Solvents solvatochromic probes

Dimroth et al. introduced 8 as a solvatochromic probe of solvent polarity having absorption in the visible region it shows the largest solvatochromic shift of any substance yet reported. Ey (30) is calculated with Eq. (8-76), like Z. (The peculiar symbolism arose because compound 8 happened to be No. 30 on the list of substances studied by Dimroth et al.) The shift is hypsochromic as solvent polarity is increased. Table 8-16 gives some Ey (30) values. - (30) is linearly... 

The relative importance of the hafide anion - HO - Cell interactions can be inferred from application of the Taft-Kamlet-Abboud equation to the UV-Vis absorbance data of solvatochromic probes, dissolved in cellulose solutions in different solvent systems, including LiCl/DMAc and LiCl/N-methyl-2-pyrrolidinone [96]. According to this equation, the microscopic polarity measured by the indicator, Ej (indicator), in kcalmol is correlated with the properties of the solvents by Eq. 1 ... 

Solvatochromic probes have been used for a variety of applications like the study polarity of pure and mixed solvents [99], and the retention behavior in reverse-phase liquid chromatography [100] among other applications. Frechet et al. used 4-(N-methylamino)-l-nitrobenzene (p-MANB), as the chromophore, to probe the microenvironment of polyaromatic ether based dendrimers [101]. 

Solvation properties, of supercritical solvents, 14 80-81 Solvatochromic materials, 22 708t Solvatochromic probes, 26 853—855 Solvatochromic spectral shifts, 23 96 Solvatochromy, 20 517 Solvay, 7 641 Solvay process, 15 63... 

Hydrogen bond donor solvents are simply those containing a hydrogen atom bound to an electronegative atom. These are often referred to as protic solvents, and the class includes water, carboxylic acids, alcohols and amines. For chemical reactions that involve the use of easily hydrolysed or solvolysed compounds, such as AICI3, it is important to avoid protic solvents. Hydrogen bond acceptors are solvents that have a lone pair available for donation, and include acetonitrile, pyridine and acetone. Kamlet-Taft a and ft parameters are solvatochromic measurements of the HBD and HBA properties of solvents, i.e. acidity and basicity, respectively [24], These measurements use the solvatochromic probe molecules V, V-die lliy I -4-n i in tan iline, which acts as a HBA, and 4-nitroaniline, which is a HBA and a HBD (Figure 1.17). 

Spectroscopic measurements of solvatochromic and fluorescent probe molecules in room temperature ILs provide an insight into solvent inter-molecular interactions, although the interpretation of the different and generally uncorrelated polarity scales is sometimes ambiguous [23]. It appears that the same solvatochromic probes work in ILs as well [24], but up to now only limited data are available on the behavior of electronic absorption and fluorescence solvatochromic probes within ILs and IL-organic solvent mixtures. 

A solvatochromic scale, based on the ultraviolet-visible, rather than the infrared, spectral band of suitable probes is that based on the Kamlet -Taft P parameter. This is again an averaged quantity, for which the wavenumber shifts of several protic indicators relative to structurally similar but aprotic homomorphs are used (Kamlet et al. 1983 Kamlet and Taft 1976). It is assumed that the nonspecific effect of a solvent on the protic probe is the same as that on the aprotic one, and that it can be expressed in terms of the n parameter for the solvent, so that the donicity of the solvent, if it is a Lewis base, causes the difference between the responses of the two probes towards the solvent. The probes originally employed were 4-nitrophenol (vs 4-nitroanisole) and 4-nitroaniline (vs 4-nitroN,N-diethylaniline), but once a n scale is known, the need for the specific aprotic homomorph values no longer exists, since the general expression ... 

Application of Solvatochromic Probes to Supercritical and Mixed Fluid Solvents... 

The solvatochromic probe molecule chosen for this work was 2-nitroanisole (Aldrich Chemical Co.). The s value reported in the literature for 2-nitroanisole is -2.428 + 0.195 ( 1 ). A known s value for the solute allows one to calculate the change in the supercritical fluid solvents it value as temperature or pressure changes. The reference absorption maxima for 2-nitroanisole is 32.56 x 10J cm"1 (vQ) in cyclohexane (1). 

Another nonreactive route to the characterization of solvent polarity is the study of the optical absorption and emission spectra of chromophores [188]. These spectra are sensitive to the molecular environment, and because different solvatochromic probes may have different capacities for specific interactions, it is possible to characterize the solvent environment in detail and to construct LFERs analogous to those described above. Studies of the spectra of solvatochromic probes in ionic liquids have in general been consistent with the results of partitioning studies described above [8-10, 69, 70, 198-200], though we will discuss one observed anomaly below [198]. 

While the study of solvatochromic dyes is well established as a means of probing solvent polarity, these are not the only solutes that can be used in this fashion. A more exotic solvatochromic probe is an excess electron in solution. Optical absorption studies of the thermalized (solvated) electron generated in the pulse radiolysis of a series of ILs show a strong dependence on cation character, with a relatively low frequency for tetraalkylammonium systems and a higher frequency for cyclic (pyrrolidinium-based) cations [48, 207]. The solvated electron spectrum is often interpreted in a particle-in-a-box framework, which would imply that the cyclic cations (which possess smaller ionic volumes) simply coordinate more closely with the electron and so create a smaller domain in which the electron must localize. The breadth of the absorptions and their maximum fall within the range of values expected for moderately polar organic solvents. 

A small selection of other strongly solvatochromic fluorophores, recommended as solvent polarity probes because of their large solvent-induced shifts of the long-wavelength emission band, is given in Scheme 1 further examples can be found in references [10, 16, 112, 486],... 

The polarities of binary solvent mixtures with limited mutual miscibility such as zz-BuOH/H20 and c-CeH /DMF [191] as well as of solid polymer mixtures (organic glasses) [195] have also been studied using solvatochromic probes such as the betaine dye (44). 

Further solvent polarity scales based on UV/Vis absorption as well as fluorescence spectra have been proposed by Brooker et al. [77], Dahne et al. [78], de Mayo et al. [217], Dubois et al. [79], Mukerjee et al. [218] and Wrona et al. [219], Walter et al. [220], Walther [81] and Lees et al. [82], Zelinskii et al. [80], Winnik et al. [222], Kamlet and Taft [84, 84a, 224, 226]. Buncel et al. [333], and Catalan et al. [296, 334-337]. In addition to these scales, a great variety of further positively and negatively solvato-chromic dyes have been recommended as solvent polarity indicators. A review describes about 60 organic and inorganic compounds, the solvatochromism of which is sufficiently large for their potential application as empirical solvent polarity probes [293]. 

In 1994, a review on the further development and improvement of the n scale was given by Laurence, Abboud et al. [227], They redetermined n values for a total of 229 solvents, this time using only two (instead of seven) solvatochromic nitroaromatics as indicator compounds, i.e. 4-nitroanisole and A,A-dimethylamino-4-nitroaniline, for good reasons see later and reference [227] for a more detailed discussion. A thermodynamic analysis of the n scale [and the t(30) scale] has been reported by Matyushov et al. [228]. Using six novel diaza merocyanine dyes of the type R-N=N-R (R = N-methylpyridinium-4-yl or A-methylbenzothiazolium-2-yl, and R = 2,6-disubstituted 4-phenolates or 2-naphtholate) instead of nitroaromatics as positively solvatochromic probe compounds, an analogous n azo scale was developed by Buncel et al., which correlates reasonable well with the n scale, but has some advantages for a detailed discussion, see references [333], Another n scale, based solely on naphthalene, anthracene, and y9-carotene, was constructed by Abe [338], n values are mixed solvent parameters, measuring the solvent dipolarity and polarizability. The differences in the various n scales are caused by the different mixture of dipolarity and polarizability measured by the respective indicator. The n scale of Abe is practically independent of the solvent dipolarity, whereas Kamlet-Taft s n and Buncel s n azo reflect different contributions of both solvent dipolarity and polarizability. 

With the use of solvatochromic probes, other non-specific forces (dispersion, dipole-induced dipole, and dipole-dipole) and specific acid-base forces have been explored in SCF solvents. In an effort to compare liquid and supercritical carbon dioxide, Hyatt(ll) measured UV-visible spectra of several solvatochromic probes. There was little difference between the Ex in the liquid and SCF states however, the data can not be interpreted fully since the density and the pressure were not given at the supercritical condition. The results indicated that the... 

This chapter examines various derivatives of aniline that have been used as solvatochromic probes of the abilities of solvents and other environments to solvate solutes. It is difficult to delimit what are aniline derivatives proper (aminonaphthalenes are not included, for instance) and not all the derivatives can be discussed in a chapter such as this. Nevertheless, certain dyes that have been extensively used as solvatochromic probes and that have... 

Laurence and coworkers18 studied also the properties of the pair 4-aminoacetophenone (17) and 4-A,A-dimethylaminoacetophenone (18) as solvatochromic probes, but with regard to 12 solvents only. The imperfect linear correlation of the normalized /i 7jS with / s,7, / kt and / 2 shown in Figure 1 for these solvents indicates the importance not only of the HBD group (—OH for / 2 and —NIL for the other quantities), but also that of the... 

Af-Butyl-4-nitroaniline (30) was also shown42 to be able to donate a hydrogen bond to HBA solvents, hence could be used as a solvatochromic probe, but has not been explored further in this respect. Drago29 reported the wavenumbers of the lowest energy absorption bands of three /V-alkyl-substituted nitroanilines 27, /V-ethyl-4-nitroanilinc (31) and N-ethyl-3-nitroaniline (32). Their spectral shifts relative to that in dioxane are shown in Figure 2 as a function of / Kt and a fair correlation is seen. 

The ability of aniline derivative solvatochromic probes (5, 9, 27, 31, 36, 61, 66, 67 and 80) to characterize also the HBD abilities of solvents was reviewed by Novaki and El-Seoud100 on the basis of data from the literature. They determined the sensitivity coefficients of these probes to the ji and a solvent parameters. 

In solvent mixtures the phenomenon of preferential solvation of the solvatochromic probe by one component of the mixed solvent often takes place. Care must therefore be taken when such combinations of mixed solvents and probes are employed for the characterization of the mixed solvent as regards its solvation properties for any arbitrary solute other than the particular probe studied5. It has been argued that, contrary to the case of neat solvents, where the use of a single probe can be justified18,27, it ought to be more... 

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