Solvent polarity dependent excited state hydrogen bond effects and intramolecular double proton transfer mechanism for 2-hydroxyphenyl-substituted benzo[1,2-d:4,5-d']bisimidazole system.

Abstract In this work, we probe into the photo-induced excited state hydrogen bonding interactions and excited state proton transfer (ESPT) behaviors for a representative benzo[1,2-d:4,5-d’]bisimidazole derivative (i.e., 2-hydroxyphenyl-substituted benzo[1,2-d:4,5-d’]bisimidazole (HPBB)) compound. In view of aprotic solvents with different polarities, cyclohexane (CYH), dichloromethane (DCM) and acetonitrile (MeCN) solvents are considered. Analyzing hydrogen-bond geometrical parameters, infrared (IR) vibrational spectra, Mayer bond order and predicting hydrogen bonding energy (E(HB)), we verify dual hydrogen bonds of HPBB are strengthened in S1 state. Particularly, in nonpolar solvent, the enhanced excited state hydrogen bonds become more obvious. The intriguing charge redistribution and frontier molecular orbitals (MOs) reveal hydrogen bonding acceptance ability of acceptor moieties becomes stronger, which plays a crucial role in capturing hydroxyl proton via photoexcitation. To check and explore ESIPT mechanism, we present the solvent polarity dependent asynchronous excited state intramolecular double proton transfer (ESIDPT) mechanism. That is, nonpolar solvent promotes excited state intramolecular single proton transfer (ESISPT) process for HPBB, while polar solvent contributes to ESIDPT behavior with the primary single proton-transfer product in S1 state. This work not only makes a rational attribution to experimental phenomena, but also clarifies detailed excited state behaviors for HPBB and presents regulating ESIPT mechanism via solvent polarity.