ESIPT-associated fluorescent property and AIE characteristic of multifunctional nanoprobe DPNAP

Abstract

The DPNAP is a multifunctional nanoprobe designed for selective illumination of fungi and targeted antimicrobial applications. By introducing hydroxyl groups into the DPNAP, the aggregation-induced emission (AIE) characteristic can be obtained. However, its optical properties and underlying theoretical mechanisms are not fully understood. In this work, we explored the stable DPNAP configurations by constructing the potential energy surfaces and elucidated the mechanism of the proton transfer reaction. Our findings indicate that proton transfer occurs through a stepwise reaction with energy barriers of < 10 kcal/mol, owing to the variation in hydrogen-bonding strength as revealed by hydrogen-bond parameters and infrared vibrational analyses. The theoretical fluorescence peak (λcal = 541 nm) based on the optimized structures is consistent with the experimental peak (λexp = 500 nm). The experimental single-fluorescence band is attributed to the overlap of emission spectra of normal structure and single- and double-proton transfer isomers. Moreover, the hydroxyl-induced AIE mechanism is attributed to increased molecular planarity and restricted intramolecular charge transfer in the aggregate state. Understanding of the AIE characteristic and ESIPT mechanism is of fundamental importance in molecular electronics and photonics, and is also beneficial to the development of novel biomedical materials.