Reconsideration of the Detection and Fluorescence Mechanism of a Pyrene-Based Chemosensor for TNT.
J Phys Chem A
; 122(5): 1400-1405, 2018 Feb 08.
Article
em En
| MEDLINE
| ID: mdl-29337555
ABSTRACT
The rapid detection of chemical explosives is crucial for national security and public safety, and the investigation of sensing mechanisms is important for designing highly efficient chemosensors. This study theoretically investigates the detection and fluorescence mechanism of a newly synthesized pyrene-based chemosensor for the detection of trinitrotoluene (TNT) through density-functional-theory (DFT) and time-dependent density-functional-theory (TDDFT) methods and suggests a different interaction product of the probe and TNT from previously reported ones [ Mosca et al. J. Am. Chem. Soc. 2015 , 137 , 7967 ]. Instead of forming Meisenheimer complexes, the energies of which are beyond those of the reactants, a low-energy product generated by a π-π-stacking interaction is more rational and favorable. The fluorescence-quenching property further confirms that the π-π-stacking product is the predicted one rather than luminescent Meisenheimer complexes. Frontier-molecular-orbital (FMO)-analysis results show that photoinduced electron transfer (PET) is the mechanism underlying the luminescence quenching of the probe upon exposure to TNT.
Texto completo:
1
Bases de dados:
MEDLINE
Tipo de estudo:
Diagnostic_studies
Idioma:
En
Revista:
J Phys Chem A
Assunto da revista:
QUIMICA
Ano de publicação:
2018
Tipo de documento:
Article