TY - JOUR
T1 - 4’-Methoxy-3-hydroxyflavone excited state intramolecular proton transfer reaction in alcoholic solutions
T2 - Intermolecular versus intramolecular hydrogen bonding effect
AU - Doroshenko, Andrey O.
AU - Kyrychenko, Alexander V.
AU - Valyashko, Oksana M.
AU - Kotlyar, Vladimir M.
AU - Svechkarev, Denis A.
N1 - Funding Information:
This work was supported in part by the Research Grants of the Ministry of Education and Science of Ukraine ( 116U000835 and 0119U002536 ).
Funding Information:
This work was supported in part by the Research Grants of the Ministry of Education and Science of Ukraine (116U000835 and 0119U002536). This work was performed using computational facilities of a joint computer cluster of SSI “Institute for Single Crystals” and Institute for Scintillation Materials of National Academy of Science of Ukraine incorporated into Ukrainian National Grid.
Publisher Copyright:
© 2019 Elsevier B.V.
PY - 2019/10/1
Y1 - 2019/10/1
N2 - 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.
AB - 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.
KW - 4’-Methoxy-3-hydroxyflavone
KW - ESIPT
KW - Fluorescence kinetics
KW - Hydrogen bonding
KW - Quantum-chemical and molecular dynamics simulations
KW - Time-resolved fluorescence spectra
UR - http://www.scopus.com/inward/record.url?scp=85070234115&partnerID=8YFLogxK
UR - http://www.scopus.com/inward/citedby.url?scp=85070234115&partnerID=8YFLogxK
U2 - 10.1016/j.jphotochem.2019.111964
DO - 10.1016/j.jphotochem.2019.111964
M3 - Article
AN - SCOPUS:85070234115
SN - 1010-6030
VL - 383
JO - Journal of Photochemistry and Photobiology A: Chemistry
JF - Journal of Photochemistry and Photobiology A: Chemistry
M1 - 111964
ER -