In situ Cyclization of Aromatic Thioethers in Emissive Materials to Generate Phosphorescent Dibenzothiophenes.

In this contribution, we explored the photocyclization of thioethers to highly substituted dibenzothiophenes (DBT) using solely UV-light without any need for additives. This cost-effective, robust and environmentally friendly approach yielded phosphorescent compounds, which were characterized by X-ray crystallography and state-of-the-art photophysical methods. The resulting DBTs feature ultralong photoluminescence lifetimes and quantum yields close to unity in frozen glassy matrices. The reaction mechanism was elucidated in detail through a combination of quantum chemical calculations and experimental results, providing evidence that triplet states are involved in the cyclization process. Additionally, the photoreaction can also be induced within materials. For this purpose, the precursors were integrated into polymer films or polymer resins suitable for 3D printing. Irradiation of these polymeric objects allows motifs with ultralong phosphorescence to be irreversibly inscribed through the proceeding photocyclization. The in situ photogeneration of DBTs from aromatic thioethers overcomes the observed incompatibilities regarding solubility in polymer resins for 3D printing.