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Lagalante, Anthony F.; Wood, Christian; Clarke, Adam M.; Bruno, Thomas J.

doi:10.1023/a:1022607127781

Cited by 24 publications

(11 citation statements)

References 13 publications

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“…The anomalous, negative a value determined forG 4u sing Burgess's dye is attributedt o its absorbance lying at an extremity of the calibration range. The data are otherwise consistentw ith expectationsa nd the literatureo ns imilarc ompounds, [29] with both glycols yielding substantially higher a values than the corresponding glymes. The most striking result here is that the a values of all of the SILs are significantly higher than those of the respective pure glymes and glycols, with the greatestd ifferenceo bserved for the glymes.…”

Section: Alpha Valuessupporting

confidence: 89%

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Kamlet–Taft Solvation Parameters of Solvate Ionic Liquids

2016

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The Kamlet-Taft solvent parameters of solvate ionic liquids (SILs) prepared from lithium salts with glyme and glycol ligands are determined. The dipolarity/polarisibilities (π*) are high, similar to those found in conventional ionic liquids. The H-bond basicities (β) depend strongly on the anion. The H-bond acidities (α) are high in both glyme and glycol SILs, indicating that the lithium is acting as a H-bond donor site. "Poor" SILs have glyme-rich and salt-rich regions. In these liquids the π* and β values are almost identical to the parent glyme or glycol, and the α values are determined by the salt alone.

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Section: Alpha Valuessupporting

confidence: 89%

“…The anomalous, negative α value determined for G4 using Burgess's dye is attributed to its absorbance lying at an extremity of the calibration range. The data are otherwise consistent with expectations and the literature on similar compounds, with both glycols yielding substantially higher α values than the corresponding glymes.…”

Section: Resultsmentioning

confidence: 99%

Kamlet–Taft Solvation Parameters of Solvate Ionic Liquids

2016

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“…These parameters attempt to separate the contributions of individual interactions such as ion-dipole, dipole-dipole, dipole induced-dipole, hydrogen bonding, electron pair donor-electron pair acceptor interactions (EPD/EPA), and solvophobic interactions. Examples include Kamlet-Taft, [114][115][116][117][118][119] Catalan [120][121][122][123] and Swain 116,124 solvatochromic parameters, as well as the Hansen, 58,75,[125][126][127][128][129] Flory Huggins [130][131][132][133] and Modified Separation of Cohesive Energy Density Model (MOSCED) 134,135 thermodynamic models.…”

Section: Multi-term Solvent Parametersmentioning

confidence: 99%

“…Kamlet-Taft parameters characterize a solvent with regards to its polarizability p, hydrogen-bond donating (the acidity parameter, a), and hydrogenbond accepting (the basicity parameter, b) terms. 79,117,136,137 The polarizability parameter originates from electrostatic and dispersive interactions. 79,117,136,137 It is obtained using the spectra of either p-nitroanisole or N,N-dimethyl-p-nitroaniline (NNDN) (Fig.…”

Section: Multi-term Solvent Parametersmentioning

confidence: 99%

To gel or not to gel: correlating molecular gelation with solvent parameters

et al. 2015

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Rational design of small molecular gelators is an elusive and herculean task, despite the rapidly growing body of literature devoted to such gels over the past decade. The process of self-assembly, in molecular gels, is intricate and must balance parameters influencing solubility and those contrasting forces that govern epitaxial growth into axially symmetric elongated aggregates. Although the gelator-gelator interactions are of paramount importance in understanding gelation, the solvent-gelator specific (i.e., H-bonding) and nonspecific (dipole-dipole, dipole-induced and instantaneous dipole induced forces) intermolecular interactions are equally important. Solvent properties mediate the self-assembly of molecular gelators into their self-assembled fibrillar networks. Herein, solubility parameters of solvents, ranging from partition coefficients (log P), to Henry's law constants (HLC), to solvatochromic parameters (ET(30)), and Kamlet-Taft parameters (β, α and π), and to Hansen solubility parameters (δp, δd, δh), are correlated with the gelation ability of numerous classes of molecular gelators. Advanced solvent clustering techniques have led to the development of a priori tools that can identify the solvents that will be gelled and not gelled by molecular gelators. These tools will greatly aid in the development of novel gelators without solely relying on serendipitous discoveries. These tools illustrate that the quest for the universal gelator should be left in the hands of Don Quixote and as researchers we must focus on identifying gelators capable of gelling classes of solvents as there is likely no one gelator capable of gelling all solvents.

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“…The following are available online. Document: Full details of the calculations and an explanation of solvatochromism and the COSMOtherm software [42,43,44,45,46,47,48,49,50,51,52,53,54,55,56,57,58,59,60,61,62,63,64,65,66,67,68]. Spreadsheet: List of experimental and calculated KAT parameters, data for 16 additional case studies, and attempts to directly predict equilibrium constants in COSMOtherm.…”

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confidence: 99%

A Method of Calculating the Kamlet–Abboud–Taft Solvatochromic Parameters Using COSMO-RS

et al. 2019

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There is demand for safer and bio-based solvents, brought on by legislation and sustainability objectives. The prediction of physical properties is highly desirable to help design new molecules. Here we present an in silico approach to obtain calculated Kamlet–Abboud–Taft solvatochromic parameters using virtual experiments. The tautomerisation equilibrium of methyl acetoacetate and dimedone was calculated in different solvents with COSMO-RS theory and converted into estimates of solvent dipolarity and hydrogen bond accepting ability, respectively. Hydrogen bond donating ability was calculated as a function of the electron deficient surface area on protic solvents. These polarity descriptors correlate with rate constants and equilibria, and so ability of calculated Kamlet–Abboud–Taft solvatochromic parameters to recreate experimental free energy relationships was tested with sixteen case studies taken from the literature. The accuracy of the calculated parameters was also satisfactory for solvent selection, as demonstrated with a 1,4-addition reaction and a multicomponent heterocycle synthesis.

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Untitled

Cited by 24 publications

References 13 publications

Kamlet–Taft Solvation Parameters of Solvate Ionic Liquids

Kamlet–Taft Solvation Parameters of Solvate Ionic Liquids

To gel or not to gel: correlating molecular gelation with solvent parameters

A Method of Calculating the Kamlet–Abboud–Taft Solvatochromic Parameters Using COSMO-RS

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