Difluoroboron β‐Diketonate Systems: Large Transformation of Photophysical Mechanism Induced by Tiny Structural Modification or Isomerization

Abstract Living system involves a plenty of delicate processes where a tiny structural variation of biological substance may lead to drastic change of the fate of the living system. Inspired by this, in artificial photofunctional systems, if tiny structural variation changes the fate of excited states, a new class of advanced material would emerge for optical analysis, sensing, and next‐generation display is reasoned. However, such delicate processes remain rarely explored in photofunctional systems, especially in room temperature organic afterglow systems. Here the attachment/detachment of methoxy group can switch off/on twisted intramolecular charge transfer property in difluoroboron β‐diketonate systems is reported. In addition, structural isomerization triggers afterglow transformation from room temperature phosphorescence to thermally activated delayed fluorescence. These observations are helpful for better photophysical understanding on luminescence systems and advanced material design.