Strongly Anharmonic Octahedral Tilting in Two-Dimensional Hybrid Halide Perovskites

[Image: see text] Recent investigations of two-dimensional (2D) hybrid organic–inorganic halide perovskites (HHPs) indicate that their optical and electronic properties are dominated by strong coupling to thermal fluctuations. While the optical properties of 2D-HHPs have been extensively studied, a comprehensive understanding of electron–phonon interactions is limited because little is known about their structural dynamics. This is partially because the unit cells of 2D-HHPs contain many atoms. Therefore, the thermal fluctuations are complex and difficult to elucidate in detail. To overcome this challenge, we use polarization-orientation Raman spectroscopy and ab initio calculations to compare the structural dynamics of the prototypical 2D-HHPs [(BA)(2)PbI(4) and (PhE)(2)PbI(4)] to their three-dimensional (3D) counterpart, MAPbI(3). Comparison to the simpler, 3D MAPbI(3) crystal shows clear similarities with the structural dynamics of (BA)(2)PbI(4) and (PhE)(2)PbI(4) across a wide temperature range. The analogy between the 3D and 2D crystals allows us to isolate the effect of the organic cation on the structural dynamics of the inorganic scaffold of the 2D-HHPs. Furthermore, using this approach, we uncover the mechanism of the order–disorder phase transition of (BA)(2)PbI(4) (274 K) and show that it involves relaxation of octahedral tilting coupled to anharmonic thermal fluctuations. These anharmonic fluctuations are important because they induce charge carrier localization and affect the optoelectronic performance of these materials.