Interplay Between Stereochemically Active Lone Pair Repulsions, Sigma Hole Interactions, and Delocalized Redox Processes in Topochemical Fluoride‐Ion Insertion

Abstract Topochemical insertion/extraction of cations has emerged as a generalizable strategy for modulating the crystal and electronic structure of periodic solids. In contrast, strategies for topochemical anion insertion are poorly explored and fundamental principles for designing insertion hosts to accommodate anions remain scarce. Here, we observe reversible room‐temperature fluoride‐ion insertion within tunnels of Sn 2 TiO 4 defined by the stereochemical expression of Sn 5 s 2 lone pairs. X‐ray scattering studies of fluoride‐ion‐insertion‐induced crystal structure modulation and X‐ray absorption/emission spectroscopy probes of electronic structure along with magnetic susceptibility measurements and first‐principles calculations are used to decipher design principles underpinning reversible fluoride‐ion insertion and bulk diffusion. Fluoride‐ion insertion is enabled by a combination of a large, polarizable tunnel, delocalized redox at Ti─O─Sn centers, inherent repulsion between the fluoride‐ion and Sn 5 s 2 electron lone pairs, and the formation of dative interactions between Sn‐centered σ‐holes and fluoride‐ions, yielding a reversible capacity of 0.5 fluoride‐ions per Sn 2 TiO 4 formula unit. Our results demonstrate that the complex interplay between dative interactions and stereochemically active lone pair repulsions is critical to defining the thermodynamics and kinetics controlling fluoride‐ion insertion and diffusion. As such, the design of fluoride‐ion insertion hosts for anion batteries requires site‐selective modification to modulate lattice—ion interactions.