Critical assessment of solvent effects on absorption and fluorescence of 3HF in acetonitrile in the QM/PCM framework: A synergic computational and experimental study
| Autor: | Daniele Loco, Alberto Mezzetti, Benedetta Mennucci, Stefano Protti |
|---|---|
| Přispěvatelé: | University of Pisa - Università di Pisa, Dept Chem, Photogreen Lab, I-27100 Pavia, Italy, Dipartimento di Chimica e Chimica Industriale, Laboratoire de Réactivité de Surface (LRS), Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS) |
| Jazyk: | angličtina |
| Rok vydání: | 2019 |
| Předmět: |
Solute-solvent interactions
010402 general chemistry 01 natural sciences Polarizable continuum model Fluorescence Analytical Chemistry Inorganic Chemistry chemistry.chemical_compound TDDFT [CHIM]Chemical Sciences Acetonitrile Spectroscopy 010405 organic chemistry 3-hydroxyflavone TDDFT Polarizable continuum model Fluorescence Solute-solvent interactions Organic Chemistry Time-dependent density functional theory 0104 chemical sciences Solvent Solvation shell chemistry 3-hydroxyflavone Physical chemistry Density functional theory Absorption (chemistry) Solvent effects |
| Zdroj: | Journal of Molecular Structure Journal of Molecular Structure, Elsevier, 2019, 1182, pp.283-291. ⟨10.1016/j.molstruc.2018.12.085⟩ |
| ISSN: | 0022-2860 |
| DOI: | 10.1016/j.molstruc.2018.12.085⟩ |
| Popis: | International audience; Absorption and fluorescence properties of 3-hydroxyflavone (3HF) dissolved in the polar aprotic solvent acetonitrile have been investigated by electronic spectroscopies, associated to mixed quantum mechanical (QM)/classical calculations, where the effect of the solvent is included at the classical level by means of the polarizable continuum model (QM/PCM).Whereas absorption and fluorescence (λexc = 342 nm) spectra confirmed previous results, a detailed spectrofluorimetric investigation of the anion, deriving from solvent-induced deprotonation of the OH group of 3-hydroxyflavone, showed for the first time that a single anionic form is present in solution, differently from what observed in another polar aprotic solvent, DMSO.A detailed computational study based on Density Functional Theory (DFT), using five different functionals, has been carried out in order to reproduce and better understand absorption and emission bands on the different existing forms for 3HF in solution: Normal (N), Tautomer (T), Anion (A).The results are discussed in terms of solvent effects on 3HF spectroscopic properties. It was found that simulations are in good agreement with the spectroscopic data for the N and T forms, whereas for the A form larger discrepancies are observed, especially for absorption properties. The effect of specific solute solvent hydrogen bond interactions involving the CO and OH moieties of 3HF was also explored, aiming to better simulate anionic spectroscopic properties. Results suggest that a more complete description of the whole solvation shell is necessary. |
| Databáze: | OpenAIRE |
| Externí odkaz: |
|
Full Text from ScienceDirect