Revised excited-state intramolecular proton transfer of the 3-Aminophthalimide molecule: A TDDFT study

The spectroscopic properties of 3-Aminophthalimide (3AP) molecule were investigated [Chem. Phys. 2002, 283, 249, New J. Chem. 2018, 42, 1181]. The result was that the 3AP molecule was exhibiting excited-state intramolecular proton transfer (ESIPT). In the research, we revised previous result using time-dependent density functional theory (TDDFT) method. The fluorescence spectrum shows that the only fluorescence peak is from initial enol form, which is different from the traditional case of ESIPT. The red shift of characteristic peaks in infrared vibration spectra is not induced by ESIPT process. The change in the vibration mode of the amino group causes the red shift of characteristic peak in the infrared spectrum. Energy curves indicate that the barrier (19.71 kcal/mol) is anomalously high in the first excited state. In addition, there are not stable points to lead the ESIPT to form a keto isomer. Together, these results demonstrate that there is not an ESIPT process happening of 3AP molecule. Infrared vibration spectra and energy curves demonstrate that ESIPT process of 3-Aminophthalimide molecule is impossible to occur. [Display omitted] •The ESIPT mechanism of 3-Aminophthalimide (3AP) molecule is revised by TDDFT method.•Optimized molecular configurations indicate that the Keto-3AP form is nonexistent.•Energy curves conclude that there aren't stable points to leads the ESIPT for the 3AP molecule.