Abstract
Solvatochromism of the twisted intramolecular charge-transfer (TICT) fluorescence of 4-(N,N-dimethylamino)benzonitrile (DMABN) in pure water, methanol, ethanol, 1-propanol, 2-propanol, acetone, acetonitrile, and in the corresponding aqueous–organic binary mixed solvents was systematically studied and an empirical solvent polarity scale (F B) based on the DMABN solvatochromism was defined. The F B parameters of the explored binary mixed solvents as a function of solvent composition were analyzed by a stepwise solvent-exchange (SSE) model to clarify the preferential solvation (PS) of the probe dye in these binary mixed solvents. Solvation diagrams toward DMABN in the mixed solvents, i.e., the local solvent composition in the solvation shell of DMABN molecules was depicted as a function of bulk solvent composition to visualize the PS in these mixed solvents. For comparison, a similar PS analysis was applied to the solvatochromism of 2,6-diphenyl-4-(2,4,6-triphenylpyridinium-1- yl)phenolate (ET-30) and pyrene (Py) in these mixed solvents; the responsive PS pattern of the mixed solvents toward the specific indicator dye of DMABN, ET-30, and Py was then discussed in terms of the chemical properties of the probe dye, the properties of the mixed solvents, and the solute–solvent and solvent–solvent interactions.
Similar content being viewed by others
REFERENCES
R. E. Majors, Liquid Chromatogr. Gas Chromatogr. 6, 298(1988), and references therein; C. Reichardt, Solvents and Solvent Effects in Organic Chemistry, 2nd edn. (Verlag Chemie, Weinheim, 1988); C. Reichardt, Chem. Rev. 94, 2319(1994).
E. Peyrin, F. X. Perrin, and Y. C. Auillaume, Anal. Chem. 71, 2708(1999).
Y. C. Guillaume and C. Guinchard, Anal. Chem. 68, 2869(1996); Anal. Chem. 69, 183(1997); Anal. Chem. 70, 608(dy1998).
M. Kumamoto, T. Sonda, K. Takedomi, and M. Tabata, Anal. Sci. 16, 139(2000).
K. Dimroth, C. Reichardt, T. Siepmann, and F. Bohlmann, Liebigs Ann Chem. 661, 1(1963).
M. J. Kamlet and R. W. Taft, J. Amer. Chem. Soc. 98, 377(1976); J. Amer. Chem. Soc. 98, 2886(1976).
H. Langhals, Angew. Chem. Intern. Ed. Engl. 21, 724(1982).
E. B. Tada, L. P. Novaki, and O. A. El Seoud, J. Phys. Org. Chem. 13, 679(2000).
E. Casassas, G. Fonrodona, and A. Juan, J. Solution Chem. 21, 147(1992).
G. Strat and M. Strat, J. Mol. Liquids 85, 279(2000).
B. D. Bursulaya, D. A. Zichi, and H. J. Kim, J. Phys. Chem. 100, 1392(1996).
J. J. Michels and J. G. Dorsey, J. Chromatogr. 457, 85(1988).
L. P. Novaki and O. A. El Seoud, Ber. Bunsenges. Phys. Chem. 101, 105, 902 (1997).
P. M. Mancini, C. Adam, A. del C. Peréz, and L. Vottero, J. Phys. Org. Chem. 13, 221(2000).
S. Nigam and S. Rutan, Appl. Spectr. 55, 362A(2001).
T. Takamuku, M. Tabata, A. Yamaguchi, J. Nishimoto, M. Kumamoto, H. Wakita, and T. Yamaguchi, J. Phys. Chem. B 102, 8880(1998).
K. L. Rowlen and J. M. Harris, Anal. Chem. 63, 964(1991).
E. Grunwald, G. Baughman, and G. Kohnstam, J. Amer. Chem. Soc. 82, 5810(1960).
A. K. Convington and K. E. Newman, Pure Appl. Chem. 51, 2041(1979); A. K. Convington, K. E. Newman, and T. H. Lilley, J. Chem. Soc. Faraday Trans. 1 69, 973(1973).
A. W. Frankel, T. R. Stengle, and C. H. Langford, J. Phys. Chem. 74, 1376(1970).
D. Banerjee, A. K. Laha, and S. Bagchi, J. Chem. Soc. Faraday Trans. 1 91, 631(1995).
Y. Marcus, Austr. J. Chem. 36, 1719(1983); J. Chem. Soc. Faraday Trans. 1 84, 1465(dy1988).
A. Ben-Naim, Cell Biophys. 12, 255(1988); Pure Appl. Chem. 62, 25(1990); J. Phys. Chem. 93, 3809(1989).
R. D. Skwierczynski and K. A. Connors, J. Chem. Soc. Perkin Trans. 2, p. 467(1994).
M. Rosés, C. Ràfols, J. Ortega, and E. Bosch, J. Chem. Soc. Perkin Trans. 2, p. 1607(1995); J. Chem. Soc. Perkin Trans. 2, p. 1497(1996).
S. Nigam, A. Juan, R. J. Stubbs, and S. C. Rutan, Anal. Chem. 72, 1956(2000).
W. Rettig, Topics of Current Chemistry, Vol. 169 (Springer Verlag, Berlin, 1994), pp. 253-299.
O. Kajimoto, Dynamics of Excited Molecules, K. Kuchitsu, Ed. (Elsevier, Amsterdam, 1994), p. 363.
P. Changenet, P. Plaza, M. M. Martin, and Y. H. Meyer, J. Phys. Chem. A, 101, 8186(1997).
F. Heisel, J. A. Miehe, and J. M. G. Martinho, Chem. Phys. 98, 243(1985).
G. S. Cox, P. J. Hauptman, and N. J. Turro, Photochem. Photobiol. 5, 597(1984).
W. E. AcreeJr., J. R. Powell, and S. A. Tucker, J. Chem. Soc. Perkin Trans. 2, p. 529(1995).
Y. Kusumoto, Y. Takeshita, J. Kurawaki, and I. Satake, Chem. Lett., p. 349(1997).
V. Gutmann, The Donor-Acceptor Approach to Molecular Interactions (Plenum Press, New York, 1978).
Author information
Authors and Affiliations
Rights and permissions
About this article
Cite this article
Wu, Y.G., Tabata, M. & Takamuku, T. Preferential Solvation in Aqueous–Organic Mixed Solvents Using Solvatochromic Indicators. Journal of Solution Chemistry 31, 381–395 (2002). https://doi.org/10.1023/A:1015859315320
Issue Date:
DOI: https://doi.org/10.1023/A:1015859315320