Pd2L4 Metal-Organic Cages with Perfluoroalkyl Edges: Ligand Design and Synthesis

[EN] Molecular cages are versatile supramolecular architectures with applications in guest encapsulation, catalysis, and sensing. This study reports the first Pd2L4 cage where vertices are bridged by-(CF2)n-chains. Cage synthesis is achieved by the self-assembly of a ligand comprising a perfluorinat...

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Detalles Bibliográficos
Autores: Fiorini, Guillermo Luciano|||0000-0003-0992-9812, Martínez-Máñez, Ramón|||0000-0001-5873-9674, Martí-Centelles, Vicente|||0000-0002-9142-9392, Pairault, Noel, Vicent, Cristian, McClenaghan, Nathan
Tipo de recurso: artículo
Fecha de publicación:2025
País:España
Institución:Universitat Politècnica de València (UPV)
Repositorio:RiuNet. Repositorio Institucional de la Universitat Politécnica de Valéncia
Idioma:inglés
OAI Identifier:oai:riunet.upv.es:10251/228465
Acceso en línea:https://riunet.upv.es/handle/10251/228465
Access Level:acceso abierto
Palabra clave:Molecular cages
Fluorous cages
Supra-molecular chemistry
Self-assembly
Ligand design
Descripción
Sumario:[EN] Molecular cages are versatile supramolecular architectures with applications in guest encapsulation, catalysis, and sensing. This study reports the first Pd2L4 cage where vertices are bridged by-(CF2)n-chains. Cage synthesis is achieved by the self-assembly of a ligand comprising a perfluorinated alkyl chain grafted with terminal pyridines and Pd(II). While the synthesis with a ligand comprising alpha,omega-monosubstituted pyridines partially produces the desired cage, the further design of two ligands with methoxy groups at the meta or para positions relative to the N-atom greatly enhances the coordination strength between the metal centre and the pyridine group. The para-substituted ligand quantitatively yields the most stable Pd2L4 cage. These findings highlight the influence of electronic effects on coordination-driven self-assembly and provide a pathway for designing robust and functional metal-organic cages containing perfluorinated edges. Additionally, we performed host-guest experiments that show a good affinity with environmentally concerning contaminant perfluorooctanoic acid. In summary, we developed Pd2L4 metal-organic cages with perfluoroalkyl edges that show good stability and promising host-guest properties.