Excited state properties of non-doped thermally activated delayed fluorescence emitters with aggregation-induced emission: a QM/MM study

Abstract

The excited state properties of dibenzothiophene-benzoyl-9,9-dimethyl-9,10-dihydroacridine (DBT-BZ-DMAC) in the solid phase are theoretically studied through a combined quantum mechanics and molecular mechanics (QM/MM) method. The results indicate that the non-radiative decay rate of the molecule in the solid phase is significantly decreased due to the suppression of the rotation of the DMAC and DBT units in the molecule, while the radiative rate is greatly increased owing to the enhancement of the transition dipole moment. Moreover, the fluorescence efficiency in the solid phase (20.5%) is shown to be much larger than that in the gas phase (0.01‰), which confirms that DBT-BZ-DMAC is a typical aggregation-induced emission (AIE) system. The results further display that both the intersystem crossing (ISC) and reverse intersystem crossing (RISC) processes take place between the first singlet excited state (S1) and the lowest degenerate triplet excited states (T1 and T2). In addition, the charge transfer rate is studied using the Marcus theory and the intrinsic charge mobility is calculated by performing the kinetic Monte Carlo method. The results show that the DBT-BZ-DMAC crystal is a p-type semiconductor with a hole mobility of 0.14 cm² V⁻¹ s⁻¹ at room temperature. Our investigation elucidates the experimental measurements and helps one to understand the AIE mechanisms of the DBT-BZ-DMAC fluorescence emitter, which is beneficial for developing new TADF emitters.