Y<sub>5</sub>F<sub>3</sub>[AsO<sub>3</sub>]<sub>4</sub> and Y<sub>5</sub>Cl<sub>3</sub>[AsO<sub>3</sub>]<sub>4</sub>: Two Non-Isostructural Yttrium Halide Oxoarsenates(III) and Their Potential as Hosts for Luminescent Eu<sup>3+</sup>- and Tb<sup>3+</sup>-Doping

Y<sub>5</sub>F<sub>3</sub>[AsO<sub>3</sub>]<sub>4</sub> and Y<sub>5</sub>Cl<sub>3</sub>[AsO<sub>3</sub>]<sub>4</sub>: Two Non-Isostructural Yttrium Halide Oxoarsenates(III) and Their Potential as Hosts for Luminescent Eu<sup>3+</sup>- and Tb<sup>3+</sup>-Doping

Y<sub>5</sub>F<sub>3</sub>[AsO<sub>3</sub>]<sub>4</sub> crystallizes needle-shaped in the tetragonal space group <i>P</i>4/<i>ncc</i> with the lattice parameters <i>a</i> = 1143.80(8) pm, <i>c</i> = 1078....

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Main Authors: Ralf J. C. Locke, Martina Mikuta, Florian Ledderboge, Frank C. Zimmer, Henning A. Höppe, Thomas Schleid
Format: Article
Language:English
Published: MDPI AG 2025-06-01
Series:Crystals
Subjects:
yttrium
halides
oxoarsenates(III)
crystal structures
luminescence
Online Access:https://www.mdpi.com/2073-4352/15/7/611
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author Ralf J. C. Locke
Martina Mikuta
Florian Ledderboge
Frank C. Zimmer
Henning A. Höppe
Thomas Schleid
author_facet Ralf J. C. Locke
Martina Mikuta
Florian Ledderboge
Frank C. Zimmer
Henning A. Höppe
Thomas Schleid
author_sort Ralf J. C. Locke
collection DOAJ
description Y<sub>5</sub>F<sub>3</sub>[AsO<sub>3</sub>]<sub>4</sub> crystallizes needle-shaped in the tetragonal space group <i>P</i>4/<i>ncc</i> with the lattice parameters <i>a</i> = 1143.80(8) pm, <i>c</i> = 1078.41(7) pm and <i>c</i>/<i>a</i> = 0.9428 for <i>Z</i> = 4. The yttrium-fluoride substructure linked via secondary contacts forms a three-dimensional network <inline-formula><math xmlns="http://www.w3.org/1998/Math/MathML" display="inline"><semantics><mrow><mtable><mtr><mtd><mn>3</mn></mtd></mtr><mtr><mtd><mo>∞</mo></mtd></mtr></mtable></mrow></semantics></math></inline-formula>{[Y<sub>5</sub>F<sub>3</sub>]<sup>12+</sup>} and the remaining part consists of ψ<sup>1</sup>-tetrahedral [AsO<sub>3</sub>]<sup>3−</sup> units, which leave lone-pair channels along [001]. In contrast, platelet-shaped Y<sub>5</sub>Cl<sub>3</sub>[AsO<sub>3</sub>]<sub>4</sub> crystals adopt the monoclinic space group <i>C</i>2/<i>c</i> with the lattice parameters <i>a</i> = 1860.56(9) pm, <i>b</i> = 536.27(3) pm, <i>c</i> = 1639.04(8) pm and <i>β</i> = 105.739(3)° for <i>Z</i> = 4. Condensation of [(Y1,2)O<sub>8</sub>]<sup>13−</sup> polyhedra via four common edges each leads to fluorite-like <inline-formula><math xmlns="http://www.w3.org/1998/Math/MathML" display="inline"><semantics><mrow><mtable><mtr><mtd><mn>2</mn></mtd></mtr><mtr><mtd><mo>∞</mo></mtd></mtr></mtable></mrow></semantics></math></inline-formula> {[(Y1,2)O <inline-formula><math xmlns="http://www.w3.org/1998/Math/MathML" display="inline"><semantics><mrow><mtable><mtr><mtd><mi>e</mi></mtd></mtr><mtr><mtd><mrow><mrow><mn>8</mn></mrow><mo>/</mo><mrow><mn>2</mn></mrow></mrow></mtd></mtr></mtable></mrow></semantics></math></inline-formula> ]<sup>5−</sup>} layers spreading out parallel to the (100) plane. Their three-dimensional linkage occurs via the (Y3)<sup>3+</sup> cations with their Cl<sup>−</sup> ligands on the one hand and the As<sup>3+</sup> cations with their lone-pairs of electrons on the other, which also form within [AsO<sub>3</sub>]<sup>3−</sup> anions lone-pair channels along [010]. Both colorless compounds can be obtained by solid-state reactions from corresponding mixtures of the binaries (Y<sub>2</sub>O<sub>3</sub>, As<sub>2</sub>O<sub>3</sub> and YX<sub>3</sub> with X = F and Cl) at elevated temperatures of 825 °C, most advantageously under halide-flux assistance (CsBr for Y<sub>5</sub>F<sub>3</sub>[AsO<sub>3</sub>]<sub>4</sub> and ZnCl<sub>2</sub> for Y<sub>5</sub>Cl<sub>3</sub>[AsO<sub>3</sub>]<sub>4</sub>). By replacing a few percent of YX<sub>3</sub> with EuX<sub>3</sub> or TbX<sub>3</sub>, Eu<sup>3+</sup>- or Tb<sup>3+</sup>-doped samples are accessible, which show red or green luminescence upon excitation with ultraviolet radiation.
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spelling doaj-art-8c290b86eebf4e70884c628ef4f5b1ce2025-08-20T03:08:10ZengMDPI AGCrystals2073-43522025-06-0115761110.3390/cryst15070611Y<sub>5</sub>F<sub>3</sub>[AsO<sub>3</sub>]<sub>4</sub> and Y<sub>5</sub>Cl<sub>3</sub>[AsO<sub>3</sub>]<sub>4</sub>: Two Non-Isostructural Yttrium Halide Oxoarsenates(III) and Their Potential as Hosts for Luminescent Eu<sup>3+</sup>- and Tb<sup>3+</sup>-DopingRalf J. C. Locke0Martina Mikuta1Florian Ledderboge2Frank C. Zimmer3Henning A. Höppe4Thomas Schleid5Institut für Anorganische Chemie, Universität Stuttgart, Pfaffenwaldring 55, 70569 Stuttgart, GermanyInstitut für Physik, Universität Augsburg, Universitätsstraße 1, 86159 Augsburg, GermanyInstitut für Anorganische Chemie, Universität Stuttgart, Pfaffenwaldring 55, 70569 Stuttgart, GermanyInstitut für Anorganische Chemie, Universität Stuttgart, Pfaffenwaldring 55, 70569 Stuttgart, GermanyInstitut für Physik, Universität Augsburg, Universitätsstraße 1, 86159 Augsburg, GermanyInstitut für Anorganische Chemie, Universität Stuttgart, Pfaffenwaldring 55, 70569 Stuttgart, GermanyY<sub>5</sub>F<sub>3</sub>[AsO<sub>3</sub>]<sub>4</sub> crystallizes needle-shaped in the tetragonal space group <i>P</i>4/<i>ncc</i> with the lattice parameters <i>a</i> = 1143.80(8) pm, <i>c</i> = 1078.41(7) pm and <i>c</i>/<i>a</i> = 0.9428 for <i>Z</i> = 4. The yttrium-fluoride substructure linked via secondary contacts forms a three-dimensional network <inline-formula><math xmlns="http://www.w3.org/1998/Math/MathML" display="inline"><semantics><mrow><mtable><mtr><mtd><mn>3</mn></mtd></mtr><mtr><mtd><mo>∞</mo></mtd></mtr></mtable></mrow></semantics></math></inline-formula>{[Y<sub>5</sub>F<sub>3</sub>]<sup>12+</sup>} and the remaining part consists of ψ<sup>1</sup>-tetrahedral [AsO<sub>3</sub>]<sup>3−</sup> units, which leave lone-pair channels along [001]. In contrast, platelet-shaped Y<sub>5</sub>Cl<sub>3</sub>[AsO<sub>3</sub>]<sub>4</sub> crystals adopt the monoclinic space group <i>C</i>2/<i>c</i> with the lattice parameters <i>a</i> = 1860.56(9) pm, <i>b</i> = 536.27(3) pm, <i>c</i> = 1639.04(8) pm and <i>β</i> = 105.739(3)° for <i>Z</i> = 4. Condensation of [(Y1,2)O<sub>8</sub>]<sup>13−</sup> polyhedra via four common edges each leads to fluorite-like <inline-formula><math xmlns="http://www.w3.org/1998/Math/MathML" display="inline"><semantics><mrow><mtable><mtr><mtd><mn>2</mn></mtd></mtr><mtr><mtd><mo>∞</mo></mtd></mtr></mtable></mrow></semantics></math></inline-formula> {[(Y1,2)O <inline-formula><math xmlns="http://www.w3.org/1998/Math/MathML" display="inline"><semantics><mrow><mtable><mtr><mtd><mi>e</mi></mtd></mtr><mtr><mtd><mrow><mrow><mn>8</mn></mrow><mo>/</mo><mrow><mn>2</mn></mrow></mrow></mtd></mtr></mtable></mrow></semantics></math></inline-formula> ]<sup>5−</sup>} layers spreading out parallel to the (100) plane. Their three-dimensional linkage occurs via the (Y3)<sup>3+</sup> cations with their Cl<sup>−</sup> ligands on the one hand and the As<sup>3+</sup> cations with their lone-pairs of electrons on the other, which also form within [AsO<sub>3</sub>]<sup>3−</sup> anions lone-pair channels along [010]. Both colorless compounds can be obtained by solid-state reactions from corresponding mixtures of the binaries (Y<sub>2</sub>O<sub>3</sub>, As<sub>2</sub>O<sub>3</sub> and YX<sub>3</sub> with X = F and Cl) at elevated temperatures of 825 °C, most advantageously under halide-flux assistance (CsBr for Y<sub>5</sub>F<sub>3</sub>[AsO<sub>3</sub>]<sub>4</sub> and ZnCl<sub>2</sub> for Y<sub>5</sub>Cl<sub>3</sub>[AsO<sub>3</sub>]<sub>4</sub>). By replacing a few percent of YX<sub>3</sub> with EuX<sub>3</sub> or TbX<sub>3</sub>, Eu<sup>3+</sup>- or Tb<sup>3+</sup>-doped samples are accessible, which show red or green luminescence upon excitation with ultraviolet radiation.https://www.mdpi.com/2073-4352/15/7/611yttriumhalidesoxoarsenates(III)crystal structuresluminescence
spellingShingle Ralf J. C. Locke
Martina Mikuta
Florian Ledderboge
Frank C. Zimmer
Henning A. Höppe
Thomas Schleid
Y<sub>5</sub>F<sub>3</sub>[AsO<sub>3</sub>]<sub>4</sub> and Y<sub>5</sub>Cl<sub>3</sub>[AsO<sub>3</sub>]<sub>4</sub>: Two Non-Isostructural Yttrium Halide Oxoarsenates(III) and Their Potential as Hosts for Luminescent Eu<sup>3+</sup>- and Tb<sup>3+</sup>-Doping
Crystals
yttrium
halides
oxoarsenates(III)
crystal structures
luminescence
title Y<sub>5</sub>F<sub>3</sub>[AsO<sub>3</sub>]<sub>4</sub> and Y<sub>5</sub>Cl<sub>3</sub>[AsO<sub>3</sub>]<sub>4</sub>: Two Non-Isostructural Yttrium Halide Oxoarsenates(III) and Their Potential as Hosts for Luminescent Eu<sup>3+</sup>- and Tb<sup>3+</sup>-Doping
title_full Y<sub>5</sub>F<sub>3</sub>[AsO<sub>3</sub>]<sub>4</sub> and Y<sub>5</sub>Cl<sub>3</sub>[AsO<sub>3</sub>]<sub>4</sub>: Two Non-Isostructural Yttrium Halide Oxoarsenates(III) and Their Potential as Hosts for Luminescent Eu<sup>3+</sup>- and Tb<sup>3+</sup>-Doping
title_fullStr Y<sub>5</sub>F<sub>3</sub>[AsO<sub>3</sub>]<sub>4</sub> and Y<sub>5</sub>Cl<sub>3</sub>[AsO<sub>3</sub>]<sub>4</sub>: Two Non-Isostructural Yttrium Halide Oxoarsenates(III) and Their Potential as Hosts for Luminescent Eu<sup>3+</sup>- and Tb<sup>3+</sup>-Doping
title_full_unstemmed Y<sub>5</sub>F<sub>3</sub>[AsO<sub>3</sub>]<sub>4</sub> and Y<sub>5</sub>Cl<sub>3</sub>[AsO<sub>3</sub>]<sub>4</sub>: Two Non-Isostructural Yttrium Halide Oxoarsenates(III) and Their Potential as Hosts for Luminescent Eu<sup>3+</sup>- and Tb<sup>3+</sup>-Doping
title_short Y<sub>5</sub>F<sub>3</sub>[AsO<sub>3</sub>]<sub>4</sub> and Y<sub>5</sub>Cl<sub>3</sub>[AsO<sub>3</sub>]<sub>4</sub>: Two Non-Isostructural Yttrium Halide Oxoarsenates(III) and Their Potential as Hosts for Luminescent Eu<sup>3+</sup>- and Tb<sup>3+</sup>-Doping
title_sort y sub 5 sub f sub 3 sub aso sub 3 sub sub 4 sub and y sub 5 sub cl sub 3 sub aso sub 3 sub sub 4 sub two non isostructural yttrium halide oxoarsenates iii and their potential as hosts for luminescent eu sup 3 sup and tb sup 3 sup doping
topic yttrium
halides
oxoarsenates(III)
crystal structures
luminescence
url https://www.mdpi.com/2073-4352/15/7/611
work_keys_str_mv AT ralfjclocke ysub5subfsub3subasosub3subsub4subandysub5subclsub3subasosub3subsub4subtwononisostructuralyttriumhalideoxoarsenatesiiiandtheirpotentialashostsforluminescenteusup3supandtbsup3supdoping
AT martinamikuta ysub5subfsub3subasosub3subsub4subandysub5subclsub3subasosub3subsub4subtwononisostructuralyttriumhalideoxoarsenatesiiiandtheirpotentialashostsforluminescenteusup3supandtbsup3supdoping
AT florianledderboge ysub5subfsub3subasosub3subsub4subandysub5subclsub3subasosub3subsub4subtwononisostructuralyttriumhalideoxoarsenatesiiiandtheirpotentialashostsforluminescenteusup3supandtbsup3supdoping
AT frankczimmer ysub5subfsub3subasosub3subsub4subandysub5subclsub3subasosub3subsub4subtwononisostructuralyttriumhalideoxoarsenatesiiiandtheirpotentialashostsforluminescenteusup3supandtbsup3supdoping
AT henningahoppe ysub5subfsub3subasosub3subsub4subandysub5subclsub3subasosub3subsub4subtwononisostructuralyttriumhalideoxoarsenatesiiiandtheirpotentialashostsforluminescenteusup3supandtbsup3supdoping
AT thomasschleid ysub5subfsub3subasosub3subsub4subandysub5subclsub3subasosub3subsub4subtwononisostructuralyttriumhalideoxoarsenatesiiiandtheirpotentialashostsforluminescenteusup3supandtbsup3supdoping

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