Theoretical Study on the Luminescence Behavior and Recognition Mechanism of Fluorescent Probe TTB toward Cyanide Ions

Cyanide (CN^-), a highly toxic substance, is prevalent across industrial, agricultural, and natural environments, posing a grave threat to human health and ecosystems. Numerous fluorescent probes for cyanide detection have been developed based on mechanisms such as photoinduced electron transfer (PET) and intramolecular charge transfer (ICT). In this study, a theoretical approach was employed to investigate the sensing mechanism, photophysical properties, and reaction pathways of the TTB fluorescent probe in tetrahydrofuran (THF) solvent. This approach integrates the polarizable continuum model (PCM), time-dependent density functional theory (TD-DFT), and the thermal vibration correlation function formalism (TVCF) to provide a comprehensive understanding of the probe's properties and behaviors. The photophysical and chemical properties of the fluorescent probe TTB and its cyanide adduct, TTB-CN, were systematically investigated. The results indicate that the TTB probe itself exhibits negligible fluorescence, whereas the product formed upon binding with cyanide demonstrates significant fluorescence emission. This difference is attributed to the substantially lower predicted radiative decay rate (<i>k</i>_r) of TTB compared to that of TTB-CN. Furthermore, the presence of a fluorine atom in TTB enhances the intersystem crossing rate (<i>k</i>_isc) by a factor of 7 relative to TTB-CN. Consequently, the calculated fluorescence quantum yield of TTB is only 0.042%, while that of TTB-CN exceeds 18.14%. These findings provide a scientific basis for the application of TTB as a fluorescent probe. Investigations into the reaction mechanism demonstrate that this reaction proceeds as a nucleophilic reaction featuring a relatively low energy barrier. Additionally, our calculations reveal that both TTB and TTB-CN exhibit two-photon absorption properties, suggesting their potential for two-photon-based detection in biological systems.