Dangling Water Molecules Bridge for ESIPT in Aggregated TMP: A Theoretical Study

We present a theoretical study on the occurrence of excited-state proton transfer in an aggregated structure of 2-(benzo[d]thiazol-2-yl)-6-methoxyphenol (TMP) exclusively in water among polar solvents, as reported in a recent experiment (Bhattacharyya, A. New J. Chem. 2019, 43, 15087). Our extensive investigation of the TMP monomer and dimer implementing density functional theory (DFT) and time-dependent density functional theory (TDDFT) methods, in three different solvents, namely, water, methanol, and dimethyl sulfoxide (DMSO), with explicit inclusion of solvent molecules demonstrated the existence of both enol and keto forms of the TMP dimer in the excited state, but only in water; this confirmed the experimental emission spectra completely and simultaneously validated the aggregation-induced emission phenomenon. Further analysis of various parameters such as potential energy scan (PES) of the hydroxyl (O-H) bond involved in hydrogen bonding, frontier molecular orbitals (FMOs), molecular electrostatic potential (MEP), and infrared (IR) stretching frequencies of both the monomer and dimer forms of TMP in different solvents clearly indicated the geometry of the dimer, with the arrangement of the solvent molecules to be the sole reason for the excited-state charge transfer. The bridging alignment of water molecules in between the stacked units of the TMP dimer results in intermolecular interactions, ultimately leading to intermolecular proton transfer in the excited state.