Photobasicity-Triggered Twisted Intramolecular Charge Transfer of Push–Pull Chromophores

• Published in: The journal of physical chemistry. B Vol. 129; no. 33; pp. 8485 - 8493
• Main Authors: Pounder, Austin, Pavlovic, Matteo, Chow, Darren, Regan, Keenan T., Chen, Aicheng, Wetmore, Stacey D., Manderville, Richard A.
• Format: Journal Article
• Language: English
• Published: United States American Chemical Society 21.08.2025
• Subjects: B: Liquids; Chemical and Dynamical Processes in Solution
• ISSN: 1520-6106; 1520-5207; 1520-5207
• DOI: 10.1021/acs.jpcb.5c03367

Fluorogenic probes that undergo excited-state proton transfer (ESPT) and twisted intramolecular charge transfer (TICT) offer tunable fluorescence properties for bioimaging and sensing applications. However, the relationship between ESPT and TICT remains poorly understood in push–pull chromophores. Despite extensive research on photoacids, photobases remain underutilized as fluorescence modulators, and the roles of solvent polarity, acidity, and donor–acceptor strength in governing photobasicity and TICT activation are not well established. We conducted photophysical experiments and (TD)-DFT calculations to explore how protonation and solvent interactions influence fluorescence behavior. Our findings reveal that while protonation consistently induces red-shifted absorption and emission, ESPT efficiency and TICT formation vary widely depending on molecular structure and solvent environment. This work provides new insights into photobasicity-driven fluorescence modulation, offering a foundation for designing next-generation probes with enhanced sensitivity to local acidity, viscosity, and microenvironmental factors.