Theoretical Investigation of Excited-State Intramolecular Double-Proton Transfer Mechanism of Substituent Modified 1, 3-Bis (2-Pyridylimino)-4,7-Dihydroxyisoindole in Dichloromethane Solution

In this paper, density functional theory (DFT) and time-dependent DFT (TDDFT) methods were used to investigate substituent effects and excited-state intramolecular double-proton transfer (ESIDPT) in 1, 3-bis (2-pyridylimino)-4, 7-dihydroxyisoindole (BPI-OH) and its derivatives. The results of a systematic study of the substituent effects of electron-withdrawing groups (F, Cl and Br) on the adjacent sites of the benzene ring were used to regulate the photophysical properties of the molecules and the dynamics of the proton-transfer process. Geometric structure comparisons and infrared (IR) spectroscopic analysis confirmed that strengthening of the intramolecular hydrogen bond in the first excited state (S-1) facilitated proton transfer. Functional analysis of the reduced density gradient confirmed these conclusions. Double-proton transfer in BPI-OH is considered to occur in two steps, i.e., BPI-OH (N) -> BPI-OH (T-1) -> BPI-OH (T-2), in the ground state (S-0) and the S-1 state. The potential-energy curves (PECs) for two-step proton transfer were scanned for both the S-0 and S-1 states to clarify the mechanisms and pathways of proton transfer. The stepwise path in which two protons are consecutively transferred has a low energy barrier and is more rational and favorable. This study shows that the presence or absence of coordinating groups, and the type of coordinating group, affect the hydrogen-bond strength. A coordinating group enhances hydrogen-bond formation, i.e., it promotes excited-state intramolecular proton transfer (ESIPT).