Sergeant‐and‐Soldier Effect in an Organic Room‐Temperature Phosphorescent Host‐Guest System

Abstract Host‐guest systems have emerged as an efficient strategy for promoting organic room temperature phosphorescence (RTP). Despite the advantages of doping guest molecules into a host matrix, the complexity of these systems and the lack of techniques to visualize host‐guest interactions at the molecular scale pose significant challenges in understanding the underlying mechanisms. Here, a novel host‐guest RTP system is developed by incorporating low concentrations (1–10 mol%) of TPP‐4C‐BI (guest) into crystalline TPP‐4C‐Cz (host). Utilizing structural isomerism, the guest molecules are regularly incorporated into the host crystal lattice, resulting in phosphorescence quantum yields almost ten times higher than the pure compounds. The system enabled resolution of the molecular packing of the single crystal through X‐ray diffraction, providing unprecedented visualization of host‐guest interactions. A “sergeant‐and‐soldier” effect, where the minority dopant molecules (sergeants) significantly influence the packing arrangement of the host molecules (soldiers), enhances RTP is identified. Further analyses revealed that due to the host molecule's inefficient phosphorescence pathway, its long‐lived dark triplets are channeled to the guest via triplet‐triplet energy transfer (TTET), allowing the excited energy to radiatively decay more efficiently. These insights advance the understanding of RTP mechanisms and offer practical implications for designing high‐efficiency phosphorescent materials.