Solvatochromism in binary mixtures: first report on a solvation free energy relationship between solvent exchange equilibrium constants and the properties of the medium.

We have employed UV-vis spectroscopy in order to investigate details of the solvation of six solvatochromicindicators, hereafter designated as "probes", namely, 2,6-diphenyl-4-(2,4,6-triphenylpyridinium-1-yl) phenolate(RB); 4-[(E)-2-(1-methylpyridinium-4-yl)ethenyl] phenolate, MePM; 1-methylquinolinium-8-olate, QB;2-bromo-4-[(E)-2-(1-methylpyridinium-4-yl)ethenyl] phenolate, MePMBr, 2,6-dichloro-4-(2,4,6-triphenylpyridinium-1-yl) phenolate (WB); and 2,6-dibromo-4-[(E)-2-(1-methylpyridinium-4-yl)ethenyl] phenolate,MePMBr2, respectively. These can be divided into three pairs, each includes two probes of similar p kappa(a) in water and different lipophilicity. Solvation has been studied in binary mixtures, BMs, of water, W, with 12protic organic solvents, S, including mono- and bifunctional alcohols (2-alkoxyethanoles, unsaturated and chlorinated alcohols). Each medium was treated as a mixture of S, W, and a complex solvent, S-W, formed by hydrogen bonding. Values of lambda max (of the probe intramolecular charge transfer) were converted into empirical polarity scales, ET(probe) in kcal/mol, whose values were correlated with the effective mole fraction of waterin the medium, chi W(effective). This correlation furnished three equilibrium constants for the exchange of solvents int he probe solvation shell; phi W/S (W substitutes S); phi S-W/W (S-W substitutes W), and phi S-W/S (S-W substitutes S), respectively. The values of these constants depend on the physicochemical properties of the probe and the medium. We tested, for the first time, the applicability of a new solvation free energy relationship: phi =constant + a alpha(BM) + b beta(BM) + s(pi* (BM) + d delta) + p log P (BM), where a, b, s, and p are regression coefficients; RBM,alpha (BM), beta(BM) and pi (BM) are solvatochromic parameters of the BM, delta is a correction term for pi*, and log P is an empirical scale of lipophilicity. Correlations were carried out with two-, three-, and four-medium descriptors.In all cases, three descriptors gave satisfactory correlations; use of four parameters gave only a marginal increase of the goodness of fit. For pi W/S, the most important descriptor was found to be the lipophilicity of the medium; for phi S-W/W and phi S-W/S, solvent basicity is either statistically relevant or is the most important descriptor. These responses are different from those of ET(probe) of many solvatochromic indicators in pure solvents, where the importance of solvent basicity is usually marginal, and can be neglected.