Iridium(III) Complex Radical and Corresponding Ligand Radical Functionalized by a Tris(2,4,6-trichlorophenyl)methyl Unit: Synthesis, Structure, and Photophysical Properties.

Organic radical luminescent materials with doublet excited state character based on tris(2,4,6-trichlorophenyl)methyl (TTM) have attracted extensive attention in recent years. However, how they affect the phosphorescent iridium(III) complex characterized by the triplet excited state has not been studied yet. Herein, a new iridium(III) complex radical ( Ir-TTM ) and corresponding ligand radical ( ppy-TTM ) with a TTM unit have been designed and synthesized, and their radical properties were confirmed by the single crystal structure and EPR spectra. Notably, the ligand radical ppy-TTM shows an efficient red light emission, whereas the iridium complex radical Ir-TTM emits no light, which resulted from the intramolecular quenching effect of the TTM radical unit on the iridium luminescence center. DFT calculations demonstrate that the lowest doublet (D 1 ) excited state of ppy-TTM shows an intramolecular charge transfer character from the 2-phenylpyridine moieties to the TTM unit, whereas the D 1 of Ir-TTM exhibits a significant charge transfer character from the iridium luminescence center moieties to the TTM unit, which further explains the luminescence quenching mechanism of the phosphorescent iridium complex radical.