Abstract Cationic cyclometalated Ir(III) complexes (Ir1-Ir5) with fluorine-substituted 2-phenylpyridine (ppy) derivatives as C^N cyclometalating ligands and 2,2′-bipyridine (bpy) as the ancillary ligand, have been synthesized and fully characterized. The influences… Click to show full abstract
Abstract Cationic cyclometalated Ir(III) complexes (Ir1-Ir5) with fluorine-substituted 2-phenylpyridine (ppy) derivatives as C^N cyclometalating ligands and 2,2′-bipyridine (bpy) as the ancillary ligand, have been synthesized and fully characterized. The influences of the number and the position of fluorine atoms at the cyclometalating ligands on the photophysical, electrochemical and oxygen sensing properties of the Ir(III) complexes have been investigated systematically. The introduction of fluorine on the C^N cyclometalating ligands of the complexes results in blue-shifts of the maximum emission wavelengths, and increases in the photoluminescence quantum yields (ΦPL), phosphorescence lifetimes and energy gaps, compared to the non-fluorinated [Ir(ppy)2(bpy)]+PF6− (Ir0). Among them, 2-(2,4-difluorophenyl)pyridine-derived Ir4 shows the maximum blue-shift (514 nm vs. 575 nm for Ir0) and the highest ΦPL (50.8% vs. 6.5% for Ir0). The complex Ir3 with 2-(4-fluorophenyl)-5-fluoropyridine as C^N ligand exhibits the highest oxygen sensitivity and excellent operational stability in 10 cycles within 4000 s.
               
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