Insights on aggregation induced room temperature phosphorescence properties: A QM/MM study

Organic room temperature phosphorescence (RTP) molecules have attracted significant attention recently due to their promising application in security, bioimaging, sensing and organic light emitting diodes (OLEDs). Nevertheless, limited RTP molecules were reported until now and most of RTP phenomena were observed in crystal. Moreover, the underlying mechanisms of RTP still remain ambiguous. In this paper, excited-state properties of CZs-CN with RTP features in three crystals are theoretically studied using the combined quantum mechanics and molecular mechanics (QM/MM) method. Moreover, the photophysical properties of CZs-CN in solvent are also investigated by polarizable continuum model (PCM). The mechanism of aggregation induced RTP is revealed which is mainly contributed by the enhanced phosphorescence rates in aggregation, rather than the traditional restricted intramolecular motion mechanisms which usually bring decreased non-radiative decay rates. In addition, different crystal structures could induce different phosphorescence properties, and the emission spectra of the molecule in three crystals and THF are explained reasonable. Furthermore, dimers are confirmed to be involved in the emission when the intermolecular interaction is strong enough in aggregation. Our theoretical results provide inner perspective for aggregation induced RTP mechanism and could help one to better understand the different light-emitting properties in aggregation and solvent.