Tuning Photophysical Properties by p-Functional Groups in Zn(II) and Cd(II) Complexes with Piperonylic Acid

Aggregation between discrete molecules is an essential factor to prevent aggregation-caused quenching (ACQ). Indeed, functional groups capable of generating strong hydrogen bonds are likely to assemble and cause ACQ and photoinduced electron transfer processes. Thus, it is possible to compare absorp...

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Autores: Sánchez-Férez, Francisco, Rius-Barta, J. M., Ayllón, J. A., Calvet Pallàs, Maria Teresa, Font Bardia, Ma. Mercedes, Pons, Josefina
Tipo de recurso: artículo
Estado:Versión publicada
Fecha de publicación:2022
País:España
Institución:Universidad de Barcelona
Repositorio:Dipòsit Digital de la UB
OAI Identifier:oai:diposit.ub.edu:2445/183276
Acceso en línea:https://hdl.handle.net/2445/183276
Access Level:acceso abierto
Palabra clave:Química organometàl·lica
Cristal·lografia
Organometallic chemistry
Crystallography
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spelling Tuning Photophysical Properties by p-Functional Groups in Zn(II) and Cd(II) Complexes with Piperonylic AcidSánchez-Férez, FranciscoRius-Barta, J. M.Ayllón, J. A.Calvet Pallàs, Maria TeresaFont Bardia, Ma. MercedesPons, JosefinaQuímica organometàl·licaCristal·lografiaOrganometallic chemistryCrystallographyAggregation between discrete molecules is an essential factor to prevent aggregation-caused quenching (ACQ). Indeed, functional groups capable of generating strong hydrogen bonds are likely to assemble and cause ACQ and photoinduced electron transfer processes. Thus, it is possible to compare absorption and emission properties by incorporating two ligands with a different bias toward intra- and intermolecular interactions that can induce a specific structural arrangement. In parallel, the π electron-donor or electron-withdrawing character of the functional groups could modify the Highest Ocuppied Molecular Orbital (HOMO)-Lowest Unocuppied Molecular Orbital (LUMO) energy gap. Reactions of M(OAc)2·2H2O (M = Zn(II) and Cd(II); OAc = acetate) with 1,3-benzodioxole-5-carboxylic acid (Piperonylic acid, HPip) and 4-acetylpyridine (4-Acpy) or isonicotinamide (Isn) resulted in the formation of four complexes. The elucidation of their crystal structure showed the formation of one paddle-wheel [Zn(μ-Pip)2(4-Acpy)]2 (1); a mixture of one dimer and two monomers [Zn(µ-Pip)(Pip)(Isn)2]2·2[Zn(Pip)2(HPip)(Isn)]·2MeOH (2); and two dimers [Cd(μ-Pip)(Pip)(4-Acpy)2]2 (3) and [Cd(μ-Pip)(Pip)(Isn)2]2·MeOH (4). They exhibit bridged (1, µ2-η1:η1), bridged, chelated and monodentated (2, µ2-η1:η1, µ1-η1:η1 and µ1-η1), or simultaneously bridged and chelated (3 and 4, µ2-η2:η1) coordination modes. Zn(II) centers accommodate coordination numbers 5 and 6, whereas Cd(II) presents coordination number 7. We have related their photophysical properties and fluorescence quantum yields with their geometric variations and interactions supported by TD-DFT calculations.MDPI2022info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersionapplication/pdfhttps://hdl.handle.net/2445/183276Articles publicats en revistes (Mineralogia, Petrologia i Geologia Aplicada)reponame:Dipòsit Digital de la UBinstname:Universidad de BarcelonaInglésReproducció del document publicat a: https://doi.org/10.3390/molecules27041365Molecules, 2022, vol. 27, num. 4, p. 1365https://doi.org/10.3390/molecules27041365cc-by (c) Sánchez-Férez, F. et al., 2022https://creativecommons.org/licenses/by/4.0/info:eu-repo/semantics/openAccessoai:diposit.ub.edu:2445/1832762026-05-27T06:46:51Z
dc.title.none.fl_str_mv Tuning Photophysical Properties by p-Functional Groups in Zn(II) and Cd(II) Complexes with Piperonylic Acid
title Tuning Photophysical Properties by p-Functional Groups in Zn(II) and Cd(II) Complexes with Piperonylic Acid
spellingShingle Tuning Photophysical Properties by p-Functional Groups in Zn(II) and Cd(II) Complexes with Piperonylic Acid
Sánchez-Férez, Francisco
Química organometàl·lica
Cristal·lografia
Organometallic chemistry
Crystallography
title_short Tuning Photophysical Properties by p-Functional Groups in Zn(II) and Cd(II) Complexes with Piperonylic Acid
title_full Tuning Photophysical Properties by p-Functional Groups in Zn(II) and Cd(II) Complexes with Piperonylic Acid
title_fullStr Tuning Photophysical Properties by p-Functional Groups in Zn(II) and Cd(II) Complexes with Piperonylic Acid
title_full_unstemmed Tuning Photophysical Properties by p-Functional Groups in Zn(II) and Cd(II) Complexes with Piperonylic Acid
title_sort Tuning Photophysical Properties by p-Functional Groups in Zn(II) and Cd(II) Complexes with Piperonylic Acid
dc.creator.none.fl_str_mv Sánchez-Férez, Francisco
Rius-Barta, J. M.
Ayllón, J. A.
Calvet Pallàs, Maria Teresa
Font Bardia, Ma. Mercedes
Pons, Josefina
author Sánchez-Férez, Francisco
author_facet Sánchez-Férez, Francisco
Rius-Barta, J. M.
Ayllón, J. A.
Calvet Pallàs, Maria Teresa
Font Bardia, Ma. Mercedes
Pons, Josefina
author_role author
author2 Rius-Barta, J. M.
Ayllón, J. A.
Calvet Pallàs, Maria Teresa
Font Bardia, Ma. Mercedes
Pons, Josefina
author2_role author
author
author
author
author
dc.subject.none.fl_str_mv Química organometàl·lica
Cristal·lografia
Organometallic chemistry
Crystallography
topic Química organometàl·lica
Cristal·lografia
Organometallic chemistry
Crystallography
description Aggregation between discrete molecules is an essential factor to prevent aggregation-caused quenching (ACQ). Indeed, functional groups capable of generating strong hydrogen bonds are likely to assemble and cause ACQ and photoinduced electron transfer processes. Thus, it is possible to compare absorption and emission properties by incorporating two ligands with a different bias toward intra- and intermolecular interactions that can induce a specific structural arrangement. In parallel, the π electron-donor or electron-withdrawing character of the functional groups could modify the Highest Ocuppied Molecular Orbital (HOMO)-Lowest Unocuppied Molecular Orbital (LUMO) energy gap. Reactions of M(OAc)2·2H2O (M = Zn(II) and Cd(II); OAc = acetate) with 1,3-benzodioxole-5-carboxylic acid (Piperonylic acid, HPip) and 4-acetylpyridine (4-Acpy) or isonicotinamide (Isn) resulted in the formation of four complexes. The elucidation of their crystal structure showed the formation of one paddle-wheel [Zn(μ-Pip)2(4-Acpy)]2 (1); a mixture of one dimer and two monomers [Zn(µ-Pip)(Pip)(Isn)2]2·2[Zn(Pip)2(HPip)(Isn)]·2MeOH (2); and two dimers [Cd(μ-Pip)(Pip)(4-Acpy)2]2 (3) and [Cd(μ-Pip)(Pip)(Isn)2]2·MeOH (4). They exhibit bridged (1, µ2-η1:η1), bridged, chelated and monodentated (2, µ2-η1:η1, µ1-η1:η1 and µ1-η1), or simultaneously bridged and chelated (3 and 4, µ2-η2:η1) coordination modes. Zn(II) centers accommodate coordination numbers 5 and 6, whereas Cd(II) presents coordination number 7. We have related their photophysical properties and fluorescence quantum yields with their geometric variations and interactions supported by TD-DFT calculations.
publishDate 2022
dc.date.none.fl_str_mv 2022
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/2445/183276
url https://hdl.handle.net/2445/183276
dc.language.none.fl_str_mv Inglés
language_invalid_str_mv Inglés
dc.relation.none.fl_str_mv Reproducció del document publicat a: https://doi.org/10.3390/molecules27041365
Molecules, 2022, vol. 27, num. 4, p. 1365
https://doi.org/10.3390/molecules27041365
dc.rights.none.fl_str_mv cc-by (c) Sánchez-Férez, F. et al., 2022
https://creativecommons.org/licenses/by/4.0/
info:eu-repo/semantics/openAccess
rights_invalid_str_mv cc-by (c) Sánchez-Férez, F. et al., 2022
https://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 MDPI
publisher.none.fl_str_mv MDPI
dc.source.none.fl_str_mv Articles publicats en revistes (Mineralogia, Petrologia i Geologia Aplicada)
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 15,300724

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