Solvatochromism and electrophilicity

Rezende, Marcos Caroli; Domínguez, Moisés; Aracena, Andrés; Millán, Daniela

doi:10.1016/j.cplett.2011.08.070

Cited by 32 publications

(20 citation statements)

References 26 publications

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“…We have been concerned for some time with the relationship between the molecular structure of these solvatochromic compounds and their behaviour.…”

Section: Introductionmentioning

confidence: 99%

“…By employing DFT‐based parameters, such as hardness, electrophilicity or the computation of fragment Fukui functions for nucleophilic attack, we have rationalized the solvatochromic behaviour of pyridinium phenolate betaine dyes and arrived at a general model that regards all kinds of solvatochromism as particular cases of a general inverted behaviour . According to this model, all solvatochromic plots of transition energies vs. solvent polarity show a minimum, which can occur within the experimentally available range of solvent polarities, characterizing a “true” reversal; or can fall beyond this range, leading to a “virtual” or “imaginary” reversal.…”

Section: Introductionmentioning

confidence: 99%

“…However, the existence of this projected reversal point is a necessary consequence of the fact that compound 1 is a negative solvatochromic dye. This implies that the difference between the electrophilicities of the pyridinium and the phenolate moieties tends to decrease with the decreased polarity of the medium . This tendency can be projected to a point where this difference is nil, corresponding to an “imaginary” polarity value.…”

Section: Introductionmentioning

confidence: 99%

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A generalized reversal model for the solvatochromism of merocyanines

Rezende

2016

J. Phys. Org. Chem.

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The solvatochromic behaviour of merocyanines can be interpreted and predicted by consideration of their molecular structure with the aid of a model that regards all kinds of solvatochromism as particular cases of a generalized reverse behaviour. This generalized reversal model is shown to be consistent with the cyanine-limit model, another independent approach that relates the merocyanine structure with its solvatochromic behaviour. Both models are validated by experimental data from the literature of 21 merocyanines of variable molecular structure.

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“…We have been concerned for some time with the relationship between the molecular structure of these solvatochromic compounds and their behaviour.…”

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

See 1 more Smart Citation

A generalized reversal model for the solvatochromism of merocyanines

Rezende

2016

J. Phys. Org. Chem.

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“…In order to better interpret these results, we performed calculations of global electrophilicity, hardness, softness and chemical potential, as well as local electrophilicity ( ω κ ) and softness ( S k ) at the site involved in the Michael addition reaction of the tested probes (C 16 , H 17 , C 18 and H 19 ; Scheme ). From the global reactivity parameters of a molecule, we may obtain local indexes at an atom k as the product of the global index by the Fukui function for nucleophilic attack ( f k + ) at that particular site …”

Section: Resultsmentioning

confidence: 99%

Nucleophilic reactivity of biothiols toward coumarin‐based derivatives containing a chalcone moiety

García‐Beltrán

González

Pérez

et al. 2012

J of Physical Organic Chem

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The Michael addition reactions of the biothiols cysteine (Cys), glutathione (GSH), homocysteine (Hcy) and cysteinylglycine (Cys‐Gly) with (E)‐3‐(3‐(2‐methoxyphenyl)acryloyl)‐7‐methoxy‐2H‐chromen‐2‐one and (E)‐3‐(3‐(3‐methoxyphenyl)acryloyl)‐7‐methoxy‐2H‐chromen‐2‐one (ChC2 and ChC3, respectively) in aqueous solution (25 °C, ionic strength 0.2 M KCl) were followed fluorimetrically and evaluated kinetically. With a large excess of biothiol, pseudo‐first‐order rate coefficients (kobsd) were found. Plots of kobsd versus [biothiolate] are linear, with a pH‐independent slope (kN). With the kinetic results obtained, the following conclusions can be drawn: (i) the reactivity increases in the sequence Cys‐Gly < Hcy < GSH < Cys; (ii) similar reactivity toward biothiols was found for ChC2 and ChC3, and both probes are more reactive than (E)‐3‐cinnamoyl‐7‐methoxy‐2H‐chromen‐2‐one (ChC1); (iii) ChC2 and ChC3 display a highly selective fluorescence enhancement with biothiols, allowing these probes to be used for fluorimetric biothiol determination in SH‐SY5Y cells. Copyright © 2012 John Wiley & Sons, Ltd.

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“…“Electrophilicity index (ω)” is used to define photostability for dyes 4a–4d and is defined by electron absorbing capacity of molecule using Equation ,

normalω = \frac{{normalμ}^{2}}{η},

where μ is the “chemical potential” of molecule. The μ and η is related with “ionization potential (IP)” and “electron affinity (EA)” of dyes and is defined by the Equations and

normalμ = - \frac{((), IP + EA)}{2},

normalη = \frac{((), IP - EA)}{2},

where IP and EA are “ionization potential” and “electron affinity,” respectively.…”

Section: Nonlinear Optical (Nlo) Propertiesmentioning

confidence: 99%

Experimental and theoretical investigation of linear and nonlinear optical properties of ethyl‐3‐hydroxy‐2‐napthoate azo dyes by solvatochromic, computational aspects, and Z‐scan technique

Yadav

Taware

Sreenath³

et al. 2020

J of Physical Organic Chem

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To investigate the effect of substituents in azo dyes on their nonlinear optical properties, four azo dyes were synthesized using ethyl‐3‐hydroxy‐2‐naphthoate as a coupler and characterized. The polarizability (α) and hyperpolarizability (β and γ) constants were determined by using solvatochromic and computational method. A group of global hybrid and range seperated hybrid functionals having different Hartree‐Fock exchange percentage were used to evaluate the NLO properties. The functional ωB97 and ωB97XD performed better in the determination of polarizability (α) and hyperpolarizability (β and γ), respectively. The observed results for polarizability and hyperpolarizability parameters were supported by highest occupied molecular orbital‐lowest unoccupied molecular orbital (HOMO‐LUMO) energy gap, Hammett‐coefficient (σ), excited‐state coefficients (σex), and hyper‐hardness (Γ) values. Third‐order NLO properties were analyzed by using Z‐scan technique. The –OCH3 substituted dye 4d shows higher value of molecular susceptibility (χ(3)), polarizability (α), and hyperpolarizability (β and γ) parameters among the studied azo dyes. They are likely to have the potential applications in optoelectronics and photonics.

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Solvatochromism and electrophilicity

Cited by 32 publications

References 26 publications

A generalized reversal model for the solvatochromism of merocyanines

A generalized reversal model for the solvatochromism of merocyanines

Nucleophilic reactivity of biothiols toward coumarin‐based derivatives containing a chalcone moiety

Experimental and theoretical investigation of linear and nonlinear optical properties of ethyl‐3‐hydroxy‐2‐napthoate azo dyes by solvatochromic, computational aspects, and Z‐scan technique

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