Journal of Solution Chemistry

, Volume 42, Issue 5, pp 1083–1095 | Cite as

Spectral Investigations of Preferential Solvation and Solute–Solvent Interactions of Free Base and Protonated 5,10,15,20-Tetrakis(4-trimethyl-ammonio-phenyl)-porphine Tetratosylate in Aqueous Organic Mixed Solvents

  • Farrokh Gharib
  • Ali Shamel
  • Fatemeh Jaberi
  • Ali Farajtabar


The solvatochromic properties of the free base and the protonated 5,10,15,20-tetrakis(4-trimethyl-ammonio-phenyl)-porphine tetratosylate (TTMAPP) were studied in pure water, methanol, ethanol, 2-propanol, and their corresponding aqueous mixtures. The correlation of the empirical solvent polarity scale (E T) values of TTMAPP with composition of the solvents were analyzed by the solvent exchange model of Bosch and Roses to clarify the preferential solvation of the probe dyes in the binary mixed solvents. The solvation shell composition effects in preferential solvation of the solute dyes were investigated in terms of both solvent–solvent and solute–solvent interactions and also the local mole fraction of each solvent composition was calculated in the cybotactic region of the probe. The effective mole fraction variation may provide significant physicochemical insights in the microscopic and molecular level of interactions between TTMAPP species and the solvent components and, therefore, can be used to interpret the solvent effect on kinetics and thermodynamics of TTMAPP.


TTMAPP Preferential solvation Methanol Ethanol 2-Propanol 



Financial support by the Research Council of Islamic Azad University, Ardabil Branch, is gratefully acknowledged.


  1. 1.
    Reichardt, C.: Solvents and Solvent Effects in Organic Chemistry, 3rd edn. VCH, New York (2004)Google Scholar
  2. 2.
    Jabbari, M., Gharib, F.: Solute–solvent interaction effects on protonation equilibrium of some water-insoluble flavonoids. J. Solution Chem. 40, 561–574 (2011)CrossRefGoogle Scholar
  3. 3.
    Shamel, A., Jaberi, F., Gharib, F.: Protonation constants of adenine and adenosine in different aqueous solutions of methanol and ethanol. J. Chem. Eng. Data 55, 5176–5181 (2010)CrossRefGoogle Scholar
  4. 4.
    Jabbari, M., Gharib, F.: Equilibrium studies of triphenyltin(IV) complexes with glycine, glycyl-glycine, and glycyl-glycyl-glycine in different aqueous solutions of ethanol. Can. J. Chem. 88, 877–885 (2010)CrossRefGoogle Scholar
  5. 5.
    Jabbari, M., Gharib, F.: Solvent effects on protonation equilibria of some amino acids and peptides in different aqueous solutions of ethanol. Acta Chim. Slov. 57, 325–331 (2010)Google Scholar
  6. 6.
    Farajtabar, A., Gharib, F.: Solvent effect on protonation constants of salicylic acid in mixed aqueous organic solutions of DMSO. Monatsh. Chem. 141, 381–386 (2010)CrossRefGoogle Scholar
  7. 7.
    Gharib, F.: Solvent effects on protonation and complexation of penicillamine and thallium(I) in different aqueous solutions of methanol. J. Chem. Eng. Data 55, 1547–1553 (2010)CrossRefGoogle Scholar
  8. 8.
    Gharib, F., Farajtabar, A., Masteri Farahani, A., Bahmani, F.: Solvent effects on protonation constants of tryptophan in some aqueous aliphatic alcohol solutions. J. Chem. Eng. Data 55, 327–332 (2010)CrossRefGoogle Scholar
  9. 9.
    Farajtabar, A., Gharib, F.: Solvent effect on protonation constants of 5, 10, 15, 20-tetrakis(4-sulfonatophenyl)porphyrin in different aqueous solutions of methanol and ethanol. J. Solution Chem. 39, 231–244 (2010)CrossRefGoogle Scholar
  10. 10.
    Giusti, L.A., Marini, G., Machado, V.G.: Solvatochromic behavior of 1-(p-dimethylaminophenyl)-2-nitroethylene in 24 binary solvent mixtures of amides and hydroxylic solvents. J. Mol. Liq. 150, 9–15 (2009)CrossRefGoogle Scholar
  11. 11.
    Izutsu, K.: Electrochemistry in Nonaqueous Solutions. Wiley-VCH, Weinheim (2002)CrossRefGoogle Scholar
  12. 12.
    Reichardt, C.: Pyridinium N-phenolate betaine dyes as empirical indicators of solvent polarity: Some new findings. Pure Appl. Chem. 76, 1903–1919 (2004)CrossRefGoogle Scholar
  13. 13.
    Marcus, Y.: Solvent Mixtures: Properties and Selective Solvation. Marcel Dekker, New York (2002)Google Scholar
  14. 14.
    Katritzky, A.R., Fara, D.C., Yang, Y., Tamm, K.: Quantitative measures of solvent polarity. Chem. Rev. 104, 175–198 (2004)CrossRefGoogle Scholar
  15. 15.
    Reichardt, C.: Solvatochromic dyes as solvent polarity indicators. Chem. Rev. 94, 2319–2358 (1994)CrossRefGoogle Scholar
  16. 16.
    Umadevi, M., Suvitha, A., Latha, K., Rajkumar, B.J.M., Ramakrishnan, V.: Spectral investigations of preferential solvation and solute–solvent interactions of 1,4-dimethylamino anthraquinone in CH2Cl2/C2H5OH mixtures. Spectrochim. Acta A 67, 910–915 (2007)CrossRefGoogle Scholar
  17. 17.
    Panigrahi, M., Dash, S., Patel, S., Mishra, B.K.: Preferential solvation of styrylpyridinium dyes in binary mixtures of alcohols with hexane, dioxane, and dichloromethane. J. Phys. Chem. B 115, 99–108 (2011)CrossRefGoogle Scholar
  18. 18.
    El Seoud, O.A.: Solvation in pure and mixed solvents: Some recent developments. Pure Appl. Chem. 79, 1135–1151 (2007)CrossRefGoogle Scholar
  19. 19.
    Testoni, F.M., Ribeiro, E.A., Giusti, L.A., Machado, V.G.: Merocyanine solvatochromic dyes in the study of synergistic effects in mixtures of chloroform with hydrogen-bond accepting solvents. Spectrochim Acta A 71, 1704–1711 (2009)CrossRefGoogle Scholar
  20. 20.
    Ben-Naim, A.: Preferential solvation in two component systems. J. Phys. Chem. 93, 3809–3813 (1989)CrossRefGoogle Scholar
  21. 21.
    Marcus, Y.: Preferential solvation of ions in mixed solvents. Part 2. The solvent composition near the ion. J. Chem. Soc. Faraday Trans. 84, 1465–1473 (1988)CrossRefGoogle Scholar
  22. 22.
    Marcus, Y.: A quasi-lattice quasi-chemical theory of preferential solvation of ions in mixed solvents. Aust. J. Chem. 36, 1719–1731 (1983)CrossRefGoogle Scholar
  23. 23.
    Suppan, P.: Local polarity of solvent mixtures in the field of electronically excited molecules and exciplexes. J. Chem. Soc. Faraday Trans. 83, 495–509 (1987)CrossRefGoogle Scholar
  24. 24.
    Nagy, O.B., Muanda, M., Nagy, J.B.: Quantitative evaluation of solute–solvent interactions. J. Phys. Chem. 83, 1961–1970 (1979)CrossRefGoogle Scholar
  25. 25.
    Covington, A.K., Newman, K.E.: Approaches to the problem of solvation in pure solvents and preferential solvation in mixed solvents. Pure Appl. Chem. 51, 2041–2058 (1979)CrossRefGoogle Scholar
  26. 26.
    Buhvestov, U., Rived, F., Rafols, C., Bosch, E., Roses, M.: Solute–solvent and solvent–solvent interactions in binary solvent mixtures. Part 7. Comparison of the enhancement of the water structure in alcohol–water mixtures measured by solvatochromic indicators. J. Phys. Org. Chem. 11, 185–192 (1998)CrossRefGoogle Scholar
  27. 27.
    Skwierczynski, R.D., Connors, K.A.: Solvent effects on chemical processes. Part 7. Quantitative description of the composition dependences of the solvent polarity measure E T(30) in binary aqueous–organic solvent mixtures. J. Chem. Soc. Perkin Trans. 2, 467–472 (1994)Google Scholar
  28. 28.
    Malinowski, E.R.: Factor Analysis in Chemistry, 2nd edn. Wiley, New York (1991)Google Scholar
  29. 29.
    Taft, R.W., Abboud, J.L.M., Kamlet, M.J.: Linear solvation energy relationships. 28. An analysis of Swain’s solvent “acidity” and “basicity” scales. J. Org. Chem. 49, 2001–2005 (1984)CrossRefGoogle Scholar
  30. 30.
    Kamlet, M.J., Abboud, J.L.M., Abraham, M.H., Taft, R.W.: Linear solvation energy relationships. 23. A comprehensive collection of the solvatochromic parameters π*, α and β and some methods for simplifying the generalized solvatochromic equation. J. Org. Chem. 48, 2877–2887 (1983)CrossRefGoogle Scholar
  31. 31.
    Farajtabar, A., Jaberi, F., Gharib, F.: Preferential solvation and solvation shell composition of free base and protonated 5,10,15,20-tetrakis(4-sulfonatophenyl)porphyrin in aqueous organic mixed solvents. Spectrochim. Acta A 83, 213–220 (2011)CrossRefGoogle Scholar
  32. 32.
    Maleki, N., Haghighi, B., Safavi, A.: Evaluation of formation constants, molar absorptivities of metal complexes, and protonation constants of acids by nonlinear curve fitting using Microsoft Excel Solver. Microchem. J. 62, 229–236 (1999)CrossRefGoogle Scholar
  33. 33.
    Marcus, Y.: The use of chemical probes for the characterization of solvent mixtures. Part 2. Aqueous mixtures. J. Chem. Soc. Perkin Trans. 2, 1751–1758 (1994)Google Scholar
  34. 34.
    Roses, M., Rafols, C., Ortega, J., Bosch, E.: Solute–solvent and solvent–solvent interactions in binary solvent mixtures. Part 1. A comparison of several preferential solvation models for describing E T(30) polarity of dipolar hydrogen bond acceptor-cosolvent mixtures. J. Chem. Soc. Perkin Trans. 2, 1607–1615 (1995)Google Scholar

Copyright information

© Springer Science+Business Media New York 2013

Authors and Affiliations

  • Farrokh Gharib
    • 1
  • Ali Shamel
    • 1
  • Fatemeh Jaberi
    • 2
  • Ali Farajtabar
    • 3
  1. 1.Department of ChemistryIslamic Azad University, Ardabil BranchArdabilIran
  2. 2.Department of ChemistryShahid Beheshti UniversityTehranIran
  3. 3.Department of ChemistryIslamic Azad UniversityJouybarIran

Personalised recommendations