TADF quenching properties of phenothiazine or phenoxazine-substituted benzanthrones emitting in deep-red/near-infrared region towards oxygen sensing

Aiming to develop new deep-red/near-infrared emitters, benzanthrone as a new acceptor moiety with a rigid molecular structure was used. For the design of target compounds phenothiazine and phenoxazine moieties with strong electron-donating ability were also used. Such combination allowed new materials demonstrating thermally activated delayed fluorescence (TADF) in the long wavelength region to be obtained. The maximum intensity of fluorescence of the solid samples of the synthesized compounds was observed at 700 nm. Electroluminescence was peaked at similar wavelength when the compounds were used as emitters for the fabrication of non-doped organic light-emitting diodes. Due to the different substitutions of benzanthrone moieties, the values of TADF lifetimes at room temperature were found to be of in the range of 291-1198 mu s which are directory related to their different oxygen sensing properties. Due to high sensitivity to the presence of oxygen in the atmosphere one of the obtained compounds was used for radiometric oxygen sensing. The film of molecular dispersion of phenoxazine containing compound in inert polymer ZEONEX (R) showed the ratio of intensity of TADF taken in vacuum and of prompt fluorescence taken under oxygen purge of 15.2. The oxygen sensitivity of the film estimated by Stern-Volmer constant was found to be of 1.6 x 10-4 ppmxfffd; 1 demonstrating good reversibility. The time dependent density functional theory (DFT) calculations were used for the interpretation of the experimental results related to the structure and photophysical properties of the compounds.

Automated summary

By combining benzanthrone, phenothiazine, and phenoxazine moieties, new materials with TADF properties in the deep-red/near-infrared region were successfully developed, as well as compounds suitable for oxygen sensing applications. Different substituents on the benzanthrone moiety were found to result in varying oxygen sensitivity, with one compound exhibiting good reversibility under oxygen isotope ratio influence.