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New perspective on the fluorescence and sensing mechanism of TNP chemosensor 2-(4,5-bis(4-chlorophenyl)-1H-imidazol-2-yl)-4-chlorolphenol
- Source :
- Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy. 213:309-317
- Publication Year :
- 2019
- Publisher :
- Elsevier BV, 2019.
-
Abstract
- For TNP chemosensor 2-(4,5-Bis(4-Chlorophenyl)-1H-Imidazol-2-yl)-4-Chlorolphenol (HPICI), previous thought with no theoretical basis was that excited-state intramolecular proton transfer (ESIPT) process and the ground-state HPICI-TNP complex are mainly responsible for its fluorescence emission and the detection of TNP. However, this interpretation has been proved to be wrong by the present theoretical DFT/TDDFT explorations. Actually, the strong fluorescence of HPICI is mainly induced by the local excitation of the enol form HPICI(E) without ESIPT, and the fluorescence quenching by TNP is due to the photo-induced electron transfer (PET) process together with the cooperative effect of hydrogen-bonding interaction and π-π stacking interaction coexisting in the HPICI-TNP complex. The strengthened excited-state hydrogen bond promotes the PET process, thus facilitates the fluorescence quenching. This mechanism is proposed on the basis of the theoretical analyses on molecule geometry, binding energy, Gibbs free energy, electronic transitions, and frontier molecular orbitals (FMOs).
- Subjects :
- Hydrogen bond
Binding energy
02 engineering and technology
Time-dependent density functional theory
010402 general chemistry
021001 nanoscience & nanotechnology
Photochemistry
01 natural sciences
Enol
Fluorescence
Atomic and Molecular Physics, and Optics
0104 chemical sciences
Analytical Chemistry
chemistry.chemical_compound
Electron transfer
chemistry
Intramolecular force
Molecular orbital
0210 nano-technology
Instrumentation
Spectroscopy
Subjects
Details
- ISSN :
- 13861425
- Volume :
- 213
- Database :
- OpenAIRE
- Journal :
- Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy
- Accession number :
- edsair.doi.dedup.....8f835318c3556ab8e2f19430b52a75a0