Dynamic Stereochemical Activity of the Sn(2+) Lone Pair in Perovskite CsSnBr3.

Journal of the American Chemical Society

PubMedID: 27583813

Fabini DH, Laurita G, Bechtel JS, Stoumpos CC, Evans HA, Kontos AG, Raptis YS, Falaras P, Van der Ven A, Kanatzidis MG, Seshadri R. Dynamic Stereochemical Activity of the Sn(2+) Lone Pair in Perovskite CsSnBr3. J Am Chem Soc. 2016;.
Stable s(2) lone pair electrons on heavy main-group elements in their lower oxidation states drive a range of important phenomena, such as the emergence of polar ground states in some ferroic materials. Here we study the perovskite halide CsSnBr3 as an embodiment of the broader materials class. We show that lone pair stereochemical activity due to the Sn(2+) s(2) lone pair causes a crystallographically hidden, locally distorted state to appear upon warming, a phenomenon previously referred to as emphanisis. The synchrotron X-ray pair distribution function acquired between 300 and 420 K reveals emerging asymmetry in the nearest-neighbor Sn-Br correlations, consistent with dynamic Sn(2+) off-centering, despite there being no evidence of any deviation from the average cubic structure. Computation based on density functional theory supports the finding of a lattice instability associated with dynamic off-centering of Sn(2+) in its coordination environment. Photoluminescence measurements reveal an unusual blue-shift with increasing temperature, closely linked to the structural evolution. At low temperatures, the structures reflect the influence of octahedral rotation. A continuous transition from an orthorhombic structure (Pnma, no. 62) to a tetragonal structure (P4/mbm, no. 127) is found around 250 K, with a final, first-order transformation at 286 K to the cubic structure (Pm3¯m, no. 221).