Clustering-Triggered Ultralong Room-Temperature Phosphorescence of Organic Crystals through Halogen-Mediated Molecular Assembly

To achieve efficient room-temperature phosphorescence of organic materials with ultralong lifetime, it is imperative to resolve the dilemma that the introduction of heavy atoms simultaneously improves emission efficiencies and shortens the emission lifetimes. Herein, we report a new molecular design approach for halogenated luminogens with a methylene bridge to avoid the lifetime shortening induced by heavy halogens and propose a general molecular engineering strategy to realize efficient and ultralong room-temperature phosphorescence via halogen-mediated molecular clustering. The halogenated N-benzylcarbazole derivatives show distinct photophysical behaviors depending on different physical states, including single-molecule state and cluster state. Their crystals demonstrate the halogen-dependent emission duration of room-temperature phosphorescence upon excitation. Experimental data and theoretical analysis indicate that halogen-regulated molecular clustering in the crystal is responsible for the generation of efficient ultralong room-temperature phosphorescence, and halogen-dominated molecular engineering favors the promotion of the intersystem crossing process and the following triplet emissions.