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Unexpected solvent effects on the UV/Vis absorption spectra of o-cresol in toluene and benzene: in contrast with non-aromatic solvents

Cresol is a prototype molecule in understanding intermolecular interactions in material and biological systems, because it offers different binding sites with various solvents and protonation states under different pH values. It is found that the UV/Vis absorption spectra of o-cresol in aromatic sol...

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Autores principales: Zheng, Dong, Yuan, Xiang-Ai, Ma, Haibo, Li, Xiaoxiong, Wang, Xizhang, Liu, Ziteng, Ma, Jing
Formato: Online Artículo Texto
Lenguaje:English
Publicado: The Royal Society Publishing 2018
Materias:
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC5882718/
https://www.ncbi.nlm.nih.gov/pubmed/29657794
http://dx.doi.org/10.1098/rsos.171928
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author Zheng, Dong
Yuan, Xiang-Ai
Ma, Haibo
Li, Xiaoxiong
Wang, Xizhang
Liu, Ziteng
Ma, Jing
author_facet Zheng, Dong
Yuan, Xiang-Ai
Ma, Haibo
Li, Xiaoxiong
Wang, Xizhang
Liu, Ziteng
Ma, Jing
author_sort Zheng, Dong
collection PubMed
description Cresol is a prototype molecule in understanding intermolecular interactions in material and biological systems, because it offers different binding sites with various solvents and protonation states under different pH values. It is found that the UV/Vis absorption spectra of o-cresol in aromatic solvents (benzene, toluene) are characterized by a sharp peak, unlike the broad double-peaks in 11 non-aromatic solvents. Both molecular dynamics simulations and electronic structure calculations revealed the formation of intermolecular π-complexation between o-cresol and aromatic solvents. The thermal movements of solvent and solute molecules render the conformations of o-cresol changing between trans and cis isomers. The π-interaction makes the cis configuration a dominant isomer, hence leading to the single keen-edged UV/Vis absorption peak at approximately 283 nm. The free conformation changes between trans and cis in aqueous solution rationalize the broader absorption peaks in the range of 260–280 nm. The pH dependence of the UV/Vis absorption spectra in aqueous solutions is also rationalized by different protonation states of o-cresol. The explicit solvent model with long-ranged interactions is vital to describe the effects of π-complexation and electrostatic interaction on the UV/Vis absorption spectra of o-cresol in toluene and alkaline aqueous (pH > 10.3) solutions, respectively.
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spelling pubmed-58827182018-04-13 Unexpected solvent effects on the UV/Vis absorption spectra of o-cresol in toluene and benzene: in contrast with non-aromatic solvents Zheng, Dong Yuan, Xiang-Ai Ma, Haibo Li, Xiaoxiong Wang, Xizhang Liu, Ziteng Ma, Jing R Soc Open Sci Chemistry Cresol is a prototype molecule in understanding intermolecular interactions in material and biological systems, because it offers different binding sites with various solvents and protonation states under different pH values. It is found that the UV/Vis absorption spectra of o-cresol in aromatic solvents (benzene, toluene) are characterized by a sharp peak, unlike the broad double-peaks in 11 non-aromatic solvents. Both molecular dynamics simulations and electronic structure calculations revealed the formation of intermolecular π-complexation between o-cresol and aromatic solvents. The thermal movements of solvent and solute molecules render the conformations of o-cresol changing between trans and cis isomers. The π-interaction makes the cis configuration a dominant isomer, hence leading to the single keen-edged UV/Vis absorption peak at approximately 283 nm. The free conformation changes between trans and cis in aqueous solution rationalize the broader absorption peaks in the range of 260–280 nm. The pH dependence of the UV/Vis absorption spectra in aqueous solutions is also rationalized by different protonation states of o-cresol. The explicit solvent model with long-ranged interactions is vital to describe the effects of π-complexation and electrostatic interaction on the UV/Vis absorption spectra of o-cresol in toluene and alkaline aqueous (pH > 10.3) solutions, respectively. The Royal Society Publishing 2018-03-14 /pmc/articles/PMC5882718/ /pubmed/29657794 http://dx.doi.org/10.1098/rsos.171928 Text en © 2018 The Authors. http://creativecommons.org/licenses/by/4.0/ Published by the Royal Society under the terms of the Creative Commons Attribution License http://creativecommons.org/licenses/by/4.0/, which permits unrestricted use, provided the original author and source are credited.
spellingShingle Chemistry
Zheng, Dong
Yuan, Xiang-Ai
Ma, Haibo
Li, Xiaoxiong
Wang, Xizhang
Liu, Ziteng
Ma, Jing
Unexpected solvent effects on the UV/Vis absorption spectra of o-cresol in toluene and benzene: in contrast with non-aromatic solvents
title Unexpected solvent effects on the UV/Vis absorption spectra of o-cresol in toluene and benzene: in contrast with non-aromatic solvents
title_full Unexpected solvent effects on the UV/Vis absorption spectra of o-cresol in toluene and benzene: in contrast with non-aromatic solvents
title_fullStr Unexpected solvent effects on the UV/Vis absorption spectra of o-cresol in toluene and benzene: in contrast with non-aromatic solvents
title_full_unstemmed Unexpected solvent effects on the UV/Vis absorption spectra of o-cresol in toluene and benzene: in contrast with non-aromatic solvents
title_short Unexpected solvent effects on the UV/Vis absorption spectra of o-cresol in toluene and benzene: in contrast with non-aromatic solvents
title_sort unexpected solvent effects on the uv/vis absorption spectra of o-cresol in toluene and benzene: in contrast with non-aromatic solvents
topic Chemistry
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC5882718/
https://www.ncbi.nlm.nih.gov/pubmed/29657794
http://dx.doi.org/10.1098/rsos.171928
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