Gold(I) Complexes with Bulky Phosphanes: A Dual Approach to Triplet Harvesting and Hydroamination Catalysis

Two families of mononuclear gold(I) complexes featuring Au-chromophore units, with chromophores being carbazole (a), phenanthrene (b), or dibenzofuran (c), were synthesized. The Au(I) atoms are coordinated to two phosphanes, either $PMe_{2}Ar^{Xyl2}(Ar^{Xyl2} = 2,6-C_{6}H{_3}-(2,6-C_{6}H{3}-Me_{2})_...

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Autores: Aquino Samper, Araceli de, Santamaría, Nazaret., Moro, Artur J., Aguilà Aviles, David, Nicasio, M. Carmen, Lima, João Carlos, Rodríguez Raurell, Laura, Prieto, Auxiliadora
Tipo de recurso: artículo
Estado:Versión publicada
Fecha de publicación:2025
País:España
Institución:Universidad de Barcelona
Repositorio:Dipòsit Digital de la UB
OAI Identifier:oai:dnet:ubarcelona__::e909b57390859764c79a9c88bd341cc2
Acceso en línea:https://hdl.handle.net/2445/228733
Access Level:acceso abierto
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spelling Gold(I) Complexes with Bulky Phosphanes: A Dual Approach to Triplet Harvesting and Hydroamination CatalysisAquino Samper, Araceli deSantamaría, Nazaret.Moro, Artur J.Aguilà Aviles, DavidNicasio, M. CarmenLima, João CarlosRodríguez Raurell, LauraPrieto, AuxiliadoraTwo families of mononuclear gold(I) complexes featuring Au-chromophore units, with chromophores being carbazole (a), phenanthrene (b), or dibenzofuran (c), were synthesized. The Au(I) atoms are coordinated to two phosphanes, either $PMe_{2}Ar^{Xyl2}(Ar^{Xyl2} = 2,6-C_{6}H{_3}-(2,6-C_{6}H{3}-Me_{2})_{2})$ (P1) or the bulkier $PCyp_{2}Ar^{Xyl2}(Cyp = cyclopentyl)$ (P2). The photophysical properties of these complexes were extensively studied, with a particular focus on the effects of phosphane bulkiness and chromophore electron-donating capacity on triplet state quantum yields ($\Phi_{T}$). Nanosecond-laser flash photolysis measurements were employed to calculate $\Phi_{T}$. Time-dependent density functional theory (TD-DFT) calculations supported the absorption and emission assignments, providing insights into the electronic state gaps involved in photophysical processes and their relative populations. The parent complex AuCl (P2) in combination with ${NaBAr_{4}}^F$, as a chloride scavenger, served as an efficient catalyst for the hydroamination of a variety of alkynes and amines, under mild conditions and with low Au loading (0.1–0.2 mol %). Luminescent studies allowed us to check the active catalytic species.American Chemical Society2025info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersionapplication/pdfhttps://hdl.handle.net/2445/228733Articles publicats en revistes (Química Inorgànica i Orgànica)reponame:Dipòsit Digital de la UBinstname:Universidad de BarcelonaInglésVersió publicada del document publicat a: https://doi.org/10.1021/acs.inorgchem.4c04964Versió publiada del document publicat a: https://doi.org/10.1021/acs.inorgchem.4c04964Inorganic Chemistry, 2025, vol. 64, num.7, p. 1-11https://doi.org/10.1021/acs.inorgchem.4c04964cc-by (c) Aquino Samper, Araceli de et al., 2025http://creativecommons.org/licenses/by/4.0/info:eu-repo/semantics/openAccessoai:dnet:ubarcelona__::e909b57390859764c79a9c88bd341cc22026-05-27T06:46:51Z
dc.title.none.fl_str_mv Gold(I) Complexes with Bulky Phosphanes: A Dual Approach to Triplet Harvesting and Hydroamination Catalysis
title Gold(I) Complexes with Bulky Phosphanes: A Dual Approach to Triplet Harvesting and Hydroamination Catalysis
spellingShingle Gold(I) Complexes with Bulky Phosphanes: A Dual Approach to Triplet Harvesting and Hydroamination Catalysis
Aquino Samper, Araceli de
title_short Gold(I) Complexes with Bulky Phosphanes: A Dual Approach to Triplet Harvesting and Hydroamination Catalysis
title_full Gold(I) Complexes with Bulky Phosphanes: A Dual Approach to Triplet Harvesting and Hydroamination Catalysis
title_fullStr Gold(I) Complexes with Bulky Phosphanes: A Dual Approach to Triplet Harvesting and Hydroamination Catalysis
title_full_unstemmed Gold(I) Complexes with Bulky Phosphanes: A Dual Approach to Triplet Harvesting and Hydroamination Catalysis
title_sort Gold(I) Complexes with Bulky Phosphanes: A Dual Approach to Triplet Harvesting and Hydroamination Catalysis
dc.creator.none.fl_str_mv Aquino Samper, Araceli de
Santamaría, Nazaret.
Moro, Artur J.
Aguilà Aviles, David
Nicasio, M. Carmen
Lima, João Carlos
Rodríguez Raurell, Laura
Prieto, Auxiliadora
author Aquino Samper, Araceli de
author_facet Aquino Samper, Araceli de
Santamaría, Nazaret.
Moro, Artur J.
Aguilà Aviles, David
Nicasio, M. Carmen
Lima, João Carlos
Rodríguez Raurell, Laura
Prieto, Auxiliadora
author_role author
author2 Santamaría, Nazaret.
Moro, Artur J.
Aguilà Aviles, David
Nicasio, M. Carmen
Lima, João Carlos
Rodríguez Raurell, Laura
Prieto, Auxiliadora
author2_role author
author
author
author
author
author
author
description Two families of mononuclear gold(I) complexes featuring Au-chromophore units, with chromophores being carbazole (a), phenanthrene (b), or dibenzofuran (c), were synthesized. The Au(I) atoms are coordinated to two phosphanes, either $PMe_{2}Ar^{Xyl2}(Ar^{Xyl2} = 2,6-C_{6}H{_3}-(2,6-C_{6}H{3}-Me_{2})_{2})$ (P1) or the bulkier $PCyp_{2}Ar^{Xyl2}(Cyp = cyclopentyl)$ (P2). The photophysical properties of these complexes were extensively studied, with a particular focus on the effects of phosphane bulkiness and chromophore electron-donating capacity on triplet state quantum yields ($\Phi_{T}$). Nanosecond-laser flash photolysis measurements were employed to calculate $\Phi_{T}$. Time-dependent density functional theory (TD-DFT) calculations supported the absorption and emission assignments, providing insights into the electronic state gaps involved in photophysical processes and their relative populations. The parent complex AuCl (P2) in combination with ${NaBAr_{4}}^F$, as a chloride scavenger, served as an efficient catalyst for the hydroamination of a variety of alkynes and amines, under mild conditions and with low Au loading (0.1–0.2 mol %). Luminescent studies allowed us to check the active catalytic species.
publishDate 2025
dc.date.none.fl_str_mv 2025
dc.type.none.fl_str_mv info:eu-repo/semantics/article
info:eu-repo/semantics/publishedVersion
format article
status_str publishedVersion
dc.identifier.none.fl_str_mv https://hdl.handle.net/2445/228733
url https://hdl.handle.net/2445/228733
dc.language.none.fl_str_mv Inglés
language_invalid_str_mv Inglés
dc.relation.none.fl_str_mv Versió publicada del document publicat a: https://doi.org/10.1021/acs.inorgchem.4c04964
Versió publiada del document publicat a: https://doi.org/10.1021/acs.inorgchem.4c04964
Inorganic Chemistry, 2025, vol. 64, num.7, p. 1-11
https://doi.org/10.1021/acs.inorgchem.4c04964
dc.rights.none.fl_str_mv cc-by (c) Aquino Samper, Araceli de et al., 2025
http://creativecommons.org/licenses/by/4.0/
info:eu-repo/semantics/openAccess
rights_invalid_str_mv cc-by (c) Aquino Samper, Araceli de et al., 2025
http://creativecommons.org/licenses/by/4.0/
eu_rights_str_mv openAccess
dc.format.none.fl_str_mv application/pdf
dc.publisher.none.fl_str_mv American Chemical Society
publisher.none.fl_str_mv American Chemical Society
dc.source.none.fl_str_mv Articles publicats en revistes (Química Inorgànica i Orgànica)
reponame:Dipòsit Digital de la UB
instname:Universidad de Barcelona
instname_str Universidad de Barcelona
reponame_str Dipòsit Digital de la UB
collection Dipòsit Digital de la UB
repository.name.fl_str_mv
repository.mail.fl_str_mv
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score 15,812455

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