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• W2893429297 endingPage "12849" @default.
• W2893429297 startingPage "12836" @default.
• W2893429297 abstract "The application of a chiral auxiliary ligand to control the diastereoselectivity in the synthesis of a cyclometalated iridium(III) complex is presented. The diastereomeric iridium(III) complexes 1a and 1b are reported, in which a phenoxyoxazoline auxiliary ligand incorporates a chiral center functionalized with a pendant pentafluorophenyl group. The diastereomers were readily separated, and their structural, electrochemical and photophysical properties are discussed. Solution-state NMR data and X-ray crystal structures establish that the pentafluorophenyl group engages in intramolecular π–π interactions. The X-ray analysis reveals that the two diastereomers display very different modes of intramolecular stacking. The variable-temperature 19F NMR data indicate that rotation of the pendant pentafluorophenyl rings in 1b and 1a is a temperature-dependent process and that there is a smaller energy barrier to rotation in 1b in comparison to 1a. This correlates with variable-temperature photoluminescence data, which show that upon heating the integrated emission intensity is reduced substantially more for 1b than for 1a, which is ascribed to the enhanced rotation in 1b, providing a more easily populated nonradiative pathway in comparison to 1a. These experimental data are supported by computational calculations. Phosphorescent organic light-emitting devices (PhOLEDs) using 1a as the dopant complex give blue-green emission with a high maximum external quantum efficiency (EQEmax) of 25.8% (at ca. 270 cd m–2) and with a low efficiency roll-off to 24.9% at 1000 cd m–2. Our results extend the scope of ligand design for cyclometalated iridium complexes which possess interesting structural and emission properties." @default.
• W2893429297 created "2018-10-05" @default.
• W2893429297 creator A5005939815 @default.
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• W2893429297 creator A5058300984 @default.
• W2893429297 date "2018-09-26" @default.
• W2893429297 modified "2023-10-16" @default.
• W2893429297 title "Intramolecular π–π Interactions with a Chiral Auxiliary Ligand Control Diastereoselectivity in a Cyclometalated Ir(III) Complex" @default.
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• W2893429297 doi "https://doi.org/10.1021/acs.inorgchem.8b02034" @default.
• W2893429297 hasPubMedId "https://pubmed.ncbi.nlm.nih.gov/30256097" @default.
• W2893429297 hasPublicationYear "2018" @default.
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