Synergetic Conformational Regulations in Ground and Excited States for Realizing Stimulus-Responsive and Wide-Tuning Room-Temperature Phosphorescence

Understanding the changes of molecular conformations is crucial for realizing multiple emissive triplet states in room-temperature phosphorescence (RTP) materials. In this work, we report two molecules, 4,4'-dimethylbenzil (DMBZ) and 4,4'-di-tert-butylbenzil (DBBZ) with conformation-dependent luminescence, and demonstrate that stimulus-responsive and wide-tuning RTP emissions can be realized via synergetic conformational regulations in ground and excited states. Due to conformational changes, DMBZ and DBBZ show abundant RTP variations upon external stimuli, including light, force, heat, and fumigation. Notably, DBBZ exhibits multiple conformational changes in both ground and excited states, which endow DBBZ with multiple emissive states and unique stimulus-responsive behaviors. DBBZ presents multiple phase transitions between the supercooled liquid state and different solid states accompanied by different phosphorescence transitions, in which the excited-state conformations are effectively regulated. Moreover, wide-range RTP regulations (between cyan, green, and yellow) are realized in both single component and host-guest systems of DBBZ, showing potential applications in temperature sensing, multicolor dynamic displays, and information encryption. These results may provide new visions for understanding the complicated conformational changes in the aggregated state, as well as unique insights into the relationship between molecular conformations, RTP emissions, and stimulus responsiveness.