Theoretical study on the influence of substitution position on the luminescence properties and charge transfer characteristics of thermally activated delayed fluorescent molecules

Abstract

Thermally active delayed fluorescence (TADF) molecules have potentially applications in organic light-emitting diodes (OLEDs) and biomedical sensing. Although TADF emitters have witnessed a rapid development, it remains challenging to study the relationship between molecular structures and luminescence properties as well as carrier mobility transfer properties in theory. In this work, the photophysical properties and luminescence mechanisms of isomers TPA-APQDCN-C (donors at para-position) and TPA-APQDCN-Y (donors at ortho-position) were studied based on density functional theory (DFT) and thermal vibration correlation function (TVCF) method. The results showed that both TPA-APQDCN-C with para-substituted donor and TPA-APQDCN-Y with ortho-substituted donors exhibit red emission in toluene and crystal state. Furthermore, compared to ortho-substituted donors, para-substituted donors promote a redshift in emission wavelength. In addition, the fluorescence efficiencies of TPA-APQDCN-C is obviously higher than that of TPA-APQDCN-Y due to its larger radiative rate and less non-radiative decay rate. Besides, para-substitution (TPA-APQDCN-C) leads to the smaller energy gap between S1 and T1 and the larger spin–orbit coupling (SOC) constant, which is beneficial for increasing the reverse crossing intersystem (RISC) rates. In addition, the carrier mobilities are studied based on the kinetic Monte Carlo simulations. The calculations show that TPA-APQDCN-C are more beneficial for the transfer of holes compared to TPA-APQDCN-Y. This study reveals TPA-APQDCN-C with donors at para-position has a better TADF properties and hole transfer ability, which holds guiding significance for the design of TADF devices with high luminescence efficiency and rapid hole transfer.