S-p Mixing in Stereochemically Active Lone Pairs Drives the Formation of 1D Chains of Lead Bromide Square Pyramids.

Abstract

In lead(II) halide compounds including virtually all lead halide perovskites, the Pb2+ 6s lone pair results in distorted octahedra, in accordance with the pseudo-Jahn-Teller effect, rather than generating hemihedral coordination polyhedra. Here, in contrast, we report the characterization of an organic-inorganic hybrid material consisting of one-dimensional edge-sharing chains of Pb-Br square pyramids, separated by [Mn(DMF)6]2+ (DMF = dimethylformamide) octahedra. Molecular orbital analysis and density-functional theory calculations indicate that square pyramidal coordination about Pb2+ results from the occupancy of the empty ligand site by a Pb2+ lone pair that has both s and p orbital character rather than the exclusively 6s lone pair. These results demonstrate that a Pb2+ lone pair can be exploited to behave like a ligand in lead halide compounds, greatly expanding the realm of possible lead halide materials to include extended solids with nonoctahedral coordination environments.