Visualizing Triplet Energy Transfer in Organic Near‐Infrared Phosphorescent Host‐Guest Materials

Abstract Limited by the energy gap law, purely organic materials with efficient near‐infrared room temperature phosphorescence are rare and difficult to achieve. Additionally, the exciton transition process among different emitting species in host–guest phosphorescent materials remains elusive, presenting a significant academic challenge. Herein, using a modular nonbonding orbital‐π bridge‐nonbonding orbital (n‐π‐n) molecular design strategy, we develop a series of heavy atom‐free phosphors. Systematic modification of the π‐conjugated cores enables the construction of a library with tunable near‐infrared phosphorescence from 655 to 710 nm. These phosphors exhibit excellent performance under ambient conditions when dispersed into a 4‐bromobenzophenone host matrix, achieving an extended lifetime of 11.25 ms and a maximum phosphorescence efficiency of 4.2 %. Notably, by eliminating the interference from host phosphorescence, the exciton transition process in hybrid materials can be visualized under various excitation conditions. Spectroscopic analysis reveals that the improved phosphorescent performance of the guest originates from the triplet‐triplet energy transfer of abundant triplet excitons generated independently by the host, rather than from enhanced intersystem crossing efficiency between the guest singlet state and the host triplet state. The findings provide in‐depth insights into constructing novel near‐infrared phosphors and exploring emission mechanisms of host–guest materials.