Citation: Hu CAO, Gai-Mei LIU, Jia CAI, Yan WANG. Excited-state Intramolecular Proton Transfer Mechanisms of Thiazole-based Chemosensor: a TD-DFT Study[J]. Chinese Journal of Structural Chemistry, ;2020, 39(11): 1933-1940. doi: 10.14102/j.cnki.0254–5861.2011–2840 shu

Excited-state Intramolecular Proton Transfer Mechanisms of Thiazole-based Chemosensor: a TD-DFT Study

Hu CAO ^a ,
Gai-Mei LIU ^a ,
Jia CAI ^a ,
Yan WANG ^{a, b,,}

a.
School of Chemistry and Environmental Engineering, Hubei Minzu University, Enshi 445000, China
b.
Key Laboratory of Magnetic Resonance in Biological Systems, National Center for Magnetic Resonance in Wuhan, State Key Laboratory of Magnetic Resonance and Atomic and Molecular Physics, Wuhan Institute of Physics and Mathematics, Chinese Academy of Sciences, Wuhan 430071, China

Corresponding author: Yan WANG, hbwangy@sohu.com
Received Date: 7 April 2020
Accepted Date: 5 August 2020

Fund Project: the National Natural Science Foundation of China 21963008he Natural Science Foundation of Hubei Province 2016CFB400the College Students' Innovative Entrepreneurial Training Plan Program of Hubei Minzu University 2016CX066the College Students' Innovative Entrepreneurial Training Plan Program of Hubei Minzu University X201910517140

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The excited-state intramolecular proton transfer (ESIPT) mechanisms of 2-(2-hydroxyphenyl)-4-phenylthiazole (HPT) and 2-(5-bromo-2-hydroxyphenyl)-4-phenylthiazole (BrHPT) have been systematically investigated by density functional theory (DFT) and time-dependent density functional theory (TDDFT) methods, approaching along with the polarizable continuum model (PCM). The calculated primary bond lengths and bond angles demonstrate that HPT and BrHPT can form intramolecular hydrogen bonds in the ground state (S₀), which can be significantly strengthened in the first excited state (S₁). Our calculated results well reproduce the experimental absorption and emission spectra. Upon addition of F^-, the proton can move close to F^- and the hydroxy moieties are deprotonated, which cause a red-shift in absorption and a new emission peak in ﬂuorescence emission with the disappearance of the dual fluorescence emission. The calculated Mulliken's charge distribution and frontier molecular orbitals further demonstrate that the ESIPT processes are more likely to occur in the S₁ state. The constructed potential energy curves of the S₀ and S₁ states confirm that the proton transfer processes are hard to occur in the S₀ state due to the high energy barriers. Moreover, much lower energy barriers are found in the S₁ state, which proves that the ESIPT processes are more likely to take place in the S₁ state. In addition, compound with electron withdrawing (–Br) group might result in much stronger intramolecular hydrogen bond and owns lower energy barrier, which can facilitate the ESIPT processes.
- density functional theory,
- ESIPT,
- 2-(2-hydroxy-phenyl)-4-phenylthiazole,
- potential energy curves
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