Insight into Regioselective Control in Aerobic Oxidative C–H/C–H Coupling for C3-Arylation of Benzothiophenes: Toward Structurally Nontraditional OLED Materials

The installation of (benzo)thiophene-containing biaryls via coupling reactions has become a staple in designing photoelectric materials. Undeniably, C–H/C–H cross-coupling reactions between two (hetero)aromatics would be a shortcut toward these structural fragments. While more reliable cross-coupling technologies are well-established to provide C2-arylated (benzo)thiophenes, efficient methods that arylate the C3-position remain underdeveloped. Herein we provide insight into the factors that determine regioselectivity switching for these cross-coupling reactions. X-ray crystallographic analysis gives solid evidence for the key roles of triflate in regioselective dearomatization and acetate in base-assisted anti-β-deprotonated rearomatization. The first isolation and X-ray characterization of a medium-sized dearomatized cyclometalated adduct involving both substrates provide extra insight into aerobic oxidative Ar–H/Ar–H cross-coupling reactions. The mechanistic breakthrough incubates the first example, enabling C–H/C–H-type C3-arylation of benzothiophenes. Finally, this chemistry is used to design blue-emitting thermally activated delayed fluorescence (TADF) materials with a helicene conformation that exhibit a high maximum external quantum efficiency of 25.4% in OLED.