The solvent-regulated excited state reaction mechanism of 2-(2'-hydroxyphenyl)benzothiazole aggregates

Abstract

The excited state relaxation dynamics of 2-(2'-hydroxyphenyl)benzothiazole (HBT) in the gas phase and the solvents have been explored experimentally and theoretically. However, the fundamental mechanism of its emission in aggregates is still unexplored. In this article, we have presented a detail investigation of solvent-regulated excited state (ES) reactions for HBT aggregates with the aid of several experimental and theoretical research. The careful investigation of solvatochromic and electrochemical behavior elucidates that the emission around 460 nm of HBT in DMSO and DMSO-water fraction correspond to the excited state internal charge transfer (ESICT). The quantum chemical analysis further supports this observation. The concentration-dependent ¹H NMR and emission studies of HBT in DMSO revealed the formation of aggregates at higher concentrations that facilitate the charge transfer. The emission pattern of HBT in the AcN-water fraction demonstrates that the sequential internal charge transfer-proton transfer (ESICT-ESIPT) occurs in HBT aggregates. The pH studies show that HBT aggregates are potential ratiometric sensors for near-physiological pH ranges. Moreover, a ground-state zwitterionic conformation of HBT is observed in the basic medium formed by ground-state internal proton transfer (GSIPT). Overall, this study provides a better understanding of solvent-regulated ES reaction mechanism in the case of HBT aggregates and other substituted HBT compound aggregates published previously.

Keywords: Aggregation induced emission; Benzothiazole; Excited state reaction mechanism; Ground-state internal proton transfer; Spectroscopy; Zwitterionic conformation.