Folding-Induced Spin–Orbit Coupling Enhancement for Efficient Pure Organic Room-Temperature Phosphorescence

For the direct luminescence of triplet excitons, different mechanisms have been proposed for realizing pure organic room-temperature phosphorescence (RTP). To further verify the mechanism of folding-induced spin–orbit coupling (SOC) enhancement, two analogues of thianthrene (TA) were introduced by gradually replacing the sulfur atom with an oxygen atom for a systematical comparison, corresponding to phenoxathiine (PX) and dioxins (DX) molecules with increasing folding dihedral angles (or decreasing degrees of folding). Photophysical measurements show an obviously enhanced RTP efficiency from DX and PX to TA, which is consistent with their greatly enhanced SOC with a decrease in folding dihedral angle. The folding angle-dependent SOC calculations for each molecule reveal that this enhanced RTP is dominated by folding-induced SOC enhancement, in contrast with the negligible heavy-atom effect from oxygen to sulfur. This work further validates the rationality of the folding-induced SOC enhancement mechanism, which provides an innovative molecular design strategy for developing efficient pure organic RTP materials using folding structures.