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Chiral‐at‐Metal BODIPY‐Based Iridium(III) Complexes: Synthesis and Luminescence Properties
Author(s) -
Avello Marta G.,
de la Torre María C.,
GuerreroMartínez Andrés,
Sierra Miguel A.,
Gornitzka Heinz,
Hemmert Catherine
Publication year - 2020
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/ejic.202000745
Subject(s) - chemistry , bodipy , sulfoxide , azide , moiety , cycloaddition , photochemistry , enantioselective synthesis , suzuki reaction , combinatorial chemistry , aryl , iridium , triazole , fluorescence , stereochemistry , organic chemistry , catalysis , physics , quantum mechanics , alkyl
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.