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

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 al...

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Detalles Bibliográficos
Autores: Fiorini, G, Pairault, N, Vicent, C, Martinez-Máñez, R, McClenaghan, N, Marti-Centelles, V
Tipo de recurso: artículo
Estado:Versión publicada
Fecha de publicación:2025
País:España
Institución:Centro de Investigación Principe Felipe (CIPF)
Repositorio:r-CIPF. Repositorio Institucional Producción Científica del Centro de Investigación Principe Felipe (CIPF)
OAI Identifier:oai:cipf.fundanetsuite.com:p4528
Acceso en línea:https://cipf.fundanetsuite.com/Publicaciones/ProdCientif/PublicacionFrw.aspx?id=4528
Access Level:acceso abierto
Palabra clave:molecular cages
fluorous cages
supra-molecular chemistry
self-assembly
ligand design
Descripción
Sumario: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.