Stepwise Excited-state Double Proton Transfer and Fluorescence Decay Analysis

This work considers excited state intramolecular proton transfers (ESIPT) occurred in multiple hydroxyl-containing compounds with one proton transfer site in the normal form. If several hydroxyl groups are located close to each other in a molecule, then the ESIPT process can lead to the next one. A proton donor site in the first ESIPT will be a proton acceptor during the second reaction. Therefore, a number of consecutive excited state proton transfers can occur. This work deals with the case of two successive proton transfers occurred in the molecular system. Such process is called as a stepwise excited state intramolecular double proton transfer (stepwise ESIDPT). It leads to the formation of two molecular tautomers. Therefore, fluorescence of such compounds can contain different emission bands correspond to emission of normal form and two tautomers. In this work, a rigorous analysis of fluorescence decay kinetics has been made using the model with three species, including a normal molecular form and two tautomers. The work presents theoretical framework of fluorescence decay analysis of ESIDPT process taking into account three species emission. Theoretically, the stepwise proton transfers can be consisted of more than two ESIPT reactions. It depends on molecular structure and number of involved hydroxyl groups. Here, a formal analysis of fluorescence decay kinetics has been made in the case of a stepwise process consisting of two proton transfers. Moreover, the quantum-chemical calculations have been performed in the case of scutellarein. It is a multiple hydroxyl-containing flavone and, therefore, it can be applied as a model molecule to study stepwise intramolecular proton transfers. The hypothetical scheme of ESIDPT has been proposed for this compound. GRAPHICAL ABSTRACT: [Image: see text] SUPPLEMENTARY INFORMATION: The online version contains supplementary material available at 10.1007/s10895-022-03042-w.