Solvatochromism

Dodsworth, Elaine S.; Hasegawa, Minoru; Bridge, Mary H.; Linert, Wolfgang

doi:10.1016/b0-08-043748-6/01158-0

Cited by 11 publications

(7 citation statements)

References 150 publications

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“…AN and DN were determined by spectroscopic methods (UV/Vis) using the solvatochromic indicators Fe(phen) 2 (CN) 2 for AN and Cu(acac)(tmen) + for DN. Solvatochromism12 describes the changes in spectra of dissolved species depending of the media. Such effects are used to visualize solvent properties; however, different indicator species may measure different aspects of solvent solute interactions.…”

Section: Introductionmentioning

confidence: 99%

Mutual Lewis Acid–Base Interactions of Cations and Anions in Ionic Liquids

Holzweber

Lungwitz

Doerfler

et al. 2012

Chemistry A European J

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Solute properties are known to be strongly influenced by solvent molecules due to solvation. This is due to mutual interaction as both the properties of the solute and of the solvent strongly depend on each other. The present paper is based on the idea that ionic liquids are cations solvated by anions and anions solvated by cations. To show this (in this system strongly pronounced) interaction the long time established donor–acceptor concept for solvents and ions in solution by Viktor Gutmann is extended to ionic liquids. A number of solvent parameters, such as the Kamlet–Abboud–Taft and the Dimroth–Reichardt ET scale for ionic liquids neglect this mutual influence, which, however, seems to be in fact necessary to get a proper description of ionic liquid properties. It is shown how strong such parameters vary when the influence of the counter ion is taken into account. Furthermore, acceptor and donor numbers for ionic liquids are presented.

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Section: Introductionmentioning

confidence: 99%

Mutual Lewis Acid–Base Interactions of Cations and Anions in Ionic Liquids

Holzweber

Lungwitz

Doerfler

et al. 2012

Chemistry A European J

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“…In order to investigate the consequence of solvents on maximum absorption and to estimate the ground and excited states, solvatochromism is usually considered for these purposes. [26] The ground state is more stable in less polar solvents than the excited state and will lead to negative solvatochromism (hypsochromic shift). Whereas, the excited state is relatively more robust in more polar solvents and will conduct positive solvatochromism (bathochromic shift).…”

Section: Resultsmentioning

confidence: 99%

Solvent Influence on Absorption Spectra and Tautomeric Equilibria of Symmetric Azomethine‐Functionalized Derivatives: Structural Elucidation and Computational Studies

Salih

2022

ChemistryOpen

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A new series of azomethine‐functionalized compounds was synthesized from the condensation of 2‐hydroxy‐1,3‐propanediamine and 2‐thienylcarboxaldehydes in the presence of a drying agent. The derivatives were spectroscopically characterized by NMR, LC‐MS, UV/Vis, IR and elemental analysis. Variable temperature 1H‐NMR (−60 to +60 °C) was performed to investigate the effect of solvent polarity; the capability of solvent to form H‐bond was found to dramatically influencing the tautomerization process of the desired structures. The calculated thermochemical parameters (ΔH298, ΔG298 and ΔS298) at DFT and MP2 levels of theory explained that 3 b exists in equilibrium with two tautomers. The basis of the electronic absorptions was pursued through Time‐Dependent Density‐Functional Theory (TD‐DFT). Analysis of the structural surfaces was inspected and the molecular electrostatic potential (MEP) demonstrated that the three functionalized compounds were relatively analogous in the electronic distributions. Furthermore, the electrophilic and nucleophilic centers lying on the molecular surfaces were probably playing a key‐role in stabilizing the compounds through the nonclassical C−H⋅⋅⋅π interactions and hydrogen bonding. The impact of solvent polarity on absorption spectra were investigated via solvatochromic shifts. For instance, compound 3 c displayed a gradual shift of the maximum absorption to the red area when the solvent polarity was increased, recording a 21 nm of bathochromic shift. In contrast, no significant solvent‐effect on 3 a and 3 b was observed. The solvation relation was pursued between Gutmann's donicity numbers the experimental λmax; exhibited almost positive linear performance with a minor oscillation, that ascribe to the possible weak interface between the molecules of solute and designated solvents. The bandgap energy of all products were assessed experimentally using optical absorption spectra following Tauc approach, giving −4.050 (3 a), −3.900 (3 b) and −3.210 (3 c) eV. However, the ΔE were computationally figured out from TD‐DFT simulation to be −4.258 (3 a), −4.022 (3 b) and −3.390 (3 c) eV.

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“…As such, it is the stabilization of the excited state by the polar solvent that shifts the emission of the fluorophore to lower energy (longer wavelength). Furthermore, as the polarity of the solvent increases, this stabilization becomes larger, which results in an emission at longer wavelengths (red shift). , Here, employing a less polar solvent, such as DCM, the emission is significantly blue shifted as the ground state of the MOF is more polar than the excited state; thus, the ground state is stabilized by the solvent . Furthermore, the emission is quenched in nonpolar solvents, toluene and hexane, as they cannot participate in hydrogen bonding with the MOF.…”

Section: Resultsmentioning

confidence: 99%

Luminescent Properties of DOBDC Containing MOFs: The Role of Free Hydroxyls

Henkelis

Rademacher

Vogel

et al. 2020

ACS Appl. Mater. Interfaces

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A novel metal−organic framework (MOF), Mn-DOBDC, has been synthesized in an effort to investigate the role of both the metal center and presence of free linker hydroxyls on the luminescent properties of DOBDC (2,5-dihydroxyterephthalic acid) containing MOFs. Co-MOF-74, RE-DOBDC (RE−Eu and Tb), and Mn-DOBDC have been synthesized and analyzed by powder X-ray diffraction (PXRD) and the fluorescent properties probed by UV−Vis spectroscopy and density functional theory (DFT). Mn-DOBDC has been synthesized by a new method involving a concurrent facile reflux synthesis and slow crystallization, resulting in yellow single crystals in monoclinic space group C2/c. Mn-DOBDC was further analyzed by single-crystal Xray diffraction (SCXRD), scanning electron microscopy−energy-dispersive spectroscopy (SEM-EDS), and photoluminescent emission. Results indicate that the luminescent properties of the DOBDC linker are transferred to the three-dimensional structures of both the RE-DOBDC and Mn-DOBDC, which contain free hydroxyls on the linker. In Co-MOF-74 however, luminescence is quenched in the solid state due to binding of the phenolic hydroxyls within the MOF structure. Mn-DOBDC exhibits a ligand-based tunable emission that can be controlled in solution by the use of different solvents.

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Solvatochromism

Cited by 11 publications

References 150 publications

Mutual Lewis Acid–Base Interactions of Cations and Anions in Ionic Liquids

Mutual Lewis Acid–Base Interactions of Cations and Anions in Ionic Liquids

Solvent Influence on Absorption Spectra and Tautomeric Equilibria of Symmetric Azomethine‐Functionalized Derivatives: Structural Elucidation and Computational Studies

Luminescent Properties of DOBDC Containing MOFs: The Role of Free Hydroxyls

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