ChemInform Abstract: THE SOLVATOCHROMIC COMPARISON METHOD. 6. THE Π* SCALE OF SOLVENT POLARITIES

Kamlet, Mortimer J.; Abboud, José‐Luis M.; Taft, R. W.

doi:10.1002/chin.197749042

Cited by 64 publications

(103 citation statements)

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“…Transition energies E T were calculated from the wavelengths of the absorption maxima according to the equation E T /kJ¨mol´1 = hcN/λ = 119625/(λ/nm). A linear solvation energy relationship was established by least-squares fitting of the data to the simplified solvatochromic equation E T = E T0 + sπ* + aα involving only the parameters π* [29] and α [30] which represent the dipolarity/polarizability and hydrogen-bond donor acidity of the solvent. The hydrogen-bond acceptor parameter β [31] did not significantly contribute to the relationship.…”

Section: Uv Spectroscopymentioning

confidence: 99%

5-Azido-4-dimethylamino-1-methyl-1,2,4-triazolium Hexafluoridophosphate and Derivatives

2016

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5-Azido-4-(dimethylamino)-1-methyl-1,2,4-triazolium hexafluoridophosphate was synthesized from the corresponding 5-bromo compound with NaN 3 . Reaction with bicyclo[2.2.1]hept-2-ene yielded a tricyclic aziridine, addition of an N-heterocyclic carbene resulted in a triazatrimethine cyanine, and reduction with triphenylphosphane gave the 5-amino derivative. The crystal structures of three nitrogen-rich salts were determined. Thermoanalysis of the cationic azide and triazene showed exothermal decomposition. The triazene exhibited negative solvatochromism in polar solvents involving the dipolarity π* and hydrogen-bond donor acidity α of the solvent.

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Section: Uv Spectroscopymentioning

confidence: 99%

5-Azido-4-dimethylamino-1-methyl-1,2,4-triazolium Hexafluoridophosphate and Derivatives

2016

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“…Importantly, the association constants do not correlate well to a purely electrostatic interaction model [26]. The evaluation of the data in comparison to solvent polarity descriptors, such as E T (30) [27], the π* [28] and the Py [29] scales ( Fig. 3) suggests that the halogen bond is affected by the polarity change of its environment to a lesser extent, yet is disrupted by solvents capable of hydrogen bond donation (Fig.…”

Section: Neutral Two-center Halogen Bond Complexesmentioning

confidence: 94%

Halogen Bonding in Solution

Carlsson

Veiga

Erdélyi

2014

Topics in Current Chemistry

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Because of its expected applicability for modulation of molecular recognition phenomena in chemistry and biology, halogen bonding has lately attracted rapidly increasing interest. As most of these processes proceed in solution, the understanding of the influence of solvents on the interaction is of utmost importance. In addition, solution studies provide fundamental insights into the nature of halogen bonding, including, for example, the relative importance of charge transfer, dispersion, and electrostatics forces. Herein, a selection of halogen bonding literature is reviewed with the discussion focusing on the solvent effect and the electronic characteristics of halogen bonded complexes. Hence, charged and neutral systems together with two- and three-center bonds are presented in separate sub-sections. Solvent polarity is shown to have a slight stabilizing effect on neutral, two-center halogen bonds while strongly destabilizes charged, two-center complexes. It does not greatly influence the geometry of three-center halogen bonds, even though polar solvents facilitate dissociation of the counter-ion of charged three-center bonds. The charged three-center bonds are strengthened by increased environment polarity. Solvents possessing hydrogen bond donor functionalities efficiently destabilize all types of halogen bonds, primarily because of halogen vs hydrogen bond competition. A purely electrostatic model is insufficient for the description of halogen bonds in polar systems whereas it may give reasonable correlation to experimental data obtained in noninteracting, apolar solvents. Whereas dispersion plays a significant role for neutral, two-center halogen bonds, charged halogen bond complexes possess a significant charge transfer characteristic.

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“…In the early 1980's, Taft & Kamlet [8][9][10][11][12] have developed the basic concept of linear solvation energy relationships (LSERs). They have demonstrated for thousands of chemical systems that some property which is linearly related to either a free energy of reaction, a free energy of transfer, or an activation energy can be correlated with various fundamental molecular properties of the solvents or solutes involved.…”

Section: Linear Solvation Energy Relationshipmentioning

confidence: 99%

The Use of Solvation Models in Gas Chromatography

Mutelet¹

2012

Chromatography - The Most Versatile Method of Chemical Analysis

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ChemInform Abstract: THE SOLVATOCHROMIC COMPARISON METHOD. 6. THE Π* SCALE OF SOLVENT POLARITIES

Cited by 64 publications

References 1 publication

5-Azido-4-dimethylamino-1-methyl-1,2,4-triazolium Hexafluoridophosphate and Derivatives

5-Azido-4-dimethylamino-1-methyl-1,2,4-triazolium Hexafluoridophosphate and Derivatives

Halogen Bonding in Solution

The Use of Solvation Models in Gas Chromatography

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