Excited-state intramolecular proton transfer on 2-(2′-hydroxy-4′-R-phenyl)benzothiazolenanoparticles and fluorescence wavelength depending on substituent and temperature

Abstract

The fluorescence emission properties of 2-(2′-hydroxy-4′-R-phenyl)benzothiazole (HBT-R) nanoparticles with different substituents (R = –COOH, –H, –CH₃, –OH, and –OCH₃) were investigated using spectroscopic and theoretical methods. HBT-Rs displayed dual enol and keto (excited-state intramolecular proton transfer (ESIPT)) emissions in nonpolar solvents. The spectral change of their ESIPT emissions was affected differently by the electron donating (or withdrawing) power of the substituents; a bathochromic shift for the electron donating group and a hypsochromic shift in electron withdrawing group. In addition, the changes in energy levels calculated by the ab initio method were consistent with the spectral shifts of HBT-R in solution. We prepared aggregated HBT-R nanoparticles using a simple reprecipitation process in tetrahydrofuran–water solvents. The ESIPT emission of aggregated HBT-R nanoparticles was strongly enhanced (over 45 times) compared to those of monomer HBT-Rs in toluene, as markedly shifted ESIPT emissions are observed at longer wavelength without any quenching by self-absorption. Aggregated HBT-R nanoparticles showed longer lifetimes than those of monomer molecules. The temperature effect on the aqueous dispersion of the aggregated HBT-R nanoparticles was also explored. It shows a fluorescent ratiometric change in a range of temperature from 7 to 65 °C. A mechanism of a temperature-dependent equilibrium between the nanoparticles and the solvated enols is proposed for the emission color change.