4’-Methoxy-3-hydroxyflavone excited state intramolecular proton transfer reaction in alcoholic solutions: Intermolecular versus intramolecular hydrogen bonding effect

[Display omitted] •Excited state proton transfer (ESIPT) reaction rates were determined experimentally for 4-methoxyphenyl-3-hydroxychromone in six alcohols.•Impact of several types of H-bonded complexes was modeled with quantum-chemical and molecular dynamics simulations.•The most important H-compl...

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Bibliographic Details
Published in:Journal of photochemistry and photobiology. A, Chemistry. Chemistry., 2019-10, Vol.383, p.111964, Article 111964
Main Authors: Doroshenko, Andrey O., Kyrychenko, Alexander V., Valyashko, Oksana M., Kotlyar, Vladimir M., Svechkarev, Denis A.
Format: Article
Language:English
Subjects:
4’-Methoxy-3-hydroxyflavone
Acidity
Alcohol
Carbonyl compounds
Carbonyl groups
Carbonyls
Emission spectra
ESIPT
Excitation
Fluorescence kinetics
Fluorescent dyes
Fluorescent indicators
Hydrogen
Hydrogen bonding
Hydrogen bonds
Molecular dynamics
Organic chemistry
Protons
Quantum chemistry
Quantum-chemical and molecular dynamics simulations
Steric hindrance
Time-resolved fluorescence spectra
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Summary:[Display omitted] •Excited state proton transfer (ESIPT) reaction rates were determined experimentally for 4-methoxyphenyl-3-hydroxychromone in six alcohols.•Impact of several types of H-bonded complexes was modeled with quantum-chemical and molecular dynamics simulations.•The most important H-complex retarding ESIPT is with the unshared electron pair of C=O group not involved in formation of the intramolecular H-bond. Influence of protic surrounding on the excited state intramolecular proton transfer (ESIPT) reaction was studied both experimentally and theoretically on the example of 4’-methoxy-3-hydroxyflavone (4M3 H F), a model fluorescent dye possessing multi-banded emission spectra. Experimentally determined 4M3 H F ESIPT rates in alcohol solutions correlate with the general acidity of a protic solvent and steric hindrance to intermolecular H-bonding caused by the space dimensions and branching of an alcohol molecule hydrocarbon residue. The role of intermolecular hydrogen bonds was elucidated by quantum-chemical and molecular dynamics modeling: several types of H-bonded complexes were examined systematically aiming to outline their accelerating or retarding effects on ESIPT reaction rate. An intermolecular hydrogen bond to the lone electron pair of the carbonyl group oxygen atom, which is not involved in the intramolecular H-bonding, was shown to be the most important factor for regulation of ESIPT rate in protic or aprotic humid surrounding.
ISSN:1010-6030
1873-2666
DOI:10.1016/j.jphotochem.2019.111964