All-orthogonal BINOLated BODIPY dimers: A synergistic strategy for advancing heavy-metal-free triplet photosensitizers

Covalently linked organic multichromophores are promising photoactive molecular scaffolds for developing valuable heavy-metal-free triplet photosensitizers. Among them, orthogonally connected BODIPY dimers and easily accessible at-boron BINOLated BODIPYs stand out owing to their efficient oxygen pho...

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Detalles Bibliográficos
Autores: Serrano Buitrago, Sergio, Prieto Montero, Ruth, Jiménez, Josué, Moreno, Florencio, Lora Maroto, Beatriz, Martínez Martínez, Virginia, Bañuelos Prieto, Jorge, de la Moya, Santiago
Tipo de recurso: artículo
Fecha de publicación:2025
País:España
Institución:Universidad del País Vasco
Repositorio:Addi. Archivo Digital para la Docencia y la Investigación
OAI Identifier:oai:addi.ehu.eus:10810/75018
Acceso en línea:http://hdl.handle.net/10810/75018
Access Level:acceso abierto
Palabra clave:triplet photosensitizer
BODIPY chemistry
fluorescence
singlet oxygen
charge transfer
Descripción
Sumario:Covalently linked organic multichromophores are promising photoactive molecular scaffolds for developing valuable heavy-metal-free triplet photosensitizers. Among them, orthogonally connected BODIPY dimers and easily accessible at-boron BINOLated BODIPYs stand out owing to their efficient oxygen photosensitization, without the need for potentially toxic heavy atoms. In both approaches, the key photophysical mechanism enabling triplet state population involves a photoinduced intramolecular charge transfer by symmetry breaking in the orthogonally connected BODIPY dimers, or by electronic push-pull effect in the BINOL-BODIPY dyads. However, the potential synergistic effect of combining both strategies within a single molecular architecture remains unexplored. This work presents the first systematic study on the impact of integrating both photosensitizing approaches within a single BODIPY-based molecular framework. Our findings demonstrate that easy at-boron 3,3′-dibromoBINOLation serves as an effective chemical strategy to enhance triplet-based photosensitizing performance, without relying on potentially toxic heavy atoms such as transition metals. These results are expected to lay the foundations for the rational design of next-generation of low-cost BODIPY-based triplet photosensitizers for applications beyond heavy-metal-free photodynamic therapy, such as photocatalysis.