A time-dependent density functional theory study of a fluorescent probe to detect hydroxyl radicals: Inhibiting the twisted intramolecular charge-transfer process

[Display omitted] •The fluorescent sensing mechanism for hydroxyl radicals is obtained by TD-DFT.•Calculated VTEs well agree with UV–Vis and fluorescent spectra of the probe.•TICT process of the probe is responsible for its weak fluorescence.•Different FMOs lead to different fluorescent properties of the probe and its oxidation product. Due to the relevance to excited-state processes, sensing mechanisms of fluorescent probes were difficult to study directly by experimental methods. This work investigated theoretically the sensing mechanism of a reported bifunctional fluorescent probe to detect intracellular hydroxyl radicals and their environmental viscosity (J. Am. Chem. Soc. 2019, 141, 18301). Calculations were performed at the B3P86/TZVP/SMD level using density functional theory and time-dependent density functional theory. The transition from the ground-state (S0) to the first singlet excited state (S1) was calculated to have the largest oscillation strength for the probe. The wavelength that corresponded to the S0-S1 vertical excitation energy (427 nm) agreed well with the maximum absorption band at 400 nm in the ultraviolet–visible spectra. Theoretical results showed that the probe had two distinct geometries in the S0 and S1 states, respectively. This difference was caused by the different distributions of frontier molecular orbitals that were involved in the S0-S1 transition and corresponds to a twisted intramolecular charge transfer. The S1-state potential energy curve of the probe molecule confirmed that the twisted intramolecular charge transfer could proceed spontaneously with a potential barrier of only 12.20 kJ/mol. This result provided an irradiative approach for the probe molecule to dissipate the S1-state energy, which explained its fluorescence quenching. In contrast, the hydroxyl oxidation reaction changed frontier molecular orbitals of the probe molecule, which made its S1 state a local S1 state with a strong fluorescence emission. Precisely due to the mechanism, the hydroxyl radicals could be detected by changes in the fluorescence signal of the probe molecule.