Synthesis, Characterization, and Photochemistry of a Ga2L3 Coordination Cage with Dithienylethene-Catecholate Ligands
Two new photoswitchable dithienylethene (DTE)-catechol ligands, specifically designed for group 13 metalcoordination, were synthesized via Suzuki coupling reactions froma dichloro-DTE building block, each with varying longitudinalextensions. The shorter DTE-catechol ligand did not efficientlyassembl...
| Autores: | , , , , , , |
|---|---|
| Tipo de recurso: | artículo |
| Fecha de publicación: | 2024 |
| País: | España |
| Institución: | Universidad de Huelva (UHU) |
| Repositorio: | Arias Montano. Repositorio Institucional de la Universidad de Huelva |
| Idioma: | inglés |
| OAI Identifier: | oai:ariasmontano.uhu.es:10272/24527 |
| Acceso en línea: | https://hdl.handle.net/10272/24527 |
| Access Level: | acceso abierto |
| Palabra clave: | Irradiation Ligands Metals Molecular structure Supramolecular structures and assemblies 23 Química |
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Synthesis, Characterization, and Photochemistry of a Ga2L3 Coordination Cage with Dithienylethene-Catecholate LigandsCarbonell, AdriánIzquierdo, IgnacioGuzmán Ríos, David BenjamínNorjmaa, GantulgaUjaque, GregoriMartínez Martínez, Antonio JesúsPischel, UweIrradiationLigandsMetalsMolecular structureSupramolecular structures and assemblies23 QuímicaTwo new photoswitchable dithienylethene (DTE)-catechol ligands, specifically designed for group 13 metalcoordination, were synthesized via Suzuki coupling reactions froma dichloro-DTE building block, each with varying longitudinalextensions. The shorter DTE-catechol ligand did not efficientlyassemble with Ga3+ metal ions; however, elongation with aphenylene-amide spacer group enabled the successful formationof a novel triply DTE-functionalized coordination [Ga2L3]6− cage.This cage represents a unique example of integrating DTEphotoswitches with main group metals in a supramolecularcoordination framework. The [Ga2L3]6− cage was thoroughlycharacterized by NMR spectroscopy, including DOSY hydro-dynamic volumetric analyses, high-resolution mass spectrometry, computational DFT, and photochemical analyses. The DFT studieshighlighted the structural integrity and dynamic interplay within the helicate and mesocate isomeric forms of the [Ga2L3]6− cageupon photoswitching. While the free ligands exhibited all-photonic reversible switching at up to mM concentrations upon alternatingirradiation at 365 and >495 nm, the [Ga2L3]6− cage demonstrated these capabilities under dilute μM conditions, albeit with lowerefficiency and fatigue resistance. This behavior highlights the intricate relationship between rigid coordination with main groupmetals and the flexibility of the photoswitchable DTE ligands within the [Ga2L3]6− cageAmerican Chemical Society20242024-10-0120242024-10-01journal articlehttp://purl.org/coar/resource_type/c_6501VoRhttp://purl.org/coar/version/c_970fb48d4fbd8a85info:eu-repo/semantics/articleapplication/pdfhttps://hdl.handle.net/10272/24527reponame:Arias Montano. Repositorio Institucional de la Universidad de Huelvainstname:Universidad de Huelva (UHU)Inglésengopen accesshttp://purl.org/coar/access_right/c_abf2Attribution 4.0 Internationalhttp://creativecommons.org/licenses/by/4.0/info:eu-repo/semantics/openAccessoai:ariasmontano.uhu.es:10272/245272026-06-02T14:58:11Z |
| dc.title.none.fl_str_mv |
Synthesis, Characterization, and Photochemistry of a Ga2L3 Coordination Cage with Dithienylethene-Catecholate Ligands |
| title |
Synthesis, Characterization, and Photochemistry of a Ga2L3 Coordination Cage with Dithienylethene-Catecholate Ligands |
| spellingShingle |
Synthesis, Characterization, and Photochemistry of a Ga2L3 Coordination Cage with Dithienylethene-Catecholate Ligands Carbonell, Adrián Irradiation Ligands Metals Molecular structure Supramolecular structures and assemblies 23 Química |
| title_short |
Synthesis, Characterization, and Photochemistry of a Ga2L3 Coordination Cage with Dithienylethene-Catecholate Ligands |
| title_full |
Synthesis, Characterization, and Photochemistry of a Ga2L3 Coordination Cage with Dithienylethene-Catecholate Ligands |
| title_fullStr |
Synthesis, Characterization, and Photochemistry of a Ga2L3 Coordination Cage with Dithienylethene-Catecholate Ligands |
| title_full_unstemmed |
Synthesis, Characterization, and Photochemistry of a Ga2L3 Coordination Cage with Dithienylethene-Catecholate Ligands |
| title_sort |
Synthesis, Characterization, and Photochemistry of a Ga2L3 Coordination Cage with Dithienylethene-Catecholate Ligands |
| dc.creator.none.fl_str_mv |
Carbonell, Adrián Izquierdo, Ignacio Guzmán Ríos, David Benjamín Norjmaa, Gantulga Ujaque, Gregori Martínez Martínez, Antonio Jesús Pischel, Uwe |
| author |
Carbonell, Adrián |
| author_facet |
Carbonell, Adrián Izquierdo, Ignacio Guzmán Ríos, David Benjamín Norjmaa, Gantulga Ujaque, Gregori Martínez Martínez, Antonio Jesús Pischel, Uwe |
| author_role |
author |
| author2 |
Izquierdo, Ignacio Guzmán Ríos, David Benjamín Norjmaa, Gantulga Ujaque, Gregori Martínez Martínez, Antonio Jesús Pischel, Uwe |
| author2_role |
author author author author author author |
| dc.contributor.none.fl_str_mv |
|
| dc.subject.none.fl_str_mv |
Irradiation Ligands Metals Molecular structure Supramolecular structures and assemblies 23 Química |
| topic |
Irradiation Ligands Metals Molecular structure Supramolecular structures and assemblies 23 Química |
| description |
Two new photoswitchable dithienylethene (DTE)-catechol ligands, specifically designed for group 13 metalcoordination, were synthesized via Suzuki coupling reactions froma dichloro-DTE building block, each with varying longitudinalextensions. The shorter DTE-catechol ligand did not efficientlyassemble with Ga3+ metal ions; however, elongation with aphenylene-amide spacer group enabled the successful formationof a novel triply DTE-functionalized coordination [Ga2L3]6− cage.This cage represents a unique example of integrating DTEphotoswitches with main group metals in a supramolecularcoordination framework. The [Ga2L3]6− cage was thoroughlycharacterized by NMR spectroscopy, including DOSY hydro-dynamic volumetric analyses, high-resolution mass spectrometry, computational DFT, and photochemical analyses. The DFT studieshighlighted the structural integrity and dynamic interplay within the helicate and mesocate isomeric forms of the [Ga2L3]6− cageupon photoswitching. While the free ligands exhibited all-photonic reversible switching at up to mM concentrations upon alternatingirradiation at 365 and >495 nm, the [Ga2L3]6− cage demonstrated these capabilities under dilute μM conditions, albeit with lowerefficiency and fatigue resistance. This behavior highlights the intricate relationship between rigid coordination with main groupmetals and the flexibility of the photoswitchable DTE ligands within the [Ga2L3]6− cage |
| publishDate |
2024 |
| dc.date.none.fl_str_mv |
2024 2024-10-01 2024 2024-10-01 |
| 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/10272/24527 |
| url |
https://hdl.handle.net/10272/24527 |
| 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 4.0 International http://creativecommons.org/licenses/by/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 4.0 International 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 |
reponame:Arias Montano. Repositorio Institucional de la Universidad de Huelva instname:Universidad de Huelva (UHU) |
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Universidad de Huelva (UHU) |
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Arias Montano. Repositorio Institucional de la Universidad de Huelva |
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Arias Montano. Repositorio Institucional de la Universidad de Huelva |
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| repository.mail.fl_str_mv |
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1869416587801395200 |
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15.812455 |