Substituent derivatives of benzothiazole-based fluorescence probes for hydrazine with conspicuous luminescence properties: A theoretical study.

In the present work, four probe molecules for detecting hydrazine have been designed based on the 2-(4-Acetoxy-3-benzothiazole-2-yl-phenyl)-4-methyl-thiazole- 5-carboxylic acid ethyl ester (HP1) to investigate the influence of the amino and cyano groups on the excited-state intramolecular proton transfer (ESIPT) behavior and photophysical properties. The changes in hydrogen bond strength indicate that the intramolecular hydrogen bond of all probe products is enhanced upon photoexcitation. Frontier molecular orbitals (FMOs) and natural bond orbital (NBO) reveal the driving force of ESIPT. In addition, the potential energy curves and transition state theory explain the reason for the single fluorescence phenomenon in the experiment. The simulated absorption and fluorescence spectra of HP1 and its product (HPP1) are completely consistent with the experimental results, which also verify the viewpoint. Meanwhile the cyano derivative HPP4 exhibits a larger Stokes-shift (201 nm) than that of HPP1 (145 nm) and has the same low energy barrier as HPP1. These excellent properties allow HPP4 to be a fluorescent probe with superior performance than the original molecule. In conclusion, this work can provide a theoretical basis for the design and synthesis of more sensitive fluorescent probes for the detection of hydrazine.

Theoretical study on the optical properties of an ESIPT-based fluorescent probe for phosgene.

A fluorescent probe Pi with the excited-state intramolecular proton transfer (ESIPT) properties was synthesized and used to detect the phosgene in solution and gas phases. However, the detection mechanism of the fluorescent probe needs to be further studied. Herein, the density functional theory (DFT) and time-dependent density functional theory (TD-DFT) methods were adopted to explore the molecular structures and electronic spectra properties of probe and its product Pio after reacting with phosgene. Through analysis for molecular structure parameters and infrared vibrations accompanied with the hydrogen bond of Pi, it is confirmed that the intramolecular hydrogen bond of Pi is enhanced under light excitation, which illustrates the occurrence of ESIPT reaction combined with the scanned potential energy curves. It can be seen from the simulated spectra that Pi shows double fluorescence through ESIPT process, while the fluorescent product Pio exhibits the single fluorescence due to the disappearance of intramolecular hydrogen bond. Through the study on the structure and optical properties of Pi and Pio, it can be helpful to deeply understand the intrinsic mechanism of the detection of phosgene by the Pi molecule probe, which also supplies a reference to the further study about the fluorescence probe.