Chiral-at-Metal BODIPY-Based Iridium(III) Complexes: Synthesis and Luminescence Properties

The synthesis of enantiomerically pure Ir(III) complexes with one or two BODIPY moieties has been achieved through the enantioselective C–H insertion from homochiral triazolium salts, containing a sulfoxide functionality in their structures. These homochiral salts were prepared by the sequential Cu-...

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Detalles Bibliográficos
Autores: Avello, Marta G., Torre, María C. de la, Guerrero-Martínez, A., Sierra, M. A., Gornitzka, H., Hemmert, Catherine
Tipo de recurso: artículo
Fecha de publicación:2020
País:España
Institución:Consejo Superior de Investigaciones Científicas (CSIC)
Repositorio:DIGITAL.CSIC. Repositorio Institucional del CSIC
OAI Identifier:oai:digital.csic.es:10261/229017
Acceso en línea:http://hdl.handle.net/10261/229017
Access Level:acceso abierto
Palabra clave:Chirality
Iridium
BODIPYs
Luminescence
7 MIC-ligands
Descripción
Sumario:The synthesis of enantiomerically pure Ir(III) complexes with one or two BODIPY moieties has been achieved through the enantioselective C–H insertion from homochiral triazolium salts, containing a sulfoxide functionality in their structures. These homochiral salts were prepared by the sequential Cu-catalyzed alkyne-azide cycloaddition (CuAAC) of an azide and one alkynyl sulfoxide, followed by a Suzuki coupling in the preformed triazole with a BODIPY containing aryl boronic acid, followed by methylation of the N3-triazole nitrogen. The configuration at the metal in these chiral complexes was established by using a combination of CD and X-ray diffraction techniques. The optical properties of these complexes were thoroughly studied using spectroscopic (absorption and fluorescence) and computational (TD-DFT and DFT) methods. The fluorescence of complexes with the BODIPY attached to the sulfoxide moiety (including the two BODIPYs-based complex) was quenched upon introduction of the Ir(III) fragment, most likely due to an a-PET mechanism. On the contrary, the fluorescence of Ir(III) complexes with the BODIPY attached to the triazolium ring remains unquenched.