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Insights into the excited state dynamical process for 3‐hydroxy‐2‐(5‐(5‐(5‐(3‐hydroxy‐4‐oxo‐4H‐chromen‐2‐yl)thiophen‐2‐yl)thiophen‐2‐yl)thiophen‐2‐yl)‐4H‐chromen‐4‐one
Author(s) -
Wang Yusheng,
Yang Guang,
Jia Min,
Song Xiaoyan,
Zhang Qiaoli,
Yang Dapeng
Publication year - 2019
Publication title -
journal of physical organic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.325
H-Index - 66
eISSN - 1099-1395
pISSN - 0894-3230
DOI - 10.1002/poc.3911
Subject(s) - intramolecular force , chemistry , excited state , time dependent density functional theory , density functional theory , hydrogen bond , molecular orbital , computational chemistry , molecule , proton , photochemistry , atomic physics , stereochemistry , physics , organic chemistry , quantum mechanics
In this present work, we theoretically investigate a novel system 3‐hydroxy‐2‐(5‐(5‐(5‐(3‐hydroxy‐4‐oxo‐4H‐chromen‐2‐yl)thiophen‐2‐yl)thiophen‐2‐yl)thiophen‐2‐yl)‐4H‐chromen‐4‐one (FT) based on density functional theory (DFT) and time‐dependent DFT (TDDFT) methods. Via calculating the reduced density gradient (RDG) versus sign(λ 2 ) ρ, we firstly verify the formation of the dual intramolecular hydrogen bonds (O1─H2···O3 and O4─H5···O6) for FT form in the S 0 state. Then comparing the primary structural parameters and corresponding infrared (IR) vibrational spectra involved in hydrogen bonds between S 0 and S 1 state, we demonstrate that these two intramolecular hydrogen bonds should be strengthened in the S 1 state. Insights into the vertical excitation process, our theoretical results reproduced experimental absorption nature, which confirms that the theoretical level (B3LYP/TZVP) is reasonable and effective in this work. And frontier molecular orbitals (MOs) depict the nature of electronically excited state and support the excited‐state intramolecular proton transfer (ESIPT) reaction. According to the calculated results of potential energy curves along stepwise and synergetic O1─H2 and O4─H5 coordinates, we verify that only the excited‐state single‐proton transfer could occur for FT molecule in the S 1 state, although it possesses two intramolecular hydrogen bonds. We not only investigate the detail excited‐state behaviors for FT system and elaborate the ESIPT mechanism but also explain previous experimental results.