Theoretical Investigation of the Excited-State Dynamics Mechanism of the Asymmetric Two-Way Proton Transfer Molecule BTHMB.

An asymmetric two-way proton transfer molecule 3-(benzo[]-thiazol-2-yl)-2-hydroxy-5-methoxybenzaldehyde (BTHMB) with the function of white-light emission was synthesized in a recent experiment (Bhattacharyya, A.; Mandal, S. K.; Guchhait, N. 2019, 123, 10246). The particularity of this molecule is that there are two possible forms, one of which contained a six-membered H-bonded network toward a N atom (BTHMB-NH) present in the molecule as a proton acceptor and the other was toward an O atom (BTHMB-OH). Unfortunately, the experimental work lacked the theoretical explanation about the determination of the BTHMB-NH form and its excited-state intramolecular proton transfer (ESIPT) process under different solvents. Therefore, this study has explored these two points by means of the time-dependent density functional theory (TDDFT) method. The calculated relative energy and potential energy profile (PEP) of the transformation between BTHMB-NH and BTHMB-OH forms illustrated that BTHMB-NH was more stable, and the transfer from BTHMB-NH to BTHMB-OH was almost impossible at both S and S states under all solvents due to high potential energy barriers (PEBs) (11.67-21.59 kcal/mol). These calculated results provided the theoretical explanation and verification for the conclusion that the BTHMB molecule exists in the BTHMB-NH form in the experiment. Subsequently, the constructed PEPs of the ESIPT process for BTHMB-NH have proved that it was prone to the ESIPT process due to low PEBs (0.11-0.28 kcal/mol) at the S state. In particular, as the solvent polarity increased, the intensity of the intramolecular hydrogen bond (IHB) (O-H···N) increased and the ESIPT process was more likely to occur. In addition, the twisted intramolecular charge-transfer (TICT) process was studied to explore the possible fluorescence quenching pathway of BTHMB-NH. Based on the PEPs of BTHMB-NH-T as a function of the N-C-C-C dihedral angle at the S and S states, it is seen that the S state TICT process was inhibited due to the large PEBs (16.45-23.93 kcal/mol). Although the S state PEBs have been greatly reduced, they were still maintained at about 3.60 kcal/mol (3.60-3.84 kcal/mol), and hence, this process was still relatively difficult to occur. Due to the fact that BTHMB can be regarded as a standard in future designs involving red light and solvent-specific white-light emitters, a certain amount of investigative work on the ESIPT process was done in detail, and it paved the way for future research on the directionality of ESIPT in double ESIPT probes.