Theory of Long-Lived Room-Temperature Phosphorescence in Organic Aggregates

Conspectus Room-temperature phosphorescence (RTP) with a long afterglow from purely organic molecular aggregates has recently attracted many investigations because traditionally only inorganic and transition-metal complexes can emit phosphorescence at room temperature. Purely organic molecules can exhibit phosphorescence only at cryogenic temperatures and under inert conditions in solution. However, recently, a number of organic compounds have been found to demonstrate bright RTP upon aggregation, sometimes with a remarkable morphology dependence. We intended to rationalize such aggregation-induced organic RTP through theoretical investigation and quantum chemistry calculations by invoking intermolecular interaction effects. And we have identified the molecular descriptors for the molecular design of RTP materials. In this Account, we started with the proposition of the mechanism of intermolecular electrostatic-interaction-induced RTP at the molecular level by using molecular dynamics simulations, hybrid quantum mechanics, and molecular mechanics (QM/MM) coupled with the thermal vibration correlation function (TVCF) formalism we developed earlier. The effective intermolecular electrostatic interactions could stem from a variety of interactions in different organic RTP crystals, such as hydrogen bonding, π–halogen bonding, anion−π + interaction, and d–pπ bonds and so forth. We find that these interactions can change the molecular orbital compositions involved in the lowest-lying singlet and triplet excited states that are responsible for phosphorescence, either through facilitating intersystem crossing from the excited-state singlet to the triplet and/or suppressing the nonradiative decay process from the lowest triplet to the ground state. This underlying RTP mechanism is believed to be very helpful in systematically and comprehensively understanding the aggregation/crystal-induced persistent organic RTP, which has been applied to explain a number of experiments. We then propose the molecular descriptors to characterize the phosphorescence efficiency and lifetime, respectively, derived from fundamental photophysical processes and requirements to obey the El-Sayed rule and generate phosphorescence. For a prototypical RTP system consisting of a carbonyl group and π-conjugated segments, the excited states can be regarded as an admixture of n → π* (with portion α) and π → π* (with portion β). The intersystem crossing (ISC) rate of S 1 → T n is mostly governed by the modification of the product of α and β, and the nonradiative rate of T 1 → S 0 is determined by the β value of T 1 . Thus, we employ γ = α × β and β to describe the phosphorescence efficiency and lifetime, respectively, which have been successfully applied in the molecular design of efficient and long-lived RTP systems in experiments. The molecular descriptors outlined in this Account, which are easily obtained from simple quantum chemistry calculations, are expected to play important roles in the machine-learning-based molecular screening in the future.