Determinant of ESIPT Mechanism by the Structure Designed for Symmetrical and Unsymmetrical Molecules

In this work, we present that different structures lead to different excited state properties based on the investigations of the systems with symmetrical and unsymmetrical properties. Our work shows that the symmetrical and unsymmetrical compounds with a modified structure play key roles in regulating the excited state intramolecular proton transfer (PT) (ESIPT) process. For N,N'-bis(salicylidene)-p-phenyle-nediamine (BSP) and N,N'-disalicylidene-1,6-pyrenediamine (BSD), when they are excited, the torsion angels result in the rematch of the spectra. By analyzing the potential energy surfaces (PESs) of the torsion angle and PT process, we conclude that the size of the π stack largely affects the molecular properties in the excited states. For 2'-hydroxychalcone derivatives, which have important applications in biotransformation reactions, investigating the molecules of M1 and M2 could promote innovation in bioengineering. The results of molecular electrostatic potential (MEP) and the real space intramolecular interactions show the state and position of the hydrogen bond (HB) in both S₀ and S₁ states. The corresponding PT PESs show that the ESIPT reaction is much easier for the M1 system due to the lack of the side chain hydroxyl compared with the M2 system. This work is not only consistent with experimental results and explains its mechanism but also presents that symmetric and nonsymmetric structures modify their own potential regulation and controlling effects for ESIPT behaviors.