Theoretical and Photoluminescent Studies on the d10-s2 Au-Tl Interaction in Extended Unsupported Chains

The reactions of solutions of TIPF6 and OPPh3 in tetrahydrofuran or acetone with NBu4[AuR2] (R= C6Cl5, C6F5) gave the new complexes [Au(C6Cl5)2]2[TI (OPPh3)] [TI(OPPh3) (L)] (L=THF (1), acetone (2)) and the previously reported [Tl(OPPh3)2]-[Au(C6 F5)2] (3). The crystal structures of complexes 1 and...

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Autores: Fernández, E.J. [0000-0002-6501-744X], Laguna, A. [0000-0003-1984-7538], López-de-Luzuriaga, J.M. [0000-0001-5767-8734], Mendizabal, F. [0000-0002-6912-8630], Monge, M. [0000-0002-9672-8279], Olmos, M.E. [0000-0001-8890-8977], Pérez, J. [0000-0001-6478-4279]
Tipo de recurso: artículo
Estado:Versión publicada
Fecha de publicación:2003
País:España
Institución:Universidad de La Rioja (UR)
Repositorio:RIUR. Repositorio Institucional de la Universidad de La Rioja
OAI Identifier:oai:portal.dialnet.es:doc/5bbc6842b750603269e80596
Acceso en línea:https://investigacion.unirioja.es/documentos/5bbc6842b750603269e80596
Access Level:acceso abierto
Palabra clave:Ab initio calculations
Density functional calculations
Gold
Luminescence
Thallium
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repository_id_str
spelling Theoretical and Photoluminescent Studies on the d10-s2 Au-Tl Interaction in Extended Unsupported ChainsFernández, E.J. [0000-0002-6501-744X]Laguna, A. [0000-0003-1984-7538]López-de-Luzuriaga, J.M. [0000-0001-5767-8734]Mendizabal, F. [0000-0002-6912-8630]Monge, M. [0000-0002-9672-8279]Olmos, M.E. [0000-0001-8890-8977]Pérez, J. [0000-0001-6478-4279]Ab initio calculationsDensity functional calculationsGoldLuminescenceThalliumThe reactions of solutions of TIPF6 and OPPh3 in tetrahydrofuran or acetone with NBu4[AuR2] (R= C6Cl5, C6F5) gave the new complexes [Au(C6Cl5)2]2[TI (OPPh3)] [TI(OPPh3) (L)] (L=THF (1), acetone (2)) and the previously reported [Tl(OPPh3)2]-[Au(C6 F5)2] (3). The crystal structures of complexes 1 and 2 display extended unsupported chains with short intermolecular interactions between alternating gold(1) and thallium(I) centres. Moreover, the Tl centres show two different types of geometrical environments, such as pseudotetrahedral and distorted trigonal-bipyramidal, due to the presence of solvent molecules that act as ligands in the solid-state structure. Quasirelativistic and nonrelativistic ab initio calculations were performed to study the nature of the intermetallic Au1-Tl1 interactions and are consistent with the presence of a high ionic contribution (80%) and dispersion-type (van der Waals) interaction with a charge-transfer contribution (20%) when relativistic effects are taken into account. All complexes are luminescent in the solid state at room temperature and at 77 K. Complexes 1 and 2 show site-selective excitation, probably due to the different environments around the Tl1 centres. The DFT and time-dependent (TD)-DFT calculations are in agreement with the experimental excitation spectra for all complexes and confirm the site-selective excitation behaviour as a function of the Tl1 geometrical environment.2003info:eu-repo/semantics/articleSubtype: Articleinfo:eu-repo/semantics/publishedVersionapplication/pdfhttps://investigacion.unirioja.es/documentos/5bbc6842b750603269e80596reponame:RIUR. Repositorio Institucional de la Universidad de La Riojainstname:Universidad de La Rioja (UR)Inglésinfo:eu-repo/semantics/altIdentifier/doi/10.1002/CHEM.200390048info:eu-repo/semantics/altIdentifier/wos/WOS:000180592000011info:eu-repo/semantics/altIdentifier/pmid/12532295info:eu-repo/semantics/altIdentifier/pissn/0947-6539Theoretical and Photoluminescent Studies on the d10-s2 Au-Tl Interaction in Extended Unsupported Chains, 2003, vol. 9, núm. 2, pág. 456-465info:eu-repo/semantics/openAccessoai:portal.dialnet.es:doc/5bbc6842b750603269e805962026-06-14T12:47:17Z
dc.title.none.fl_str_mv Theoretical and Photoluminescent Studies on the d10-s2 Au-Tl Interaction in Extended Unsupported Chains
title Theoretical and Photoluminescent Studies on the d10-s2 Au-Tl Interaction in Extended Unsupported Chains
spellingShingle Theoretical and Photoluminescent Studies on the d10-s2 Au-Tl Interaction in Extended Unsupported Chains
Fernández, E.J. [0000-0002-6501-744X]
Ab initio calculations
Density functional calculations
Gold
Luminescence
Thallium
title_short Theoretical and Photoluminescent Studies on the d10-s2 Au-Tl Interaction in Extended Unsupported Chains
title_full Theoretical and Photoluminescent Studies on the d10-s2 Au-Tl Interaction in Extended Unsupported Chains
title_fullStr Theoretical and Photoluminescent Studies on the d10-s2 Au-Tl Interaction in Extended Unsupported Chains
title_full_unstemmed Theoretical and Photoluminescent Studies on the d10-s2 Au-Tl Interaction in Extended Unsupported Chains
title_sort Theoretical and Photoluminescent Studies on the d10-s2 Au-Tl Interaction in Extended Unsupported Chains
dc.creator.none.fl_str_mv Fernández, E.J. [0000-0002-6501-744X]
Laguna, A. [0000-0003-1984-7538]
López-de-Luzuriaga, J.M. [0000-0001-5767-8734]
Mendizabal, F. [0000-0002-6912-8630]
Monge, M. [0000-0002-9672-8279]
Olmos, M.E. [0000-0001-8890-8977]
Pérez, J. [0000-0001-6478-4279]
author Fernández, E.J. [0000-0002-6501-744X]
author_facet Fernández, E.J. [0000-0002-6501-744X]
Laguna, A. [0000-0003-1984-7538]
López-de-Luzuriaga, J.M. [0000-0001-5767-8734]
Mendizabal, F. [0000-0002-6912-8630]
Monge, M. [0000-0002-9672-8279]
Olmos, M.E. [0000-0001-8890-8977]
Pérez, J. [0000-0001-6478-4279]
author_role author
author2 Laguna, A. [0000-0003-1984-7538]
López-de-Luzuriaga, J.M. [0000-0001-5767-8734]
Mendizabal, F. [0000-0002-6912-8630]
Monge, M. [0000-0002-9672-8279]
Olmos, M.E. [0000-0001-8890-8977]
Pérez, J. [0000-0001-6478-4279]
author2_role author
author
author
author
author
author
dc.subject.none.fl_str_mv Ab initio calculations
Density functional calculations
Gold
Luminescence
Thallium
topic Ab initio calculations
Density functional calculations
Gold
Luminescence
Thallium
description The reactions of solutions of TIPF6 and OPPh3 in tetrahydrofuran or acetone with NBu4[AuR2] (R= C6Cl5, C6F5) gave the new complexes [Au(C6Cl5)2]2[TI (OPPh3)] [TI(OPPh3) (L)] (L=THF (1), acetone (2)) and the previously reported [Tl(OPPh3)2]-[Au(C6 F5)2] (3). The crystal structures of complexes 1 and 2 display extended unsupported chains with short intermolecular interactions between alternating gold(1) and thallium(I) centres. Moreover, the Tl centres show two different types of geometrical environments, such as pseudotetrahedral and distorted trigonal-bipyramidal, due to the presence of solvent molecules that act as ligands in the solid-state structure. Quasirelativistic and nonrelativistic ab initio calculations were performed to study the nature of the intermetallic Au1-Tl1 interactions and are consistent with the presence of a high ionic contribution (80%) and dispersion-type (van der Waals) interaction with a charge-transfer contribution (20%) when relativistic effects are taken into account. All complexes are luminescent in the solid state at room temperature and at 77 K. Complexes 1 and 2 show site-selective excitation, probably due to the different environments around the Tl1 centres. The DFT and time-dependent (TD)-DFT calculations are in agreement with the experimental excitation spectra for all complexes and confirm the site-selective excitation behaviour as a function of the Tl1 geometrical environment.
publishDate 2003
dc.date.none.fl_str_mv 2003
dc.type.none.fl_str_mv info:eu-repo/semantics/article
Subtype: Article
info:eu-repo/semantics/publishedVersion
format article
status_str publishedVersion
dc.identifier.none.fl_str_mv https://investigacion.unirioja.es/documentos/5bbc6842b750603269e80596
url https://investigacion.unirioja.es/documentos/5bbc6842b750603269e80596
dc.language.none.fl_str_mv Inglés
language_invalid_str_mv Inglés
dc.relation.none.fl_str_mv info:eu-repo/semantics/altIdentifier/doi/10.1002/CHEM.200390048
info:eu-repo/semantics/altIdentifier/wos/WOS:000180592000011
info:eu-repo/semantics/altIdentifier/pmid/12532295
info:eu-repo/semantics/altIdentifier/pissn/0947-6539
Theoretical and Photoluminescent Studies on the d10-s2 Au-Tl Interaction in Extended Unsupported Chains, 2003, vol. 9, núm. 2, pág. 456-465
dc.rights.none.fl_str_mv info:eu-repo/semantics/openAccess
eu_rights_str_mv openAccess
dc.format.none.fl_str_mv application/pdf
dc.source.none.fl_str_mv reponame:RIUR. Repositorio Institucional de la Universidad de La Rioja
instname:Universidad de La Rioja (UR)
instname_str Universidad de La Rioja (UR)
reponame_str RIUR. Repositorio Institucional de la Universidad de La Rioja
collection RIUR. Repositorio Institucional de la Universidad de La Rioja
repository.name.fl_str_mv
repository.mail.fl_str_mv
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