Perhalophenyl Three-Coordinate Gold(I) Complexes as TADF Emitters: A Photophysical Study from Experimental and Computational Viewpoints

We report the synthesis of novel perhalophenyl three-coordinated gold(I) complexes using 1,2-bis(diphenylphosphino)benzene (dppBz) as the chelating ligand and [AuR(tht)] (R = C 6 F 5 , C 6 Cl 2 F 3 , C 6 Cl 5 ) as the perhalophenyl-gold(I) source, leading to [AuR(dppBz)] (R = C 6 F 5 ( 1 ), C 6 Cl 2 F 3 ( 2 ), C 6 Cl 5 ( 3 )) complexes. The solid-state structures of compounds 2 and 3 consist of discrete three-coordinated Au(I) complexes, which show a distorted trigonal planar geometry for the gold center with dissimilar Au-P distances. The distorted structural arrangement is closely related to its photophysical properties. The studied complexes display very intense emissions at room temperature (RT) and at 77 K in the solid state. Studies of the emissive properties of the complexes at different temperatures suggest that the emissions are phosphorescent at 77 K and exhibit thermally activated delayed fluorescence (TADF) at RT. First-principle calculations of the photophysical processes yielded rate constants for intersystem crossing and reverse intersystem crossing that are in excellent agreement with experimental data.