Chemistry in Molten Alkali Metal Polyselenophosphate Fluxes. Influence of Flux Composition on Dimensionality. Layers and Chains in APbPSe4, A4Pb(PSe4)3 (A = Rb, Cs), and K4Eu(PSe4)2

Konstantinos Chondroudis, Timothy J. McCarthy, Mercouri G Kanatzidis

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Abstract

The reaction of Pb and Eu with a molten mixture of A2Se/P2Se5/Se produced the quaternary compounds APbPSe4, A4Pb(PSe4)2 (A = Rb,Cs), and K4Eu(PSe4)2. The red crystals of APbPSe4 are stable in air and water. The orange crystals of A4Pb(PSe4)2 and K4Eu(PSe4)2 disintegrate in water and over a long exposure to air. CsPbPSe4 crystallizes in the orthorhombic space group Pnma (No. 62) with a = 18.607(4) Å, b = 7.096(4) Å, c = 6.612(4) Å, and Z = 4. Rb4Pb(PSe4)2 crystallizes in the orthorhombic space group Ibam (No. 72) with a = 19.134(9) Å, b = 9.369(3) Å, c = 10.488(3) Å, and Z = 4. The isomorphous K4Eu(PSe4)2 has a = 19.020(4) Å, b = 9.131(1) Å, c = 10.198(2) Å, and Z = 4. The APbPSe4 have a layered structure with [PbPSe4]nn- layers separated by A+ ions. The coordination geometry around Pb is trigonal prismatic. The layers are composed of chains of edge sharing trigonal prisms running along the b-direction. [PSe4]3- tetrahedra link these chains along the c-direction by sharing edges and corners with the trigonal prisms. A4M(PSe4)2 (M = Pb, Eu) has an one-dimensional structure in which [M(PSe4)2]nn- chains are separated by A+ ions. The coordination geometry around M is a distorted dodecahedron. Two [PSe4]3- ligands bridge two adjacent metal atoms, using three selenium atoms each, forming in this way a chain along the c-direction. The solid state optical absorption spectra of the compounds are reported. All compounds melt congruently in the 597-620 °C region.

Original languageEnglish
Pages (from-to)840-844
Number of pages5
JournalInorganic Chemistry
Volume35
Issue number4
Publication statusPublished - 1996

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Alkali Metals
alkali metals
Molten materials
chemistry
Fluxes
Prisms
Chemical analysis
Ions
prisms
Atoms
Crystals
Geometry
Water
Selenium
Air
Light absorption
Absorption spectra
air
geometry
selenium

ASJC Scopus subject areas

  • Inorganic Chemistry

Cite this

@article{148b379d195649028ac81df7e8e67311,
title = "Chemistry in Molten Alkali Metal Polyselenophosphate Fluxes. Influence of Flux Composition on Dimensionality. Layers and Chains in APbPSe4, A4Pb(PSe4)3 (A = Rb, Cs), and K4Eu(PSe4)2",
abstract = "The reaction of Pb and Eu with a molten mixture of A2Se/P2Se5/Se produced the quaternary compounds APbPSe4, A4Pb(PSe4)2 (A = Rb,Cs), and K4Eu(PSe4)2. The red crystals of APbPSe4 are stable in air and water. The orange crystals of A4Pb(PSe4)2 and K4Eu(PSe4)2 disintegrate in water and over a long exposure to air. CsPbPSe4 crystallizes in the orthorhombic space group Pnma (No. 62) with a = 18.607(4) {\AA}, b = 7.096(4) {\AA}, c = 6.612(4) {\AA}, and Z = 4. Rb4Pb(PSe4)2 crystallizes in the orthorhombic space group Ibam (No. 72) with a = 19.134(9) {\AA}, b = 9.369(3) {\AA}, c = 10.488(3) {\AA}, and Z = 4. The isomorphous K4Eu(PSe4)2 has a = 19.020(4) {\AA}, b = 9.131(1) {\AA}, c = 10.198(2) {\AA}, and Z = 4. The APbPSe4 have a layered structure with [PbPSe4]nn- layers separated by A+ ions. The coordination geometry around Pb is trigonal prismatic. The layers are composed of chains of edge sharing trigonal prisms running along the b-direction. [PSe4]3- tetrahedra link these chains along the c-direction by sharing edges and corners with the trigonal prisms. A4M(PSe4)2 (M = Pb, Eu) has an one-dimensional structure in which [M(PSe4)2]nn- chains are separated by A+ ions. The coordination geometry around M is a distorted dodecahedron. Two [PSe4]3- ligands bridge two adjacent metal atoms, using three selenium atoms each, forming in this way a chain along the c-direction. The solid state optical absorption spectra of the compounds are reported. All compounds melt congruently in the 597-620 °C region.",
author = "Konstantinos Chondroudis and McCarthy, {Timothy J.} and Kanatzidis, {Mercouri G}",
year = "1996",
language = "English",
volume = "35",
pages = "840--844",
journal = "Inorganic Chemistry",
issn = "0020-1669",
publisher = "American Chemical Society",
number = "4",

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T1 - Chemistry in Molten Alkali Metal Polyselenophosphate Fluxes. Influence of Flux Composition on Dimensionality. Layers and Chains in APbPSe4, A4Pb(PSe4)3 (A = Rb, Cs), and K4Eu(PSe4)2

AU - Chondroudis, Konstantinos

AU - McCarthy, Timothy J.

AU - Kanatzidis, Mercouri G

PY - 1996

Y1 - 1996

N2 - The reaction of Pb and Eu with a molten mixture of A2Se/P2Se5/Se produced the quaternary compounds APbPSe4, A4Pb(PSe4)2 (A = Rb,Cs), and K4Eu(PSe4)2. The red crystals of APbPSe4 are stable in air and water. The orange crystals of A4Pb(PSe4)2 and K4Eu(PSe4)2 disintegrate in water and over a long exposure to air. CsPbPSe4 crystallizes in the orthorhombic space group Pnma (No. 62) with a = 18.607(4) Å, b = 7.096(4) Å, c = 6.612(4) Å, and Z = 4. Rb4Pb(PSe4)2 crystallizes in the orthorhombic space group Ibam (No. 72) with a = 19.134(9) Å, b = 9.369(3) Å, c = 10.488(3) Å, and Z = 4. The isomorphous K4Eu(PSe4)2 has a = 19.020(4) Å, b = 9.131(1) Å, c = 10.198(2) Å, and Z = 4. The APbPSe4 have a layered structure with [PbPSe4]nn- layers separated by A+ ions. The coordination geometry around Pb is trigonal prismatic. The layers are composed of chains of edge sharing trigonal prisms running along the b-direction. [PSe4]3- tetrahedra link these chains along the c-direction by sharing edges and corners with the trigonal prisms. A4M(PSe4)2 (M = Pb, Eu) has an one-dimensional structure in which [M(PSe4)2]nn- chains are separated by A+ ions. The coordination geometry around M is a distorted dodecahedron. Two [PSe4]3- ligands bridge two adjacent metal atoms, using three selenium atoms each, forming in this way a chain along the c-direction. The solid state optical absorption spectra of the compounds are reported. All compounds melt congruently in the 597-620 °C region.

AB - The reaction of Pb and Eu with a molten mixture of A2Se/P2Se5/Se produced the quaternary compounds APbPSe4, A4Pb(PSe4)2 (A = Rb,Cs), and K4Eu(PSe4)2. The red crystals of APbPSe4 are stable in air and water. The orange crystals of A4Pb(PSe4)2 and K4Eu(PSe4)2 disintegrate in water and over a long exposure to air. CsPbPSe4 crystallizes in the orthorhombic space group Pnma (No. 62) with a = 18.607(4) Å, b = 7.096(4) Å, c = 6.612(4) Å, and Z = 4. Rb4Pb(PSe4)2 crystallizes in the orthorhombic space group Ibam (No. 72) with a = 19.134(9) Å, b = 9.369(3) Å, c = 10.488(3) Å, and Z = 4. The isomorphous K4Eu(PSe4)2 has a = 19.020(4) Å, b = 9.131(1) Å, c = 10.198(2) Å, and Z = 4. The APbPSe4 have a layered structure with [PbPSe4]nn- layers separated by A+ ions. The coordination geometry around Pb is trigonal prismatic. The layers are composed of chains of edge sharing trigonal prisms running along the b-direction. [PSe4]3- tetrahedra link these chains along the c-direction by sharing edges and corners with the trigonal prisms. A4M(PSe4)2 (M = Pb, Eu) has an one-dimensional structure in which [M(PSe4)2]nn- chains are separated by A+ ions. The coordination geometry around M is a distorted dodecahedron. Two [PSe4]3- ligands bridge two adjacent metal atoms, using three selenium atoms each, forming in this way a chain along the c-direction. The solid state optical absorption spectra of the compounds are reported. All compounds melt congruently in the 597-620 °C region.

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