s–p Mixing in Stereochemically Active Lone Pairs Drives the Formation of 1D Chains of Lead Bromide Square Pyramids
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 org...
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Veröffentlicht in: | Inorganic chemistry 2021-09, Vol.60 (17), p.12676-12680 |
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Format: | Artikel |
Sprache: | eng |
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Zusammenfassung: | 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. |
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ISSN: | 0020-1669 1520-510X |
DOI: | 10.1021/acs.inorgchem.1c01277 |