Theoretical Study of Conversion and Decay Processes of Excited Triplet and Singlet States in a Thermally Activated Delayed Fluorescence Molecule

Quantitative understanding of the photophysical processes is essential for developing novel thermally activated delayed fluorescence (TADF) materials. Taking as an example 1,2,3,5-tetrakis(carbazol-9-yl)-4,6-dicyanobenzene, a typical TADF-active molecule, we calculated the interconversion and decay rates of the lowest excited singlet and triplet states at different temperatures as well as the prompt and delayed fluorescence efficiencies at 300 K at the first-principles level. Our results can reproduce well the experimentally available data. It is found that the reverse intersystem crossing rate (kRISC) is sharply increased by 3 orders of magnitude, while the other rates increase slightly or remain unchanged when the temperature rises from 77 to 300 K. Importantly, kRISC reaches up to 1.23 × 106 s–1 and can compete with the radiative and nonradiative decay rates of S1 (1.11 × 107 and 2.37 × 105 s–1) at 300 K, leading to an occurrence of delayed fluorescence. In addition, our calculations indicate that it is the freely rotational motions of the carbazolyl between two cyano groups that are responsible for the interconversion between S1 and T1. The large torsional barriers of other three adjacent carbazolyl groups block the nonradiative decay channels of S1 → S0, leading to strong fluorescence. This work would provide useful insight into the molecular design of high-efficiency TADF emitters.