首页|Unveiling the effects of atomic electronegativity on the ESIPT mechanism and luminescence property of new coumarin benzothiazole Fluorophore: A TD-DFT exploration

Unveiling the effects of atomic electronegativity on the ESIPT mechanism and luminescence property of new coumarin benzothiazole Fluorophore: A TD-DFT exploration

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  • NSTL
  • Elsevier
The excited-state intramolecular proton transfer (ESIPT) mechanism, photophysical properties of 8-(benzo[D] thiazole-2-yl)-7-hydroxy-2H-benzopyran-2-one (L-HKS) and the effect of O/Se atomic substitution on L-HKS have been studied in detail based on density functional theory (DFT) and timedependent DFT (TD-DFT) methods. The S atom in the thiazole ring of L-HKS has been replaced by O/Se atom (denoted to L-HKO/L-HKSe) to analyze the effects of atomic electronegativity on the intramolecular H-bond, absorption/emission spectrum and ESIPT process. Through the analysis of series of calculated results, it can be found that the intramolecular H-bonds at normal form and tautomer form are enhanced and weakened in the S-1 state, respectively, which is favorable to ESIPT process. The potential energy curves revealed that the ESIPT process is much easier to occur gradually from L-HKO to L-HKS and L-HKSe, as the electron-withdrawing ability of atom (from O to S and Se) is weakened. The atomic substitution also has an effect on the photophysical properties. From L-HKO to L-HKS, the emission peak at tautomer form red-shifts 70 nm. The energy gaps of the three compounds follow the decreased order of L-HKO (4.866 eV) > L-HKS (4.753 eV) > L-HKSe (4.371 eV) with the weakened electron-withdrawing ability of atom (from O to S and Se), which leads to the gradual red-shift of the absorption spectra from L-HKO to L-HKS and L-HKSe. (C) 2022 Elsevier B.V. All rights reserved.

Excited state intramolecular proton transfer (ESIPT)Atomic electronegativityTime-dependent density functional theoryElectronic spectrumPotential energy curveINTRAMOLECULAR PROTON-TRANSFERFLUORESCENT-PROBEPEROXYNITRITE3-HYDROXYFLAVONEPHOTOPHYSICSDERIVATIVESHETEROATOMKINETICSFLUORIDESENSOR

Yin, Feiyang、Fang, Hua

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Nanjing Forestry Univ

2022

10.1016/j.saa.2022.121118

Spectrochimica acta

Spectrochimica acta

ISSN：1386-1425
年,卷(期)：2022.275
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