Cyclization-Promoted Ultralong Low-Temperature Phosphorescence via Boosting Intersystem Crossing.

Ultralong organic phosphorescence holds great promise as an important approach for optical materials and devices. Most of phosphorescent organic molecules with long lifetimes are substituted with heavy atoms or carbonyl groups to enhance the intersystem crossing (ISC), which requires complicated design and synthesis. Here, we report a cyclization-promoted phosphorescence phenomenon by boosting ISC. -butyl carbazole exhibits a phosphorescence lifetime (τ) of only 1.45 ms and a low phosphorescence efficiency in the solution state at 77 K due to the lack of efficient ISC. In order to promote its phosphorescence behavior, we explored the influence of conjugation. By linear conjugation of four carbazole units, possible ISC channels are increased so that a longer τ of 2.24 s is observed. Moreover, by cyclization, the energy gap between the singlet and triplet states is dramatically decreased to 0.04 eV for excellent ISC efficiency accompanied by increased rigidification to synergistically suppress the nonradiative decay, resulting in satisfactory phosphorescence efficiency and a prolonged τ to 3.41 s in the absence of any heavy atom or carbonyl group, which may act as a strategy to prepare ultralong phosphorescent organic materials by enhancing the ISC and rigidification.