2,5-difluorenyl-substituted siloles for the fabrication of high-performance yellow organic light-emitting diodes.

2,3,4,5-Tetraarylsiloles are a class of important luminogenic materials with efficient solid-state emission and excellent electron-transport capacity. However, those exhibiting outstanding electroluminescence properties are still rare. In this work, bulky 9,9-dimethylfluorenyl, 9,9-diphenylfluorenyl, and 9,9'-spirobifluorenyl substituents were introduced into the 2,5-positions of silole rings. The resulting 2,5-difluorenyl-substituted siloles are thermally stable and have low-lying LUMO energy levels. Crystallographic analysis revealed that intramolecular π-π interactions are prone to form between 9,9'-spirobifluorene units and phenyl rings at the 3,4-positions of the silole ring. In the solution state, these new siloles show weak blue and green emission bands, arising from the fluorenyl groups and silole rings with a certain extension of π conjugation, respectively. With increasing substituent volume, intramolecular rotation is decreased, and thus the emissions of the present siloles gradually improved and they showed higher fluorescence quantum yields (Φ(F) =2.5-5.4%) than 2,3,4,5-tetraphenylsiloles. They are highly emissive in solid films, with dominant green to yellow emissions and good solid-state Φ(F) values (75-88%). Efficient organic light-emitting diodes were fabricated by adopting them as host emitters and gave high luminance, current efficiency, and power efficiency of up to 44,100 cd m(-2), 18.3 cd A(-1), and 15.7 lm W(-1), respectively. Notably, a maximum external quantum efficiency of 5.5% was achieved in an optimized device.