Palladium-Catalyzed C-H Bond Arylation of Cyclometalated Difluorinated 2-Arylisoquinolinyl Iridium(III) Complexes.

The utility of C-H bond functionalization of metalated ligands for the elaboration of aryl-functionalized difluorinated-1-arylisoquinolinyl Ir(III) complexes has been explored. Bis[(3,5-difluorophenyl)isoquinolinyl](2,2,6,6-tetramethyl-3,5-heptanedionato) iridium(III) undergoes Pd-catalyzed C-H bond arylation with aryl bromides. The reaction regioselectively occurred at the C-H bond flanked by the two fluorine atoms of the difluoroaryl unit, and on both cyclometalated ligands. This post-functionalization gives a straightforward access to modified complexes in only one manipulation and allows to introduce thermally sensitive functional groups, such as trifluoromethyl, nitrile, benzoyl, or ester. The X-ray crystallography, photophysical, and electrochemical properties of the diarylated complexes were investigated. Whatever the nature of the incorporated substituted aryl groups is, all obtained complexes emit red phosphorescence (622-632 nm) with similar lifetimes (1.9-2 μs).