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Title: Dynamic Stereochemical Activity of the Sn 2+ Lone Pair in Perovskite CsSnBr 3

Authors:
; ; ; ; ; ; ; ; ; ;
Publication Date:
Research Org.:
Argonne National Lab. (ANL), Argonne, IL (United States). Advanced Photon Source (APS)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1326088
Resource Type:
Journal Article
Resource Relation:
Journal Name: Journal of the American Chemical Society; Journal Volume: 138; Journal Issue: 36
Country of Publication:
United States
Language:
ENGLISH

Citation Formats

Fabini, Douglas H., Laurita, Geneva, Bechtel, Jonathon S., Stoumpos, Constantinos C., Evans, Hayden A., Kontos, Athanassios G., Raptis, Yannis S., Falaras, Polycarpos, Van der Ven, Anton, Kanatzidis, Mercouri G., and Seshadri, Ram. Dynamic Stereochemical Activity of the Sn 2+ Lone Pair in Perovskite CsSnBr 3. United States: N. p., 2016. Web. doi:10.1021/jacs.6b06287.
Fabini, Douglas H., Laurita, Geneva, Bechtel, Jonathon S., Stoumpos, Constantinos C., Evans, Hayden A., Kontos, Athanassios G., Raptis, Yannis S., Falaras, Polycarpos, Van der Ven, Anton, Kanatzidis, Mercouri G., & Seshadri, Ram. Dynamic Stereochemical Activity of the Sn 2+ Lone Pair in Perovskite CsSnBr 3. United States. doi:10.1021/jacs.6b06287.
Fabini, Douglas H., Laurita, Geneva, Bechtel, Jonathon S., Stoumpos, Constantinos C., Evans, Hayden A., Kontos, Athanassios G., Raptis, Yannis S., Falaras, Polycarpos, Van der Ven, Anton, Kanatzidis, Mercouri G., and Seshadri, Ram. 2016. "Dynamic Stereochemical Activity of the Sn 2+ Lone Pair in Perovskite CsSnBr 3". United States. doi:10.1021/jacs.6b06287.
@article{osti_1326088,
title = {Dynamic Stereochemical Activity of the Sn 2+ Lone Pair in Perovskite CsSnBr 3},
author = {Fabini, Douglas H. and Laurita, Geneva and Bechtel, Jonathon S. and Stoumpos, Constantinos C. and Evans, Hayden A. and Kontos, Athanassios G. and Raptis, Yannis S. and Falaras, Polycarpos and Van der Ven, Anton and Kanatzidis, Mercouri G. and Seshadri, Ram},
abstractNote = {},
doi = {10.1021/jacs.6b06287},
journal = {Journal of the American Chemical Society},
number = 36,
volume = 138,
place = {United States},
year = 2016,
month = 9
}
  • Flux-grown single crystals of the new compound PbSn(PO{sub 4}){sub 2} have been studied by X-ray diffraction. It crystallizes in monoclinic space group P2{sub 1}/n (no. 14), with cell parameters a = 4.861(6) {angstrom}, b = 14.75(2) {angstrom}, c = 8.80(2) {angstrom}, {beta} = 93.0(1){degree}, Z = 4. Its structure is related to the yavapaiite type with a skeleton made up of corner-linked SnO{sub 6} octahedra and PO{sub 4} tetrahedra, but the lead atoms are located in double tunnels instead of sheets. An active Pb{sup II} lone pair has been localized from electrostatic interactions in order to explain this original structure.
  • Synchrotron powder diffraction data from methylammonium tin bromide, CH{sub 3}NH{sub 3}SnBr{sub 3}, taken as a function of temperature, reveal the existence of a phase between 230 and 188 K crystallizing in Pmc2{sub 1}, a = 5.8941 (2), b = 8.3862 (2), c = 8.2406 (2) {angstrom}. Strong ferroelectric distortions of the octahedra, associated with stereochemical activity of the Sn 5s{sup 2} lone pair, are evident. A group analysis and decomposition of the distortion modes of the inorganic framework with respect to the cubic parent is given. The primary order parameters driving this upper transition appear to be an in-phase tiltmore » (rotation) of the octahedra coupled to a ferroelectric mode. The precise nature of the lower-temperature phase remains uncertain, although it appears likely to be triclinic. Density-functional theory calculations on such a triclinic cell suggest that directional bonding of the amine group to the halide cage is coupled to the stereochemical activity of the Sn lone pair via the Br atoms, i.e. that the bonding from the organic component may have a strong effect on the inorganic sublattice (principally via switching the direction of the lone pair with little to no energy cost).« less
  • The solid solution Sr{sub 2{minus}x}Pb{sub x}V{sub 3}O{sub 9}, 0 {le} x {le} 2, was prepared by solid state reactions and characterized by X-ray diffraction, IR spectroscopy, and magnetic susceptibility measurements. Single crystals of the pure strontium phase and mixed Sr/Pb compounds were prepared by high temperature treatment of the respective powder compositions. Pb{sub 2}V{sub 3}O{sub 9} crystals could only be obtained by the electrochemical reduction of molten PbV{sub 2}O{sub 6}. These crystals were always twinned. The previously reported crystal structure of Sr{sub 2}V{sub 3}O{sub 9} was confirmed. It was refined to R = 0.050, R{sub 2} = 0.057, in spacemore » group C2/c, a = 7.555(1) {angstrom}, b = 16.275(2) {angstrom}, c = 6.948(1) {angstrom}, {beta} = 119.78(1){degree}. The single crystal structural studies of the Sr{sub 1.02}Pb{sub 0.98}V{sub 3}O{sub 9} and Sr{sub 0.67}Pb{sub 1.33}V{sub 3}O{sub 9} members of the series show that the introduction of lead gives rise to a progressively complicated splitting of Sr{sup 2+}/Pb{sup 2+} and the tetrahedral vanadium ion crystallographic sites. As a consequence the vanadium framework distorts and beyond the Sr{sub 0.5}Pb{sub 1.5}V{sub 3}O{sub 9} composition the crystal symmetry becomes triclinic. This distortion is ascribed to the stereochemical effect of the 6s{sup 2} lone pair of Pb{sup 2+}. The crystallographic parameters of Pb{sub 2}V{sub 3}O{sub 9} are a = 7.598(1) {angstrom}, b = 16.393(3) {angstrom}, c = 6.972(2) {angstrom}, {alpha} = 91.38(1){degree}, {beta} = 119.35(1){degree}, {gamma} 90.47(1){degree}. Pb{sub 2}V{sub 3}O{sub 9} exhibits a more complex IR spectrum than the monoclinic phases. Despite the similarity between the triclinic and monoclinic phases the magnetic susceptibilities indicate differences in the coupling between 4{sup 4+} ions at low temperatures.« less
  • This paper explains how the Bi/sup 3 +/ lone pair exerts stereochemical effects on the structures of three Bi/sub 2/WO/sub 6/ polymorphs, i.e., the low-temperature form (Bi/sub 2/WO/sub 6/(1), orthorhombic), the intermediate form (Bi/sub 2/WO/sub 6/(i), orthorhombic), and the high-temperature modification (Bi/sub 2/WO/sub 6/(h), monoclinic); all their structures consist of alternating Bi/sub 2/O/sub 2/ layers and WO/sub 4/ layers. The monoclinic deformation of Bi/sub 2/WO/sub 6/(h) is explained by assuming appreciable repulsion between two facing lone pairs, each of which belongs to neighboring Bi/sub 2/O/sub 2/ layers, in a hypothetical transient state with the La/sub 2/MoO/sub 6/-related structure under themore » Bi/sub 2/WO/sub 6/(i) ..-->.. Bi/sub 2/WO/sub 6/ (h) transition. The polymorphism of Bi/sub 2/MoO/sub 6/, which has a Bi/sub 2/WO/sub 6/ (1)-related structure in a koechlinite phase, is also discussed on the basis of the stereochemistry of the Bi/sup 3 +/ lone pair.« less