Thia[]helicenes with long persistent phosphorescence.

Helicenes with persistent luminescence have received relatively little attention, despite their demonstrated highly efficient intersystem crossing (ISC) from the excited singlet to the triplet state. Herein, we designed a series of -fused aromatics by combining dithieno[2,3-:3',2'-]thiophene (DTT) with annulated benzene fragments, denoted as TB[]H ( = 3-8), to achieve persistent luminescence. Wherein, thia[]helicenes ( = 5-8) exhibited intense phosphorescence with millisecond-range lifetimes () at 77 K. Particularly interesting was the observation that the odd-numbered ring helicenes displayed longer values than their neighboring even-numbered counterparts. Notably, TB[7]H showcased the longest of 628 ms. This phenomenon can be attributed to the more favorable ISC channels and stronger spin-orbital coupling (SOC) of old-numbered helicenes than even-numbered ones. Furthermore, both conformers of TB[7]H exhibited significant circularly polarized phosphorescent (CPP) responses, with luminescence dissymmetry factors () of 0.015 and -0.014. These discoveries suggest that thiahelicenes may be a specific class of organic phosphorescent and CPP materials.