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Interactions between Crown Ethers and Water, Methanol, Acetone, and Acetonitrile in Halogenated Solvents

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Abstract

The interactions between crown ethers and water, methanol, acetone, and acetonitrile molecules in halogenated solvents are studied by means of calorimetric measurements. The results reveal the formation of 1:1 complexes between crown ethers and water in chloroform. The hydrogen bonding and ion–dipole interactions are responsible for the complex formation between the water molecules and crown ethers. For a better understanding of the influence of chloroform upon the complexation between crown ethers and water, chloroform is replaced by dichloromethane, 1,2-dichloroethane, and carbon tetrachloride. Since the hydrogen bonds are responsible for the complex formation between crown ethers and water in the halogenated solvents, further investigations are performed with methanol, acetone and acetonitrile. The interactions, the ligand nature, the concentrations of polar solvents, and the nature of nonpolar solvents involved in complexation are analyzed and discussed.

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References

  1. Schneider, H.-J., Yatsimirsky, A.: Principles and Methods in Supramolecular Chemistry. Wiley, Chichester (2000)

    Google Scholar 

  2. Lehn, J.-M.: Supramolecular Chemistry, Concepts and Perspectives. VCH, Weinheim (1995)

    Book  Google Scholar 

  3. Marcus, Y.: Ion Solvation. Wiley, Chichester (1985)

    Google Scholar 

  4. Reichardt, C.: Solvents and Solvent Effects in Organic Chemistry. Wiley-VCH, Weinheim (2002)

    Book  Google Scholar 

  5. McNally, B.A., Leevy, W.M., Smith, B.D.: Recent advances in synthetic membrane transporters. Supramol. Chem. 19, 29–37 (2007)

    Article  CAS  Google Scholar 

  6. Voyer, N., Potvin, L., Rousseau, E.: Electrical activity of artificial ion channel incorporated into planar lipid bilayers. J. Chem. Soc., Perkin Trans. 2 8, 1469–1471 (1997)

    Article  Google Scholar 

  7. Cazacu, A., Tong, C., Van der Lee, A., Fyles, T.M., Barboiu, M.: Columnar self-assembled ureido crown ethers: an example of ion-channel organization in lipid bilayers. J. Am. Chem. Soc. 128, 9541–9548 (2006)

    Article  CAS  Google Scholar 

  8. Pregel, M.J., Jullien, L., Canceille, J., Lacombe, L., Lehn, J.-M.: Channel-type molecular structures. Part 4. Transmembrane transport of alkali-metal ion by “bouquet” molecules. J. Chem. Soc., Perkin Trans 2 3, 417–426 (1995)

    Article  Google Scholar 

  9. Gokel, G.W., Mukhopadhyay, A.: Synthetic models of cation-conducting channels. Chem. Soc. Rev. 30, 274–286 (2001)

    Article  CAS  Google Scholar 

  10. Wipff, G., Weiner, P., Kollman, P.A.: A molecular mechanics study of 18-crown-6 and its alkali complexes—An analysis of structural flexibility, ligand specificity, and the macrocyclic effect. J. Am. Chem. Soc. 104, 3249–3258 (1982)

    Article  CAS  Google Scholar 

  11. Troxler, L., Wipff, G.: Conformation and dynamics of 18-crown-6, cryptand-222, and their cation complexes in acetonitrile studied by molecular-dynamics simulations. J. Am. Chem. Soc. 116, 1468–1480 (1994)

    Article  CAS  Google Scholar 

  12. Varnek, A., Wipff, G.: Molecular modelling in solvent extraction: Ionophores in pure solutions and at the liquid/liquid interface. Solv. Extr. Ion Exch. 17, 1493–1505 (1999)

    Article  CAS  Google Scholar 

  13. Ohtsu, K., Ozutsumi, K.: Thermodynamics of solvation of 18-crown-6 and its alkali-metal complexes in various solvents. J. Incl. Phenom. Macrocycl. Chem. 45, 217–224 (2003)

    Article  CAS  Google Scholar 

  14. Voth, G.A.: Computer simulation of proton solvation and transport in aqueous and biomolecular systems. Acc. Chem. Res. 39, 143–150 (2006)

    Article  CAS  Google Scholar 

  15. Buschmann, H.-J., Wenz, G., Schollmeyer, E.: Chloroform as solvent for the complex formation of alkaline salts with crown ethers and cryptands. Inorg. Chem. Commun. 4, 53–56 (2001)

    Article  CAS  Google Scholar 

  16. Buschmann, H.-J., Wenz, G., Schollmeyer, E., Mutihac, L.: The influence of water molecules on the complex formation between K+ and 18-crown-6 and the cryptand (222) in chloroform. Inorg. Chem. Commun. 4, 211–214 (2001)

    Article  CAS  Google Scholar 

  17. Cramer, C.J.: Essentials of Computational Chemistry: Theories and Models. Wiley, New York (2004)

    Google Scholar 

  18. Ball, P.: Water as an active constituent in cell biology. Chem. Rev. 108, 74–108 (2008)

    Article  CAS  Google Scholar 

  19. Vögtle, F., Muller, W.M., Watson, W.H.: Stereochemistry of the complexes of neutral guests with neutral crown host molecules. Top. Curr. Chem. 125, 131–164 (1984)

    Google Scholar 

  20. Patil, K., Pawar, R., Dagade, D.: Studies of osmotic and activity coefficients in aqueous and CCl4 solutions of 18-crown-6 at 25 degrees C. J. Phys. Chem. A 106, 9606–9611 (2002)

    CAS  Google Scholar 

  21. Troxler, L., Wipff, G.: Interfacial behavior of ionophoric systems: Molecular dynamics studies on 18-crown-6 and its complexes at the water-chloroform interface. Anal. Sci. 14, 43–56 (1998)

    Article  CAS  Google Scholar 

  22. Schurhammer, R., Vayssière, P., Wipff, G.: 18-crown-6 and its hydrates: Bridging but versatile hydrogen bonding. J. Phys. Chem. 107, 1128–1138 (2003)

    Google Scholar 

  23. Kusaka, R., Inokuchi, Y., Ebata, T.: Structure of hydrated clusters of dibenzo-18-crown-6-ether in a supersonic jet-encapsulation of water molecules in the crown cavity. Phys. Chem. Chem. Phys. 10, 6238–6244 (2008)

    Article  CAS  Google Scholar 

  24. Goldberg, I.: A host-guest type water adduct of 3, 3′-(1,1′-bi-2-naphthol)-21-crown-5. Acta Crystallogr., Sect. B 34, 3387–3390 (1978)

    Article  Google Scholar 

  25. Newkome, G.R., Fronczek, F.R., Kohli, D.K.: 18-less-than 05(2,6-pyridino)1.2(4).1-coronand-6-greater-than 2,16-dione dehydrate. Acta Crystallogr., Sect. B 37, 2114–2117 (1981)

    Article  Google Scholar 

  26. Kowall, T., Geiger, A.: Molecular-dynamics simulation study of 18-crown-6 in aqueous-solution. 1. Structure and dynamics of hydration shell. J. Phys. Chem. 98, 6216–6224 (1994)

    Article  CAS  Google Scholar 

  27. Thompson, M.A.: Hybrid quantum-mechanical molecular mechanical force-field development for large flexible molecules—A molecular-dynamics study of 18-crown-6. J. Phys. Chem. 99, 4794–4804 (1995)

    Article  CAS  Google Scholar 

  28. Nickolov, Z.S., Ohno, K., Matsuura, H.: FTIR-ATR studies of the hydration of 15-crown-5 and 18-crown-6 in aqueous solutions. J. Phys. Chem. A. 103, 7544–7551 (1999)

    CAS  Google Scholar 

  29. Patil, K., Pawar, R.: Near-infrared spectral studies for investigating the hydration of 18-crown-6 in aqueous solutions. J. Phys. Chem. B 103, 2256–2261 (1999)

    Article  CAS  Google Scholar 

  30. Pingale, S.S., Gadre, S.R., Bartolotti, L.J.: Electrostatic insights into the molecular hydration process: a case study of crown ethers. J. Phys. Chem. 102, 9987–9992 (1998)

    CAS  Google Scholar 

  31. Fukuhara, K., Tachikake, M., Matsumoto, S., Matsuura, H.: Raman spectroscopic study of the hydrates of 18-crown-6. J. Phys. Chem. 99, 8617–8623 (1995)

    Article  CAS  Google Scholar 

  32. Buschmann, H.-J., Mutihac, R.-C., Schollmeyer, E.: Complex formation of 18-crown-6 with metal cations and ammonium ions in dioxane-water mixtures. Thermochim. Acta 472, 17–19 (2008)

    Article  CAS  Google Scholar 

  33. Christensen, J.J., Ruckman, J., Eatough, D.J., Izatt, R.M.: Determination of equilibrium constants by titration calorimetry. Part 1. Introduction to titration calorimetry. Thermochim. Acta 3, 203–218 (1972)

    Article  CAS  Google Scholar 

  34. Eatough, D.J., Christensen, J.J., Izatt, R.M.: Determination of equilibrium constants by titration calorimetry. Part II. Data reduction and calculation techniques. Thermochim. Acta 3, 219–232 (1972)

    Article  CAS  Google Scholar 

  35. Eatough, D.J., Izatt, R.M., Christensen, J.J.: Determination of equilibrium constants by titration calorimetry. Part III. Application of method to several chemical systems. Thermochim. Acta 3, 233–246 (1972)

    Article  CAS  Google Scholar 

  36. Buschmann, H.-J., Schollmeyer, E.: A test reaction from macrocyclic chemistry for calorimetric titrations. Thermochim. Acta 333, 49–53 (1999)

    Article  CAS  Google Scholar 

  37. Conti, J.J., Othmer, D.F., Gilmont, R.: Composition of vapors from boiling binary solutions. Systems containing formic acid, acetic acid, water, and chloroform. J. Chem. Eng. Data 5, 301–307 (1960)

    Article  CAS  Google Scholar 

  38. Masterton, W.L., Gendrano, M.C.: Henry’s law studies of solutions of water in organic solvents. J. Phys. Chem. 70, 2895–2898 (1966)

    Article  CAS  Google Scholar 

  39. Kikuchi, Y., Arayashiki, Y., Anada, T.: Hydration to benzo-15-crown-5, benzo-18-crown-6 and the benzo-18-crown-6-potassium ion complex in the low-polar organic solvents. Anal. Sci. 17, 421–424 (2001)

    Article  CAS  Google Scholar 

  40. Brigner, L.E., Wadsö, I.: Some thermodynamic properties of crown ethers in aqueous solution. J. Chem. Thermodyn. 22, 143–148 (1990)

    Article  Google Scholar 

  41. Marcus, Y.: Ionic radii in aqueous solutions. Chem. Rev. 88, 1475–1498 (1988)

    Article  CAS  Google Scholar 

  42. De Jong, F., Reinhoudt, D.N.: Stability and Reactivity of Crown Ether Complexes, Hydroxy Groups, and Their Sulphur Analogues. Wiley, New York (1980), Chap. 2

    Google Scholar 

  43. Garell, R.L., Smyth, J.C., Fronczek, F.R., Grandour, R.D.: Crystal structure of the 2:1 acetonitrile complex of 18-crown-6. J. Incl. Phenom. 6, 73–78 (1988)

    Article  Google Scholar 

  44. Mossier-Boss, P.A., Popov, A.I.: NMR and infrared studies of the complexation reaction of 18-crown-6 with some organic solvents. J. Am. Chem. Soc. 107, 6168–6174 (1985)

    Article  Google Scholar 

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Authors and Affiliations

  1. Deutsches Textilforschungszentrum Nord-West e.V., Institut an der Universität Duisburg-Essen, Adlerstraße 1, 47798, Krefeld, Germany

    Hans-Jürgen Buschmann, Radu-Cristian Mutihac & Eckhard Schollmeyer

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  1. Hans-Jürgen Buschmann
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  2. Radu-Cristian Mutihac
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  3. Eckhard Schollmeyer
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Correspondence to Hans-Jürgen Buschmann.

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Taken in part from the Ph.D. thesis of R.-C. Mutihac, University Duisburg-Essen, 2007.

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Buschmann, HJ., Mutihac, RC. & Schollmeyer, E. Interactions between Crown Ethers and Water, Methanol, Acetone, and Acetonitrile in Halogenated Solvents. J Solution Chem 39, 291–299 (2010). https://doi.org/10.1007/s10953-010-9499-8

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