A computer simulation of the solvation of a solvatochromic pyridinium betaine

Beckett, Michael A.; Dawber, J. Graham

doi:10.1039/f19898500727

Cited by 18 publications

(17 citation statements)

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“…This limitation of a continuum model that ignores specific solute-solvent interactions has been recognized by different authors, when trying to reproduce solvent effects on solvatochromic dyes [26,30,31].…”

Section: Calculation Of Halochromic Shifts In Solutionmentioning

confidence: 99%

“…Examples of cationic halochromism are found in solutions of solvatochromic phenolate dyes [6][7][8]. For example, addition of increased concentrations of alkaline or alkaline-earth perchlorates to alcoholic solutions of Reichardt's E T (30) betaine leads to significant colour changes, and hypsochromic shifts of its solvatochromic charge-transfer band [6], as a result of ion-pair formation between the cation and the phenolate donor moiety [7,8]. This ion-pair association *Corresponding author.…”

Section: Introductionmentioning

confidence: 99%

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The cationic halochromism of phenolate betaines: Molecular dynamics and quantum mechanics studies

Domínguez

Rezende

2010

JICS

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The cationic halochromism of phenolate betaines was reproduced with the aid of a simple theoretical model, by calculation of the longest wavelength transition energies of supermolecules obtained by positioning a cation M n+ at a variable distance from the oxygen atom of the dye. The theoretical results were compared with experimental data for three systems, Reichardt's betaine 1, Brooker's merocyanine 2 and the N-methyl-8-oxyquinolinium dye 3. The model was validated by molecular dynamics simulations of solutions of dye 3, in methanol and DMSO, in the presence of variable concentrations of Na + .

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Section: Calculation Of Halochromic Shifts In Solutionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

The cationic halochromism of phenolate betaines: Molecular dynamics and quantum mechanics studies

Domínguez

Rezende

2010

JICS

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“…[26,[31][32][33][34][35][36] Beckett and Dawber combined ad ynamic study with CNDO calculations to estimate solvent-solute interactions of B30 with ten different solvents. [33] These authors found that Coulombic and van der Waals components contributet he most to the total docking energy.R auhute tal. used NDDO in combination with as elf-consistent reaction field (SCRF) approacht om odel both the ground-statea nd the excited-state of B30 in several solvents.…”

Section: Introductionmentioning

confidence: 99%

Exploring the Solvatochromism of Betaine 30 with Ab Initio Tools: From Accurate Gas‐Phase Calculations to Implicit and Explicit Solvation Models

Budzák

Jaunet-Lahary

Laurent

et al. 2017

Chemistry A European J

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Betaine 30 is known for the extraordinary solvatochromism of its visible absorption band that goes from λ=882 nm in tetrachloromethane to λ=453 nm in water (Δλ=-429 nm). This large blueshift partly originates from a dramatic decrease of the dipole moment upon excitation. Despite several decades of research, experimental works still disagree on the exact value of the excess dipole moment, the orientation of the dipole moment of the excited-state, the role and amplitude of the change of the polarisability upon excitation as well as on the gas-phase excitation energy. In this work, we present an in-depth theoretical investigation. First, we carefully tested several levels of theory on the model system and next calculated the electric properties of betaine 30 at the CC2 level. Our best estimates are Δμ=-7 D for the excess dipole moment, that is, a significant decrease but no change of direction, a Δα value of -120 a.u. and a gas-phase vertical excitation energy of 1.127 eV. The implicit solvation models are able to reproduce the experimental trends, with large correlation coefficients for non-hydrogen-bond-donating solvents, the smallest root-mean-square deviation error being reached with the vertical excitation model (VEM). The explicit effective fragment potential method combined with time-dependent density functional theory (TD-DFT) in a QM/MM framework provides accurate estimates for hydrogen-bond-donating solvents, whereas the addition of a dispersion correction is needed to restore the correct solvatochromic direction in tetrachloromethane.

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“…The measurement of 2PA cross-sections is performed for three solvents (chloroform, dimethyl formamide, and dimethyl sulfoxide) using the Z-scan technique. [39,40,42,67,80,[84][85][86][87][88][89][90][91][92][93][94][95][96][97][98][99][100] The spectroscopic studies of RD are mainly focused on the behavior of its long-wavelength CT absorption band in a variety of media to obtain E T (30) and/or E T N values. To unravel the solvent dependence of the 2PA cross-section, the electronic structure of RD is determined using a hybrid quantum mechanics/molecular mechanics (QM/MM) approach, in which polarization between the solute and solvent is taken into account by using a self-consistent scheme in the solvent polarization.…”

Section: Introductionmentioning

confidence: 99%

“…[56][57][58][59][60] Since it was first synthesized in 1920, RD and its derivatives have been extensively examined both experimentally, [61] to better understand its unusual sensitivity for changes in the environment, [36-38, 40, 41, 44, 46, 50-60, 62-83] and theoretically. [39,40,42,67,80,[84][85][86][87][88][89][90][91][92][93][94][95][96][97][98][99][100] The spectroscopic studies of RD are mainly focused on the behavior of its long-wavelength CT absorption band in a variety of media to obtain E T (30) and/or E T N values. [1, 15-17, 36, 44-46, 50, 51] Extensive experimental data show that RD is also sensitive to other stimuli, such as temperature [1, 15-17, 38, 40, 50, 63-68] (thermochromism), pH (halochromism), [1, 15-17, 38, 68, 69] or external pressure (piezochromism).…”

Section: Introductionmentioning

confidence: 99%

Two‐Photon Solvatochromism II: Experimental and Theoretical Study of Solvent Effects on the Two‐Photon Absorption Spectrum of Reichardt’s Dye

et al. 2013

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In this study, we report on the influence of solvent on the two-photon absorption (2PA) spectra of Reichardt's dye (RD). The measurement of 2PA cross-sections is performed for three solvents (chloroform, dimethyl formamide, and dimethyl sulfoxide) using the Z-scan technique. The key finding of this study is the observation that the cross-section, corresponding to the 2PA of the intramolecular charge-transfer state, diminishes substantially upon increasing the solvent polarity. To unravel the solvent dependence of the 2PA cross-section, the electronic structure of RD is determined using a hybrid quantum mechanics/molecular mechanics (QM/MM) approach, in which polarization between the solute and solvent is taken into account by using a self-consistent scheme in the solvent polarization. The two-state approximation proves to be adequate for the studied system, and allowed the observed solvent-polarity-induced decrease of the 2PA cross-section to be related to the decrease of the transition moment and the increase in the excitation energy.

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A computer simulation of the solvation of a solvatochromic pyridinium betaine

Cited by 18 publications

References 0 publications

The cationic halochromism of phenolate betaines: Molecular dynamics and quantum mechanics studies

The cationic halochromism of phenolate betaines: Molecular dynamics and quantum mechanics studies

Exploring the Solvatochromism of Betaine 30 with Ab Initio Tools: From Accurate Gas‐Phase Calculations to Implicit and Explicit Solvation Models

Two‐Photon Solvatochromism II: Experimental and Theoretical Study of Solvent Effects on the Two‐Photon Absorption Spectrum of Reichardt’s Dye

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