TD-DFT study on fluoride-sensing mechanism of 2-(2′-phenylureaphenyl)benzoxazole: the way to inhibit the ESIPT process

The fluoride-sensing mechanism of the sensor 2-(2'-phenylurea-phenyl) benzoxazole (PUBO) has been investigated by means of the TD-DFT method. The present theoretical study indicates that there is an excited-state intramolecular proton transfer (ESIPT) process in the sensor PUBO. The added fluoride anion could capture the proton in the free N-H moiety instead of the hydrogen-bonding one. The experimental UV/Vis and fluorescence spectra (J. Org. Chem. 2007, 72, 62) are well reproduced by the calculated vertical excitation energies in the ground state and the first singlet excited state. For example, the calculated emission wavelength of PUBO at 534 nm is very close to the fluorescence band at 554 nm. Furthermore, we theoretically confirmed that the added fluoride anions could inhibit the ESIPT process in PUBO. But different from the classical ESIPT-inhibition mechanism, the ESIPT process in the sensor PUBO is inhibited by the high energy barrier of its deprotonated form rather than by the absence of the transferred proton.