Exploiting the Reactivity of Metal Trifluoroacetates to Access Alkali–Niobium(V) Oxyfluorides

Motivated by the lack of facile routes to alkali–niobium(V) oxyfluorides KNb2O5F and CsNb2O5F, we investigated the reactivity of alkali trifluoroacetates KH(tfa)2 and CsH(tfa)2 (tfa = CF3COO–) toward Nb2O5 in the solid state. Tetragonal tungsten bronze KNb2O5F and pyrochlore CsNb2O5F were obtained b...

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Autores: Imer, Marcos R., Szlag, Regina G., Oreskovic, Benjamin D. E., Urones Garrote, Esteban, García Martín, Susana, Rabuffetti, Federico A.
Tipo de recurso: artículo
Fecha de publicación:2024
País:España
Institución:Universidad Complutense de Madrid (UCM)
Repositorio:Docta Complutense
Idioma:inglés
OAI Identifier:oai:docta.ucm.es:20.500.14352/118651
Acceso en línea:https://hdl.handle.net/20.500.14352/118651
Access Level:acceso abierto
Palabra clave:547
Atmospheric chemistry
Crystal structure
Diffraction
Mixtures
Precursors
Ciencias
23 Química
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spelling Exploiting the Reactivity of Metal Trifluoroacetates to Access Alkali–Niobium(V) OxyfluoridesImer, Marcos R.Szlag, Regina G.Oreskovic, Benjamin D. E.Urones Garrote, EstebanGarcía Martín, SusanaRabuffetti, Federico A.547Atmospheric chemistryCrystal structureDiffractionMixturesPrecursorsCiencias23 QuímicaMotivated by the lack of facile routes to alkali–niobium(V) oxyfluorides KNb2O5F and CsNb2O5F, we investigated the reactivity of alkali trifluoroacetates KH(tfa)2 and CsH(tfa)2 (tfa = CF3COO–) toward Nb2O5 in the solid state. Tetragonal tungsten bronze KNb2O5F and pyrochlore CsNb2O5F were obtained by simply reacting the corresponding trifluoroacetate with Nb2O5 at 600 °C under air, without the need for specialized containers or a controlled atmosphere. Thermolysis of KH(tfa)2 in the presence of Nb2O5 yielded single-phase polycrystalline KNb2O5F. By contrast, the reaction between CsH(tfa)2 and Nb2O5 produced a mixture of CsNb2O5F and a new oxyfluoride of formula CsNb3O7F2, whose crystal structure was solved using powder X-ray and electron diffraction. CsNb3O7F2 (space group P6/mmm) belongs to the family of hexagonal tungsten bronzes and features an open-framework structure consisting of corner-sharing Nb(O,F)6 octahedra with hexagonal channels occupied by Cs+ ions. Isomorphous RbNb3O7F2 was obtained upon reacting RbH(tfa)2 with Nb2O5. Synthetic optimization enabled the preparation of RbNb3O7F2 and CsNb3O7F2 as single-phase polycrystalline solids at 500 °C under flowing synthetic air. Both oxyfluorides were found to be semiconductors with a band gap of ≈3.5 eV. The discovery of these two oxyfluorides highlights the importance of probing the reactivity of solids whose full potential as fluorinated precursors is yet to be realized.ACSUniversidad Complutense de Madrid20242024-06-1020242024-06-10journal articlehttp://purl.org/coar/resource_type/c_6501VoRhttp://purl.org/coar/version/c_970fb48d4fbd8a85info:eu-repo/semantics/articleapplication/pdfhttps://hdl.handle.net/20.500.14352/118651reponame:Docta Complutenseinstname:Universidad Complutense de Madrid (UCM)Inglésengopen accesshttp://purl.org/coar/access_right/c_abf2Attribution-NonCommercial-NoDerivatives 4.0 Internationalhttp://creativecommons.org/licenses/by-nc-nd/4.0/info:eu-repo/semantics/openAccessoai:docta.ucm.es:20.500.14352/1186512026-06-02T12:44:21Z
dc.title.none.fl_str_mv Exploiting the Reactivity of Metal Trifluoroacetates to Access Alkali–Niobium(V) Oxyfluorides
title Exploiting the Reactivity of Metal Trifluoroacetates to Access Alkali–Niobium(V) Oxyfluorides
spellingShingle Exploiting the Reactivity of Metal Trifluoroacetates to Access Alkali–Niobium(V) Oxyfluorides
Imer, Marcos R.
547
Atmospheric chemistry
Crystal structure
Diffraction
Mixtures
Precursors
Ciencias
23 Química
title_short Exploiting the Reactivity of Metal Trifluoroacetates to Access Alkali–Niobium(V) Oxyfluorides
title_full Exploiting the Reactivity of Metal Trifluoroacetates to Access Alkali–Niobium(V) Oxyfluorides
title_fullStr Exploiting the Reactivity of Metal Trifluoroacetates to Access Alkali–Niobium(V) Oxyfluorides
title_full_unstemmed Exploiting the Reactivity of Metal Trifluoroacetates to Access Alkali–Niobium(V) Oxyfluorides
title_sort Exploiting the Reactivity of Metal Trifluoroacetates to Access Alkali–Niobium(V) Oxyfluorides
dc.creator.none.fl_str_mv Imer, Marcos R.
Szlag, Regina G.
Oreskovic, Benjamin D. E.
Urones Garrote, Esteban
García Martín, Susana
Rabuffetti, Federico A.
author Imer, Marcos R.
author_facet Imer, Marcos R.
Szlag, Regina G.
Oreskovic, Benjamin D. E.
Urones Garrote, Esteban
García Martín, Susana
Rabuffetti, Federico A.
author_role author
author2 Szlag, Regina G.
Oreskovic, Benjamin D. E.
Urones Garrote, Esteban
García Martín, Susana
Rabuffetti, Federico A.
author2_role author
author
author
author
author
dc.contributor.none.fl_str_mv Universidad Complutense de Madrid
dc.subject.none.fl_str_mv 547
Atmospheric chemistry
Crystal structure
Diffraction
Mixtures
Precursors
Ciencias
23 Química
topic 547
Atmospheric chemistry
Crystal structure
Diffraction
Mixtures
Precursors
Ciencias
23 Química
description Motivated by the lack of facile routes to alkali–niobium(V) oxyfluorides KNb2O5F and CsNb2O5F, we investigated the reactivity of alkali trifluoroacetates KH(tfa)2 and CsH(tfa)2 (tfa = CF3COO–) toward Nb2O5 in the solid state. Tetragonal tungsten bronze KNb2O5F and pyrochlore CsNb2O5F were obtained by simply reacting the corresponding trifluoroacetate with Nb2O5 at 600 °C under air, without the need for specialized containers or a controlled atmosphere. Thermolysis of KH(tfa)2 in the presence of Nb2O5 yielded single-phase polycrystalline KNb2O5F. By contrast, the reaction between CsH(tfa)2 and Nb2O5 produced a mixture of CsNb2O5F and a new oxyfluoride of formula CsNb3O7F2, whose crystal structure was solved using powder X-ray and electron diffraction. CsNb3O7F2 (space group P6/mmm) belongs to the family of hexagonal tungsten bronzes and features an open-framework structure consisting of corner-sharing Nb(O,F)6 octahedra with hexagonal channels occupied by Cs+ ions. Isomorphous RbNb3O7F2 was obtained upon reacting RbH(tfa)2 with Nb2O5. Synthetic optimization enabled the preparation of RbNb3O7F2 and CsNb3O7F2 as single-phase polycrystalline solids at 500 °C under flowing synthetic air. Both oxyfluorides were found to be semiconductors with a band gap of ≈3.5 eV. The discovery of these two oxyfluorides highlights the importance of probing the reactivity of solids whose full potential as fluorinated precursors is yet to be realized.
publishDate 2024
dc.date.none.fl_str_mv 2024
2024-06-10
2024
2024-06-10
dc.type.none.fl_str_mv journal article
http://purl.org/coar/resource_type/c_6501
VoR
http://purl.org/coar/version/c_970fb48d4fbd8a85
dc.type.openaire.fl_str_mv info:eu-repo/semantics/article
format article
dc.identifier.none.fl_str_mv https://hdl.handle.net/20.500.14352/118651
url https://hdl.handle.net/20.500.14352/118651
dc.language.none.fl_str_mv Inglés
eng
language_invalid_str_mv Inglés
language eng
dc.rights.none.fl_str_mv open access
http://purl.org/coar/access_right/c_abf2
Attribution-NonCommercial-NoDerivatives 4.0 International
http://creativecommons.org/licenses/by-nc-nd/4.0/
dc.rights.openaire.fl_str_mv info:eu-repo/semantics/openAccess
rights_invalid_str_mv open access
http://purl.org/coar/access_right/c_abf2
Attribution-NonCommercial-NoDerivatives 4.0 International
http://creativecommons.org/licenses/by-nc-nd/4.0/
eu_rights_str_mv openAccess
dc.format.none.fl_str_mv application/pdf
dc.publisher.none.fl_str_mv ACS
publisher.none.fl_str_mv ACS
dc.source.none.fl_str_mv reponame:Docta Complutense
instname:Universidad Complutense de Madrid (UCM)
instname_str Universidad Complutense de Madrid (UCM)
reponame_str Docta Complutense
collection Docta Complutense
repository.name.fl_str_mv
repository.mail.fl_str_mv
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