Catellani-Inspired BN-Aromatic Expansion: A Versatile Tool toward π-Extended 1,2-Azaborines with Tunable Photosensitizing Properties

BN-isosterism, the replacement of carbon-carbon units with boron-nitrogen pairs in organic frameworks, offers a powerful means to create novel compounds, yet methods to access larger BN-containing polyaromatic cores remain scarce. Leveraging our recently developed multigram-scale synthesis of BN-nap...

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Detalles Bibliográficos
Autores: Rulli, Federica, Ordeix, Sergi, Bresolí-Obach, Roger, Nonell, Santi, Saurí, Josep, Ribas-Font, Cristina, Shafir, Alexandr, Puig de la Bellacasa, Raimon, Cuenca, Ana B.
Tipo de recurso: artículo
Estado:Versión publicada
Fecha de publicación:2026
País:España
Institución:Consejo Superior de Investigaciones Científicas (CSIC)
Repositorio:DIGITAL.CSIC. Repositorio Institucional del CSIC
OAI Identifier:oai:digital.csic.es:10261/417709
Acceso en línea:http://hdl.handle.net/10261/417709
https://api.elsevier.com/content/abstract/scopus_id/105028986261
Access Level:acceso abierto
Palabra clave:BN-isosterism
Aromatic compounds
Fluorescence
Hydrocarbons
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Descripción
Sumario:BN-isosterism, the replacement of carbon-carbon units with boron-nitrogen pairs in organic frameworks, offers a powerful means to create novel compounds, yet methods to access larger BN-containing polyaromatic cores remain scarce. Leveraging our recently developed multigram-scale synthesis of BN-naphthalene, we now combine it with a Catellani-type arene extension (Pd(OAc)2/P(2-furyl)3, norbornene) to rapidly access diverse extended BN-embedded polyaromatic cores. This strategy delivers BN-embedded benzo[c]phenanthridines and curved 8- and 7-membered ring-fused derivatives, as well as BN-embedded benzofluorenones in both normal and inverse BN-vector orientations. Importantly, the ability to access both directional BN isomers, in addition to the parent C═C core, provides a rare opportunity to directly interrogate the effect of the presence and sense of the BN moiety. Most notably, light-induced singlet oxygen (1O2) generation promoted by the benzofluorenone core shows a more than 10-fold enhancement in the "boron-up" BN isostere, while dropping to negligible levels upon inversion of the BN unit. This work thus offers a blueprint for experimental electronic tuning of optically responsive organic materials through BN-mapping.