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 metal coordination, were synthesized via Suzuki coupling reactions from a dichloro-DTE building block, each with varying longitudinal extensions. The shorter DTE-catechol ligand did not efficiently ass...

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Detalles Bibliográficos
Autores: Carbonell, Adrián|||0000-0003-0737-5924, Izquierdo, Ignacio|||0000-0002-9554-8452, Guzmán Ríos, David B.|||0000-0001-6881-0139, Norjmaa, Gantulga|||0000-0001-5209-895X, Ujaque, Gregori|||0000-0001-5896-9998, Martínez-Martínez, Antonio J.|||0000-0002-0684-1244, Pischel, Uwe|||0000-0001-8893-9829
Tipo de recurso: artículo
Fecha de publicación:2024
País:España
Institución:Universitat Autònoma de Barcelona
Repositorio:Dipòsit Digital de Documents de la UAB
Idioma:inglés
OAI Identifier:oai:ddd.uab.cat:319958
Acceso en línea:https://ddd.uab.cat/record/319958
https://dx.doi.org/urn:doi:10.1021/acs.inorgchem.4c03279
Access Level:acceso abierto
Palabra clave:Irradiation
Ligands
Metals
Molecular structure
Supramolecular structures and assemblies
Descripción
Sumario:Two new photoswitchable dithienylethene (DTE)-catechol ligands, specifically designed for group 13 metal coordination, were synthesized via Suzuki coupling reactions from a dichloro-DTE building block, each with varying longitudinal extensions. The shorter DTE-catechol ligand did not efficiently assemble with Ga 3+ metal ions; however, elongation with a phenylene-amide spacer group enabled the successful formation of a novel triply DTE-functionalized coordination [Ga2L3] 6- cage. This cage represents a unique example of integrating DTE photoswitches with main group metals in a supramolecular coordination framework. The [Ga2L3] 6- cage was thoroughly characterized by NMR spectroscopy, including DOSY hydrodynamic volumetric analyses, high-resolution mass spectrometry, computational DFT, and photochemical analyses. The DFT studies highlighted the structural integrity and dynamic interplay within the helicate and mesocate isomeric forms of the [Ga2L3] 6- cage upon photoswitching. While the free ligands exhibited all-photonic reversible switching at up to mM concentrations upon alternating irradiation at 365 and.