Abstract
| Original language | English |
|---|---|
| Pages (from-to) | 5370-5374 |
| Number of pages | 5 |
| Journal | Journal of physical chemistry A |
| Volume | 122 |
| Issue number | 24 |
| DOIs | |
| Publication status | Published - 21 Jun 2018 |
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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. / Zutterman, Freddy; Louant, Orian; Mercier, Gabriel; Leyssens, Tom; Champagne, Benoît.
In: Journal of physical chemistry A, Vol. 122, No. 24, 21.06.2018, p. 5370-5374.Research output: Contribution to journal › Article
TY - JOUR
T1 - Predicting Keto–Enol Equilibrium from Combining UV/Visible Absorption Spectroscopy with Quantum Chemical Calculations of Vibronic Structures for Many Excited States
T2 - A Case Study on Salicylideneanilines
AU - Zutterman, Freddy
AU - Louant, Orian
AU - Mercier, Gabriel
AU - Leyssens, Tom
AU - Champagne, Benoît
PY - 2018/6/21
Y1 - 2018/6/21
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.
UR - http://www.scopus.com/inward/record.url?scp=85047392974&partnerID=8YFLogxK
U2 - 10.1021/acs.jpca.8b03389
DO - 10.1021/acs.jpca.8b03389
M3 - Article
VL - 122
SP - 5370
EP - 5374
JO - The journal of physical chemistry. A
JF - The journal of physical chemistry. A
SN - 1089-5639
IS - 24
ER -