Switching between TADF and RTP: anion-regulated photoluminescence in organic salts and co-crystals

Thermally activated delayed fluorescence (TADF) and room temperature phosphorescence (RTP) are two photophysical phenomena which utilize triplet excitons. In this work, we demonstrate how variation of the anion in organic salts with carbazole and phenothiazine-5,5-dioxide donors and pyridinium and quinolinium acceptors may be used to switch between TADF and RTP. These compounds adopt similar molecular structures and packing modes with different anions and exhibit different types of photophysical behavior due to the electronic effects of the anions. With bromide anions, the salts exhibit TADF with some RTP. These compounds show fast reverse intersystem crossing and a short delayed lifetime, which is key to application in efficient and robust OLEDs. With BF₄ ^- and PF₆ ^- anions, RTP with long-lived lifetimes and afterglow are observed by eye. This behavior can be utilized for data encryption and anti-counterfeiting applications. Emission wavelengths and lifetimes are also anion-dependent. These results open up an avenue for developing novel luminescent materials through anion tuning and present a molecular model to understand the interplay of RTP and TADF.