研究目的
To provide a new perspective on the fluorescence and sensing mechanism of TNP chemosensor HPICI using theoretical DFT/TDDFT methods, correcting previous misconceptions about ESIPT and elucidating the roles of local excitation, PET, hydrogen-bonding, and π-π stacking interactions.
研究成果
The fluorescence emission of HPICI is primarily due to local excitation of the enol form without ESIPT, and fluorescence quenching by TNP is caused by a PET process facilitated by strengthened excited-state hydrogen bonding and π-π stacking interactions. This new mechanism corrects previous misconceptions and provides deeper insights into the sensing process, with implications for designing improved fluorescent chemosensors.
研究不足
The study is purely theoretical and relies on computational methods, which may have inherent approximations and errors. Experimental validation is not conducted, and the findings are based on simulations rather than empirical data. The scope is limited to the specific molecule HPICI and its interaction with TNP, potentially not generalizable to other systems.
1：Experimental Design and Method Selection:
The study employs density functional theory (DFT) and time-dependent DFT (TDDFT) methods for quantum-chemical computations to investigate molecular geometries, potential energy surfaces, binding energies, Gibbs free energy, electronic transitions, and frontier molecular orbitals. The IEF-PCM solvation model is used to account for solvent effects.
2：Sample Selection and Data Sources:
The probe molecule HPICI and its interaction with TNP (2,4,6-trinitrophenol) are studied. Data sources include optimized molecular structures and experimental results from prior literature for comparison.
3：List of Experimental Equipment and Materials:
Computational software Gaussian16 is used for all calculations. No physical equipment or materials are mentioned as the study is purely theoretical.
4：Experimental Procedures and Operational Workflow:
Geometry optimizations are performed using B3LYP/6-31+g(d,p) with frequency calculations to verify stationary points. Excited-state calculations use various functionals (B3LYP, CAM-B3LYP, M062X, PBE0) with benchmark studies. Binding energies and Gibbs free energy are calculated with BSSE corrections. 1H NMR spectra are computed using the GIAO method.
5：Data Analysis Methods:
Analysis involves comparing calculated absorption and emission wavelengths with experimental data, examining potential energy curves, binding energies, Gibbs free energy differences, electronic transitions, FMOs, and IR vibrational spectra to infer mechanisms.
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