New Lanthanide Selenophosphates. Influence of Flux Composition on the Distribution of [PSe4]3-/[P2Se6]4- Units and the Stabilization of the Low-Dimensional Compounds A3REP2Se8, and A2(RE)P2Se7 (A = Rb, Cs; RE = Ce, Gd)

Konstantinos Chondroudis, Mercouri G Kanatzidis

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Abstract

The reaction of Ce or Gd with a molten mixture of A2Se/P2Se5/Se (A = Rb, Cs) produced the quaternary compounds Rb3CeP2Se8 (I) and Cs3GdP2Se8 (II), as well as Rb2CeP2Se7 (III) and Rb2GdP2Se7 (IV). The orange crystals of I, II and the red crystals of III, IV are air- and water-sensitive. Compounds I, II crystallize in the monoclinic space group P21/c, and for I, a = 9.6013(2) Å, b = 18.0604(1) Å, c = 10.0931(1) Å, β= 90.619(1)°, and Z = 4. Compounds III, IV crystallize in the monoclinic space group P21/n, and for IV, a = 10.137(2) Å, b = 7.212-(1) Å, c = 20.299(2) Å, β = 98.23(1)°, and Z= 4. Compounds I, II have a 1-D structure with [(RE)P2Se8Jn 3n- chains separated by A+ cations. The RE3+ lanthanide cation is in a bicapped trigonal prismatic coordination with four tridentate [PSe4]3- ligands. Compounds III, IV possess a 2-D structure. Each layer consists of [RE(PSe4)]x "chains" interstitched in two dimensions by hexadentate [P2SC6]4- ligands. The trivalent RE cation is in a square antiprismatic coordination. The compounds were characterized with differential thermal analysis, far-IR, and solid-state UV/vis diffuse reflectance spectroscopy. Magnetic measurements indicate that the compounds obey the Curie law with μeff values close to those of the free RE3+ ions.

Original languageEnglish
Pages (from-to)3792-3797
Number of pages6
JournalInorganic Chemistry
Volume37
Issue number15
Publication statusPublished - Jul 27 1998

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Lanthanoid Series Elements
Cations
Stabilization
stabilization
Fluxes
cations
Chemical analysis
Ligands
Crystals
ligands
Magnetic variables measurement
Differential thermal analysis
crystals
magnetic measurement
Molten materials
thermal analysis
Spectroscopy
Ions
solid state
reflectance

ASJC Scopus subject areas

  • Inorganic Chemistry

Cite this

@article{e17ba20d573e41068bc1590c710b09fb,
title = "New Lanthanide Selenophosphates. Influence of Flux Composition on the Distribution of [PSe4]3-/[P2Se6]4- Units and the Stabilization of the Low-Dimensional Compounds A3REP2Se8, and A2(RE)P2Se7 (A = Rb, Cs; RE = Ce, Gd)",
abstract = "The reaction of Ce or Gd with a molten mixture of A2Se/P2Se5/Se (A = Rb, Cs) produced the quaternary compounds Rb3CeP2Se8 (I) and Cs3GdP2Se8 (II), as well as Rb2CeP2Se7 (III) and Rb2GdP2Se7 (IV). The orange crystals of I, II and the red crystals of III, IV are air- and water-sensitive. Compounds I, II crystallize in the monoclinic space group P21/c, and for I, a = 9.6013(2) {\AA}, b = 18.0604(1) {\AA}, c = 10.0931(1) {\AA}, β= 90.619(1)°, and Z = 4. Compounds III, IV crystallize in the monoclinic space group P21/n, and for IV, a = 10.137(2) {\AA}, b = 7.212-(1) {\AA}, c = 20.299(2) {\AA}, β = 98.23(1)°, and Z= 4. Compounds I, II have a 1-D structure with [(RE)P2Se8Jn 3n- chains separated by A+ cations. The RE3+ lanthanide cation is in a bicapped trigonal prismatic coordination with four tridentate [PSe4]3- ligands. Compounds III, IV possess a 2-D structure. Each layer consists of [RE(PSe4)]x {"}chains{"} interstitched in two dimensions by hexadentate [P2SC6]4- ligands. The trivalent RE cation is in a square antiprismatic coordination. The compounds were characterized with differential thermal analysis, far-IR, and solid-state UV/vis diffuse reflectance spectroscopy. Magnetic measurements indicate that the compounds obey the Curie law with μeff values close to those of the free RE3+ ions.",
author = "Konstantinos Chondroudis and Kanatzidis, {Mercouri G}",
year = "1998",
month = "7",
day = "27",
language = "English",
volume = "37",
pages = "3792--3797",
journal = "Inorganic Chemistry",
issn = "0020-1669",
publisher = "American Chemical Society",
number = "15",

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T1 - New Lanthanide Selenophosphates. Influence of Flux Composition on the Distribution of [PSe4]3-/[P2Se6]4- Units and the Stabilization of the Low-Dimensional Compounds A3REP2Se8, and A2(RE)P2Se7 (A = Rb, Cs; RE = Ce, Gd)

AU - Chondroudis, Konstantinos

AU - Kanatzidis, Mercouri G

PY - 1998/7/27

Y1 - 1998/7/27

N2 - The reaction of Ce or Gd with a molten mixture of A2Se/P2Se5/Se (A = Rb, Cs) produced the quaternary compounds Rb3CeP2Se8 (I) and Cs3GdP2Se8 (II), as well as Rb2CeP2Se7 (III) and Rb2GdP2Se7 (IV). The orange crystals of I, II and the red crystals of III, IV are air- and water-sensitive. Compounds I, II crystallize in the monoclinic space group P21/c, and for I, a = 9.6013(2) Å, b = 18.0604(1) Å, c = 10.0931(1) Å, β= 90.619(1)°, and Z = 4. Compounds III, IV crystallize in the monoclinic space group P21/n, and for IV, a = 10.137(2) Å, b = 7.212-(1) Å, c = 20.299(2) Å, β = 98.23(1)°, and Z= 4. Compounds I, II have a 1-D structure with [(RE)P2Se8Jn 3n- chains separated by A+ cations. The RE3+ lanthanide cation is in a bicapped trigonal prismatic coordination with four tridentate [PSe4]3- ligands. Compounds III, IV possess a 2-D structure. Each layer consists of [RE(PSe4)]x "chains" interstitched in two dimensions by hexadentate [P2SC6]4- ligands. The trivalent RE cation is in a square antiprismatic coordination. The compounds were characterized with differential thermal analysis, far-IR, and solid-state UV/vis diffuse reflectance spectroscopy. Magnetic measurements indicate that the compounds obey the Curie law with μeff values close to those of the free RE3+ ions.

AB - The reaction of Ce or Gd with a molten mixture of A2Se/P2Se5/Se (A = Rb, Cs) produced the quaternary compounds Rb3CeP2Se8 (I) and Cs3GdP2Se8 (II), as well as Rb2CeP2Se7 (III) and Rb2GdP2Se7 (IV). The orange crystals of I, II and the red crystals of III, IV are air- and water-sensitive. Compounds I, II crystallize in the monoclinic space group P21/c, and for I, a = 9.6013(2) Å, b = 18.0604(1) Å, c = 10.0931(1) Å, β= 90.619(1)°, and Z = 4. Compounds III, IV crystallize in the monoclinic space group P21/n, and for IV, a = 10.137(2) Å, b = 7.212-(1) Å, c = 20.299(2) Å, β = 98.23(1)°, and Z= 4. Compounds I, II have a 1-D structure with [(RE)P2Se8Jn 3n- chains separated by A+ cations. The RE3+ lanthanide cation is in a bicapped trigonal prismatic coordination with four tridentate [PSe4]3- ligands. Compounds III, IV possess a 2-D structure. Each layer consists of [RE(PSe4)]x "chains" interstitched in two dimensions by hexadentate [P2SC6]4- ligands. The trivalent RE cation is in a square antiprismatic coordination. The compounds were characterized with differential thermal analysis, far-IR, and solid-state UV/vis diffuse reflectance spectroscopy. Magnetic measurements indicate that the compounds obey the Curie law with μeff values close to those of the free RE3+ ions.

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