Correlating photophysical properties with stereochemical expression of 6s${}^2$ lone pairs in two-dimensional lead halide perovskites

Two-dimensional (2D) lead halide perovskites (LHPs) have shown great promises for light-emitting applications and excitonic devices. Fulfilling these promises demands an in-depth understanding on the relationships between the structural dynamics and exciton-phonon interactions that govern the optical properties. Here, we unveil the structural dynamics of 2D lead iodide perovskites with different spacer cations. Loose packing of an undersized spacer cation leads to out-of-plane octahedral tilting, whereas compact packing of an oversized spacer cation stretches Pb-I bond length, resulting in Pb${}^{2+}$ off-center displacement driven by stereochemical expression of the Pb${}^{2+}$ 6s${}^2$ lone pair electrons. Density functional theory calculations indicate that the Pb${}^{2+}$ cation is off-center displaced mainly along the direction where the octahedra are stretched the most by the spacer cation. We find dynamic structural distortions associated with either octahedral tilting or Pb${}^{2+}$ off-centering lead to a broad Raman central peak background and phonon softening, which increase the non-radiative recombination loss via exciton-phonon interactions and quench the photoluminescence intensity. The correlations between the structural, phonon, and optical properties are further confirmed by the pressure tuning of the 2D LHPs. Our results demonstrate that minimizing the dynamic structural distortions via a judicious selection of the spacer cations is essential to realize high luminescence properties in 2D LHPs. (© 2023 Wiley‐VCH GmbH)