A Database of Dispersion-Induction DI, Electrostatic ES, and Hydrogen Bonding α₁ and β₁ Solvent Parameters and Some Applications to the Multiparameter Correlation Analysis of Solvent Effects

Abstract

For about 300 solvents, we propose a database of new solvent parameters describing empirically solute/solvent interactions: DI for dispersion and induction, ES for electrostatic interactions between permanent multipoles, α1 for solute Lewis base/solvent Lewis acid interactions, and β1 for solute hydrogen-bond donor/solvent hydrogen-bond acceptor interactions. The main advantage over previous parametrizations is the easiness of extension of this database to newly designed solvents, since only three probes, the betaine dye 30, 4-fluorophenol, and 4-fluoroanisole are required. These parameters can be entered into the linear solvation energy relationship A = A0 + di(DI) + eES + aα1 + bβ1 to predict a large number of varied physicochemical properties A and to rationalize the multiple intermolecular forces at the origin of solvent effects through a simple examination of the sign and magnitude of regression coefficients di, e, a, and b. Such a rationalization is illustrated for conformational and tautomeric equilibria and is supported by quantum-mechanical calculations.

Strong Dipolar Effects on an Octupolar Luminiscent Chromophore: Implications on their Linear and Nonlinear Optical Properties

“…As it is was discussed before, charge transfer mechanisms influenced the TPA response. The ICT properties were studied by a combined solvatochromic analysis of Lippert-Mataga, Catalan, Kamlet-Taft and the recently proposed solvent interaction scale by Laurence, et al 50 All these methods combined allow obtaining quantitative evidence of the static dipole moment change between S 1 and S 0 and the effect of acidity, basicity, polarity and polarizability solvent parameters in the photophysical properties. Figure 5 shows the absorption and fluorescence emission spectra of DS and OS in different solvents and Table 3 presents a summary of the main results from this data.…”

Replacement of Hazardous Chemicals Used in Engineering Plastics with Safe and Renewable Hydrogen-Bond Donor and Acceptor Solvent-Pair Mixtures

“…15,28,30,31 In this work, K-T parameters are used in the methodology for selecting the solvent-pair mixtures. Figure 2 shows the methodology developed in this research for selecting solvent-pair mixtures that have favorable characteristics for preparing polymer precursor solutions.…”

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

“…In the future,w ep lan to study am ore extended panel of strongly solvatochromic molecules with such multiscale approaches. [a] Calculated as the difference between the solvent E T (30) value [23,48] and the extrapolated gas-phase value of 1083 nm. [27] [b] Calculated as the difference betweent he solvent E T (30) value [23,48] and the extrapolated gasphase value of 951 nm.…”

“…The importance of these "non-specific" solvation components on the solvatochromism of B30 is consistent with several recent analyses of the experimental data based on empirical solvation models. [22,23,48] In apolars olvents, mutual solvent-solute polarisation can lead to small redshifts with the VEM level of theory. This effect together with the impact of hydrogen bonding on the vertical excitation are discussed in the framework of explicit solvation modelsi nt he next section.…”

“…[23] To this end, they selected the CAM-B3LYP/6-31 ++G(d,p) methoda nd two versions of the PCM solvent model.L aurence et al applied as imilar protocol for estimating electrostatic empirical parameters for about 300 solvents. [48] In ac ombination of experimental measurements and theoretical calculations, Kharlanov and Rettig [15] and Catalµne tal. [27] investigated the thermosolvatochromic behaviour of B30, that is, the shift of the absorption due to av ariation of the temperature.…”