Solid state tautomerism in 2-((phenylimino)methyl)naphthalene-1-ol

Nedeltcheva, Daniela; Kamounah, Fadhil S.; Mirolo, Laurent; Fromm, Katharina M.; Antonov, L.

doi:10.1016/j.dyepig.2009.04.002

Cited by 15 publications

(6 citation statements)

References 46 publications

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“…Currently, structural data for the enol and keto tautomers of 1 are available in the literature [18] along with data for the fixed enol tautomer (OMe compound) of 6 [69]. In the case of compounds 2 – 5 even if crystallographic data are available the structures contain contribution of both tautomers [70,71], which makes the structural information unsuitable for benchmarking.…”

Section: Resultsmentioning

confidence: 99%

Tautomerism in Azo and Azomethyne Dyes: When and If Theory Meets Experiment

Antonov

2019

Molecules

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The performance of 26 hybrid density functionals was tested against a tautomeric dataset (TautData), containing experimental information for the keto-enol tautomeric equilibrium in 16 tautomeric azodyes and Schiff bases in cyclohexane, carbon tetrachloride and acetonitrile. The results have shown that MN12-SX, BHandH and M06-2X can be used to describe the tautomeric state of the core structures in the frame of ~0.5 kcal/mol error and correctly predict the tautomeric state in respect of dominating tautomeric form. Among them MN12-SX is the best performer, although it fails to describe the nonplanarity of some of the enol tautomers. The same experimental dataset was used to develop and test a special DFT functional (TautLYP) aimed at describing the tautomeric state in azo- and azomethyne compounds in solution when nonspecific solvents are used.

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Section: Resultsmentioning

confidence: 99%

Tautomerism in Azo and Azomethyne Dyes: When and If Theory Meets Experiment

Antonov

2019

Molecules

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“…This is consistent with recent work on similar compounds. 27 Table 2 reports the relative Gibbs free energies (∆G) and the activation barriers (∆G q ) calculated for a temperature of 298.15 K for the E / K equilibrium, as well as the values of the imaginary frequencies associated with the transition states. Both in the gas phase and in solution, the small energy differences and activation barriers indicate the coexistence of the E and K forms at room temperature.…”

Section: Resultsmentioning

confidence: 99%

“…The main geometrical features (distances and dihedral angles) of the two tautomeric forms and transition state, as optimized in the gas phase and in solvent at the B3LYP/6-311G(d) level, are listed in Table S1 (Supporting Information). Theoretical values are compared to X-ray data of the N -(2-hydroxynaphthylidene)aniline compound, in which the NMe 2 group has been replaced by an H atom . The last line of Table S1 reports the bond length alternation (BLA), defined as ( d 14−4 + d N−17 − 2 d N−14 )/2, as an indicator for the strength of the electron delocalization along the compounds.…”

Section: Resultsmentioning

confidence: 99%

Solvent Effects on the Second-Order Nonlinear Optical Responses in the Keto−Enol Equilibrium of a 2-Hydroxy-1-naphthaldehyde Derivative

et al. 2010

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Hyper-Rayleigh scattering experiments and ab initio calculations are combined to investigate the solvent effects on the second-order nonlinear optical responses of a 2-hydroxy-1-naphthaldehyde derivative that commutes between an enol and a keto form. Different binary mixtures of cyclohexane and ethanol are used to displace the tautomeric equilibrium. We show that increasing the solvent polarity increases the population of the keto form, shifts the lowest energy band of the absorption spectra to lower energy, and gives rise to a large enhancement of the first hyperpolarizability. Using theoretical calculations, the global solvent effect on the latter is shown to originate from both the displacement of the tautomeric equilibrium and the modification of the second-order nonlinear optical response of the individual tautomeric forms.

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“…Several theoretical and experimental studies on the azo-hydrazone tautomeric equilibrium can be found in the literature. − However, due to the dependence of the tautomeric forms on the surrounding chemical environment, their structural and spectroscopic characterizations are not trivial. Indeed, many issues concerning the relative stability of these species and related with the intramolecular proton transfer that interconvert them into each other remain unclear.…”

Section: Introductionmentioning

confidence: 99%

Tautomers and UV-Induced Photoisomerization of a Strongly Intramolecularly H-Bonded Aromatic Azo-Dye: 1-(Cyclopropyl)diazo-2-naphthol

et al. 2013

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Aromatic azo compounds have a wide range of industrial applications as dyes in optical and color-changing materials and can also be exploited in the design of new photodynamic molecular systems. The azo derivative 1-(cyclopropyl)diazo-2-naphthol was isolated in low-temperature cryogenic matrices, and its molecular structure, tautomeric equilibrium, and photochemical transformations were characterized by infrared spectroscopy and theoretical calculations. Only azo-enol forms having the OH group involved in a strong intramolecular hydrogen bond, forming a six-membered ring with the azo group, were found experimentally. Irradiation with a narrowband source in the near-UV range generates different rotameric and tautomeric azo-enol and keto-hydrazone forms that can be interconverted at different irradiation wavelengths.

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Solid state tautomerism in 2-((phenylimino)methyl)naphthalene-1-ol

Cited by 15 publications

References 46 publications

Tautomerism in Azo and Azomethyne Dyes: When and If Theory Meets Experiment

Tautomerism in Azo and Azomethyne Dyes: When and If Theory Meets Experiment

Solvent Effects on the Second-Order Nonlinear Optical Responses in the Keto−Enol Equilibrium of a 2-Hydroxy-1-naphthaldehyde Derivative

Tautomers and UV-Induced Photoisomerization of a Strongly Intramolecularly H-Bonded Aromatic Azo-Dye: 1-(Cyclopropyl)diazo-2-naphthol

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