Manipulating Lone-Pair-Driven Luminescence in 0D Tin Halides by Pressure-Tuned Stereochemical Activity from Static to Dynamic.

The excellent luminescence properties and structural dynamics driven by the stereoactivity of the lone pair in a variety of low-dimensional ns2 metal halides have attracted growing investigations for optoelectronic applications. However, the structural and photophysical aspects of the excited state associated with the lone pair expression are currently open questions. Herein, zero-dimensional Sn-based halides with static stereoactive 5s2 lone pairs are selected as a model system to understand the correlations between the distinctive lone pair expression and the excited-state structural relaxation and charge carrier dynamics by continuous lattice manipulation. Lattice compression drives 5s2 lone pair active switching and self-trapped exciton (STE) redistribution by suppressing excited-state structural deformation of the isolated SnBr42- units. Our results demonstrate that the static expression of the 5s2 lone pair results in a red broadband triplet STE emission with a large Stokes shift, while its dynamic expression creates a sky-blue narrowband emission dominated by the radiative recombination of singlet STEs. Our findings and the photophysical mechanism proposed highlight the stereochemical effects of lone pair expression in controlling light emission properties and offer constructive guidelines for tuning the optoelectronic properties in diverse ns2 metal halides.