Effects of the change of isomers on room-temperature phosphorescence, thermally activated delayed fluorescence, and long persistent luminescence of organic hole-transporting materials with the selective potential for the application in electronic devices and optical sensors of oxygen

Competition of room-temperature phosphorescence (RTP) and thermally activated delayed fluorescence (TADF) was investigated on the example of four newly synthesised organic isomeric compounds containing two electron-donating triphenylamine moieties and single electron-accepting dibenzothiophene-2-yl(phenyl)methanone unit by numerous theoretical and experimental approaches. The different emission origin (RTP or TADF) of the isomeric compounds was caused by the different energy gaps between the lowest singlet and triplet states locally exited and charge transfer in nature. Very different external quantum efficiencies ranging from 2.8 to 13.9% were observed for green phosphorescent organic light-emitting diodes fabricated using the isomeric compounds as the hosts. Such device efficiency differences were related to the different hole mobility values. The hole mobilities of ca. 1 × 10−3 cm2V−1s−1 were observed at an electric field of 6.4 × 105 V/cm for the derivatives having triphenylamine moieties at C-2, C-4, and at C-3, C-5 positions of the central benzene ring. Considerably lower hole mobilities of ca. 1 × 10−5 cm2 V−1 s−1 were recorded at the same electric field for the compounds with triphenylamine groups at C-2, C-3, and at C-2, C-6 positions. Depending to the great extent on RTP and TADF processes, different efficiencies of long persistent luminescence (LPL) of the exciplex-forming solid-state mixtures of the isomers and bis[2-(diphenylphosphine)phenyl] ether oxide (DPEPO) were detected. The compound with triphenylamine groups at C-3, and C-5 positions as RTP emitter and its molecular mixture with DPEPO as LPL emitter the active layers of optical sensors of oxygen were prepared. They showed the Stern–Volmer constant of 4.55 × 10−4 ppm in the range of oxygen concentrations up to 10000 ppm.