The theoretical study of excited-state intramolecular proton transfer of 2,5-bis(benzoxazol-2-yl)thiophene-3,4-diol.

The symmetrical structures 2,5-bis(benzoxazol-2-yl)thiophene-3,4-diol (BBTD) can take shape two intramolecular hydrogen bonds in chloroform. In order to research the molecular dynamic behavior of BBTD upon photo-induced process, we utilize density functional theory (DFT) and time-dependent density functional theory (TDDFT) to complete theoretical calculation. Through the comparison of bond length, bond angle, IR spectra, and frontier molecular orbitals between ground state (S0 ) and first excited state (S1 ), it clearly indicates that photoexcitation have slightly influence for intensity of hydrogen bond. For the sake of understanding the mechanism of excited state intramolecular proton transfer (ESIPT) of BBTD in chloroform, potential energy surfaces have been scanned along with the orientation of O1 -H2 and O4 -H5 in S0 and S1 state, respectively. A intrigued hydrogen bond dynamic phenomenon has been found that ESIPT of BBTD is not a synergetic double proton transfer process, but a stepwise single proton transfer process BBTD→BBTD-S→BBTD-D. Moreover, the proton transfer process of BBTD-S→BBTD-D is easier to occur than that of BBTD→BBTD-S in S1 state.