Solvent property scales hydrogen bonding

The p scale was proposed to measure solvent hydrogen bond basicity, i.e. the ability of a bulk solvent to act as hydrogen bond acceptor. This scale was derived by systematic application of the solvatochromic comparison method the final p values were calculated by averaging 13 p parameters for each solvent obtained with different solutes and different physicochemical properties [Kamlet et al, 1981a Kamlet et al, 1983]. 

Tfaeie have been a number of attempts to develop solvent parameter scales that could be used to correlate ttiermodynamic and kinetic results in terms of these patametois. Gutmann s Donor Numbers, discussed previously, are sometimes used as a solvent property scale. Kamlet and Taft and co-workers developed the solvatochromic parameters, Uj, B, and n that are related to the hydrogen bonding acidity, basicity and polarity, respectively, of the solvent. Correlations with these parameters also use the square of tte Hildebrand solubility parameter, (5, that gives the solvent cohesive energy density. Parameters for some common solvents are collected in Table 3.6. 

The applicabiUty of the 4-fluorophenol affinity scale to solvents other than the definition solvent ecu is difficult to test rigorously because of a lack of data. However, the data for 3-CF3C6H4OH and 3-FC6H4OH [120-122] can be used to test the application of Equation 4.26 to the effects of solvents, because these phenols have structures and hydrogen-bond donor properties very close to those of 4-FC6H4OH. Table 4.32 lists the values of hydrogen-bond affinities of various bases in six solvents cyclohexane, carbon tetrachloride, benzene, 1,2-dichlorobenzene, dichloromethane and 1,2-dichloroethane. It also gives the values of the solvent polarity parameter Ej [103], which increases in the above order from cyclohexane to 1,2-dichloroethane. 

One of the most popular applications of molecular rotors is the quantitative determination of solvent viscosity (for some examples, see references [18, 23-27] and Sect. 5). Viscosity refers to a bulk property, but molecular rotors change their behavior under the influence of the solvent on the molecular scale. Most commonly, the diffusivity of a fluorophore is related to bulk viscosity through the Debye-Stokes-Einstein relationship where the diffusion constant D is inversely proportional to bulk viscosity rj. Established techniques such as fluorescent recovery after photobleaching (FRAP) and fluorescence anisotropy build on the diffusivity of a fluorophore. However, the relationship between diffusivity on a molecular scale and bulk viscosity is always an approximation, because it does not consider molecular-scale effects such as size differences between fluorophore and solvent, electrostatic interactions, hydrogen bond formation, or a possible anisotropy of the environment. Nonetheless, approaches exist to resolve this conflict between bulk viscosity and apparent microviscosity at the molecular scale. Forster and Hoffmann examined some triphenylamine dyes with TICT characteristics. These dyes are characterized by radiationless relaxation from the TICT state. Forster and Hoffmann found a power-law relationship between quantum yield and solvent viscosity both analytically and experimentally [28]. For a quantitative derivation of the power-law relationship, Forster and Hoffmann define the solvent s microfriction k by applying the Debye-Stokes-Einstein diffusion model (2)... 

Attention should be paid to the additional hydrogen bonding effect in protic solvents like alcohols. It has indeed been observed that correlations of solvent-dependent properties (especially positions and intensities of absorption and emission bands) with the fcT(30) scale often follow two distinct lines, one for non-protic solvents and one for protic solvents. 

It has been stated that, when specific hydrogen-bonding effects are excluded, and differential polarizability effects are similar or minimized, the solvent polarity scales derived from UV/Vis absorption spectra Z,S,Ei 2Qi),n, Xk E- ), fluorescence speetra Py), infrared spectra (G), ESR spectra [a( " N)], NMR spectra (P), and NMR spectra AN) are linear with each other for a set of select solvents, i.e. non-HBD aliphatic solvents with a single dominant group dipole [263]. This result can be taken as confirmation that all these solvent scales do in fact describe intrinsic solvent properties and that they are to a great extent independent of the experimental methods and indicators used in their measurement [263], That these empirical solvent parameters correlate linearly with solvent dipole moments and functions of the relative permittivities (either alone or in combination with refractive index functions) indicates that they are a measure of the solvent dipolarity and polarizability, provided that specific solute/ solvent interactions are excluded. 

Over the last few years, the development of solvents of desired properties with a particular use in mind has been challenging. To evaluate the behaviour of a liquid as solvent, it is necessary to understand the solvation interactions at molecular level. In this vein, it is of interest to quantify its most relevant molecular-microscopic solvent properties, which determine how it will interact with potential solutes. An appropriate method to study solute-solvent interactions is the use of solvatochromic indicators that reflect the specific and non-specific solute-solvent interactions on the UV-Vis spectral band shifts. In this sense, a number of empirical solvatochromic parameters have been proposed to quantify molecular-microscopic solvent properties. In most cases, only one indicator is used to build the respective scale. Among these, the E (30) parameter proposed by Dimroth and Reichardt [23] to measure solvent dipolarity/polarisability which is also sensitive to the solvent s hydrogen-bond donor capability. On the other hand, the n, a and P (Kamlet, Abboud and Taft)... 

Several solvent polarity scales vere proposed to quantify the polar effects of solvents on physical properties and reactivity parameters in solution, such as rate of solvolyses, energy of electronic transitions, solvent induced shifts in IR, or NMR spectroscopy. Most of the polarity scales vere derived by an empirical approach based on the principles of the linear free energies relationships applied to a chosen reference property and system vhere hydrogen bonding effects are assumed negligible [Reichardt,1965, 1990 Kamlet, Abboud et al., 1981, 1983]. 

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