Crystal Engineering of Room Temperature Phosphorescence in Organic Solids.

We report a series of highly emissive azatriangulenetrione (TANGO) solids in which the luminescent properties are controlled by engineering the molecular packing by adjusting the steric size of substituents. The co-alignment of "phosphorogenic" carbonyl groups within the π-stacks results in an almost pure triplet emission in HTANGO, TCTANGO, TBTANGO and TITANGO, while their rotation by ≈60° in the sterically hindered tBuTANGO leads to an almost pure singlet emission. Despite strong π-interactions, aggregation-induced quenching and triplet-triplet annihilation are avoided in HTANGO and TCTANGO which display efficient phosphorescence in the solid state. To our knowledge, HTANGO with the solid-state phosphorescence quantum yield of 42 % at room temperature is the most efficient phosphor composed of the 1st /2nd raw elements only.