Theoretical investigation of the excited-state intramolecular double proton transfer process of 2,2′-(benzo[1,2-d:4,5-d′]bis(thiazole)-2,6-diyl)diphenol

Abstract

In this work, the excited state intramolecular double proton transfer (ESIDPT) mechanism of 2,2′-(benzo[1,2-d:4,5-d′]bis(thiazole)-2,6-diyl)diphenol (BTAP) is proposed using density functional theory (DFT) and time-dependent DFT (TDDFT). The changes in bond lengths, bond angles and IR vibrational spectra associated with two intramolecular hydrogen bonds of BTAP upon photoexcitation indicate that the hydrogen bonds are strengthened in the excited state, facilitating the ESIDPT process. Investigation of the constructed S₁-state potential energy surface proposes that BTAP prefers a stepwise ESIDPT mechanism. Electronic spectra and frontier molecular orbitals (FMOs) are also presented to illustrate the luminescent properties of BTAP.