sn NMR results are consistent with magnetic shielding parameters obtained by density functional theory computations to verify random halogen distribution in mixed-halide analogues. Finally, we demonstrate the difference in the local structures and optical absorption properties of Cs₂SnI₆ samples prepared by solvent-assisted and solvent-free synthesis routes.