Theoretical insights into room temperature phosphorescence emission with anti-Kasha behavior in aggregate

Organic room temperature phosphorescence (RTP) materials with long lifetimes have shown promising applications in organic light emitting diodes and bioimaging fields. However, the inner luminescent mechanisms for RTP especially for high lying triplet state emission, have not been unveiled. Herein, based on density functional theory (DFT) and time-dependent density functional theory (TD-DFT), the photophysical properties of four RTP systems with triphenylethylene derivatives as skeletons are studied. Excited state dynamic process in aggregate is systematically studied by combining quantum mechanics with molecular mechanics (QM/MM) method coupled with thermal vibration correlation function (TVCF) method. Moreover, the intermolecular interactions are measured by the independent gradient model based on Hirshfeld partition (IGMH) method, the Huang-Rhys factor, reorganization energy and spin-orbit coupling (SOC) constant are calculated, radiative and non-radiative decay as well as intersystem crossing (ISC) and reverse intersystem crossing (RISC) processes are all investigated. Results indicate that the radiative decay process from the lowest triplet excited state (T1) to ground state (S0) is low and the non-radiative decay process is high, various calculations are also performed to exclude the emission process from T1 to S0, thus non-luminescence is determined for T1. Furthermore, a large energy gap between T2 and T1 is observed, and high radiative decay and low non-radiative decay processes from T2 to S0 are confirmed. Thus, the mechanisms of RTP from high lying triplet state T2 are revealed. Furthermore, through wise molecular design and detailed calculations, the mechanical insights are detected that the RTP emissions with anti-Kasha behavior are largely related to the unique molecular configurations with triphenylethylene derivatives as skeletons. Our studies give reasonable explanations for the previous experimental measurements and provide underlying perspectives for RTP mechanisms from high lying triplet state T2, which could promote the development of new efficient RTP emitters.