Predicting Keto–Enol Equilibrium from Combining UV/Visible Absorption Spectroscopy with Quantum Chemical Calculations of Vibronic Structures for Many Excited States: A Case Study on Salicylideneanilines

Freddy Zutterman, Orian Louant, Gabriel Mercier, Tom Leyssens, Benoît Champagne

Résultats de recherche: Contribution à un journal/une revueArticle

Résumé

Salicylideneanilines are characterized by a tautomer equilibrium, between an enol and a keto form of different colors, at the origin of their remarkable thermochromic, solvatochromic, and photochromic properties. The enol form is usually the most stable but appropriate choice of substituents and conditions (solvent, crystal, host compound) can displace the equilibrium toward the keto form so that there is a need for fast prediction of the keto:enol abundance ratio. Here we demonstrate the reliability of a combined theoretical−experimental method, based on comparing simulated and measured UV/visible absorption spectra, to determine this keto/enol ratio. The calculations of the excitation energies, oscillator strengths, and vibronic structures of both enol and keto forms are performed for all excited states absorbing in the relevant (visible and near-UV) wavelength range at the time-dependent density functional theory level by accounting for solvent effects using the polarizable continuum model. This approach is illustrated for two salicylideneaniline derivatives, which are present, in solution, under the form of keto−enol mixtures. The results are compared to those of chemometric analysis as well as ab initio predictions of the reaction free enthalpies.
langue originaleAnglais
Pages (de - à)5370-5374
Nombre de pages5
journalJournal of physical chemistry A
Volume122
Numéro de publication24
Les DOIs
étatPublié - 21 juin 2018

Empreinte digitale

Absorption spectroscopy
Excited states
absorption spectroscopy
Excitation energy
tautomers
predictions
visible spectrum
oscillator strengths
excitation
Density functional theory
Absorption spectra
Enthalpy
enthalpy
density functional theory
continuums
Color
Derivatives
absorption spectra
color
Wavelength

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title = "Predicting Keto–Enol Equilibrium from Combining UV/Visible Absorption Spectroscopy with Quantum Chemical Calculations of Vibronic Structures for Many Excited States: A Case Study on Salicylideneanilines",
abstract = "Salicylideneanilines are characterized by a tautomer equilibrium, between an enol and a keto form of different colors, at the origin of their remarkable thermochromic, solvatochromic, and photochromic properties. The enol form is usually the most stable but appropriate choice of substituents and conditions (solvent, crystal, host compound) can displace the equilibrium toward the keto form so that there is a need for fast prediction of the keto:enol abundance ratio. Here we demonstrate the reliability of a combined theoretical−experimental method, based on comparing simulated and measured UV/visible absorption spectra, to determine this keto/enol ratio. The calculations of the excitation energies, oscillator strengths, and vibronic structures of both enol and keto forms are performed for all excited states absorbing in the relevant (visible and near-UV) wavelength range at the time-dependent density functional theory level by accounting for solvent effects using the polarizable continuum model. This approach is illustrated for two salicylideneaniline derivatives, which are present, in solution, under the form of keto−enol mixtures. The results are compared to those of chemometric analysis as well as ab initio predictions of the reaction free enthalpies.",
author = "Freddy Zutterman and Orian Louant and Gabriel Mercier and Tom Leyssens and Beno{\^i}t Champagne",
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AU - Zutterman, Freddy

AU - Louant, Orian

AU - Mercier, Gabriel

AU - Leyssens, Tom

AU - Champagne, Benoît

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N2 - Salicylideneanilines are characterized by a tautomer equilibrium, between an enol and a keto form of different colors, at the origin of their remarkable thermochromic, solvatochromic, and photochromic properties. The enol form is usually the most stable but appropriate choice of substituents and conditions (solvent, crystal, host compound) can displace the equilibrium toward the keto form so that there is a need for fast prediction of the keto:enol abundance ratio. Here we demonstrate the reliability of a combined theoretical−experimental method, based on comparing simulated and measured UV/visible absorption spectra, to determine this keto/enol ratio. The calculations of the excitation energies, oscillator strengths, and vibronic structures of both enol and keto forms are performed for all excited states absorbing in the relevant (visible and near-UV) wavelength range at the time-dependent density functional theory level by accounting for solvent effects using the polarizable continuum model. This approach is illustrated for two salicylideneaniline derivatives, which are present, in solution, under the form of keto−enol mixtures. The results are compared to those of chemometric analysis as well as ab initio predictions of the reaction free enthalpies.

AB - Salicylideneanilines are characterized by a tautomer equilibrium, between an enol and a keto form of different colors, at the origin of their remarkable thermochromic, solvatochromic, and photochromic properties. The enol form is usually the most stable but appropriate choice of substituents and conditions (solvent, crystal, host compound) can displace the equilibrium toward the keto form so that there is a need for fast prediction of the keto:enol abundance ratio. Here we demonstrate the reliability of a combined theoretical−experimental method, based on comparing simulated and measured UV/visible absorption spectra, to determine this keto/enol ratio. The calculations of the excitation energies, oscillator strengths, and vibronic structures of both enol and keto forms are performed for all excited states absorbing in the relevant (visible and near-UV) wavelength range at the time-dependent density functional theory level by accounting for solvent effects using the polarizable continuum model. This approach is illustrated for two salicylideneaniline derivatives, which are present, in solution, under the form of keto−enol mixtures. The results are compared to those of chemometric analysis as well as ab initio predictions of the reaction free enthalpies.

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