Design of Intramolecular Dihedral Angle between Electronic Donor and Acceptor in Thermally Activated Delayed Fluorescence Molecules

In order to improve the exciton utilization efficiency (ηexc) of organic light-emitting materials, we addressed the ideal donor–acceptor dihedral angle (θD–A) in the TADF molecule by striking a balance between two photophysical processes. One is the conversion of triplet excitons into singlet excitons, and the other is the radiative process from a low-lying excited state to the ground state. Using a combination of first-principles calculations and molecular dynamics simulations, we investigated the impact of θD–A on the splitting energy and spin–orbit coupling between singlet and triplet excitons as well as the transition dipole moment for carbazole benzonitrile (CzBN) derivatives. By comparison with the reverse intersystem crossing rate (k rISC), fluorescence emission rate (k r), and ηexc, we proposed a potential highest ηexc (of 94.4%) with the ideal θD–A of 77° for blue light CzBN derivatives; the calculated results have a good agreement with experimental measurement. The structure–efficiency physical connection between the molecular structure (θD–A) and efficiency provided an ideal parameter for a potential candidate for blue TADF-OLED materials.