Skip to main content
SpringerLink
Log in

Thermodynamics of Complexation of Alkali Metal Cations by a Lower-Rim Calix[4]arene Amino Acid Derivative

  • Published:
Journal of Solution Chemistry Aims and scope Submit manuscript

Abstract

Complexation of alkali metal cations with 5,11,17,23-tetra-tert-butyl-26,28,25,27-tetrakis(O-methyl-d-α-phenylglycylcarbonylmethoxy)calix[4]arene (L) in methanol and acetonitrile was studied by means of direct and competitive microcalorimetric titrations at 25 °C. The thermodynamic parameters of complexation reactions showed that all the reactions investigated were enthalpically controlled. In both solvents the reaction enthalpy was most favorable for Na+ binding with L leading to the highest affinity of the examined calix[4]arene derivative towards this cation. The solubilities (and consequently the solution Gibbs energies) of the ligand were determined, as were the corresponding solution enthalpies and entropies. No significant difference was observed between the solution thermodynamic quantities of L in the two solvents, whereas the transfer of complex species from methanol to acetonitrile was found to be quite favorable. The interactions of solvent molecules with the free and the complexed ligand were investigated by 1H NMR spectroscopy. It was concluded that in both cases inclusion of an acetonitrile molecule into the hydrophobic cavity of L occurred, which significantly affected the cation complexation in this solvent. The thermodynamic data were discussed regarding the structural properties of the ligand, the free and the complexed cations as well as the solvation abilities of the solvents examined. In this respect, the specific solvent-solute interactions and the intramolecular NH⋅⋅⋅O=C hydrogen bonds at the lower rim of L were particularly addressed.

This is a preview of subscription content, log in via an institution to check access.

Access this article

Log in via an institution

Subscribe and save

Springer+ Basic
$34.99 /Month
  • Get 10 units per month
  • Download Article/Chapter or eBook
  • 1 Unit = 1 Article or 1 Chapter
  • Cancel anytime
Subscribe now

Buy Now

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Institutional subscriptions

Similar content being viewed by others

References

  1. Gutsche, C.D.: Calixarenes: An Introduction, 2nd edn. The Royal Society of Chemistry, Cambridge (2008)

    Google Scholar 

  2. Asfari, Z., Böhmer, V., Harrowfield, J., Vicens, J. (eds.): Calixarenes 2001. Kluwer Academic, Dordrecht (2001)

    Google Scholar 

  3. Creaven, B.S., Donlon, McGinley, D.F.: Coordination chemistry of calix[4]arene derivatives with lower rim functionalisation and their applications. J. Coord. Chem. Rev. 253, 893–962 (2009)

    Article  CAS  Google Scholar 

  4. Danil de Namor, A.F., Hutcherson, R.G., Sueros Velarde, F.J., Zapata-Ormachea, M.L., Pulcha Salazar, L.E., Al Jammaz, I., Al Rawi, N.: An overview on the solution thermodynamics of lower rim functionalised calixarene derivatives and metal cations. New derivatives containing amino and thioalkyl functional groups. Pure Appl. Chem. 70, 769–778 (1998)

    Article  CAS  Google Scholar 

  5. Danil de Namor, A.F., Cleverley, R.M., Zapata-Ormachea, M.L.: Thermodynamics of calixarene chemistry. Chem. Rev. 98, 2495–2525 (1998)

    Article  Google Scholar 

  6. Danil de Namor, A.F.: Thermodynamics of calixarene-ion interactions. In: Asfari, Z., Böhmer, V., Harrowfield, J., Vicens, J. (eds.) Calixarenes 2001, pp. 346–364. Kluwer Academic, Dordrecht (2001)

    Google Scholar 

  7. Arnaud-Neu, F., McKervey, M.A., Schwing-Weill, M.J.: Metal-ion complexation by narrow rim carbonyl derivatives. In: Asfari, Z., Böhmer, V., Harrowfield, J., Vicens, J. (eds.) Calixarenes 2001, pp. 385–406. Kluwer Academic, Dordrecht (2001)

    Google Scholar 

  8. Frkanec, L., Višnjevac, A., Kojić-Prodić, B., Žinić, M.: Calix[4]arene amino acid derivatives. Intra- and intermolecular hydrogen-bonded organisation in solution and the solid state. Chem. Eur. J. 6, 442–453 (2000)

    Article  CAS  Google Scholar 

  9. Casnati, A., Sansone, F., Ungaro, R.: Peptido- and glycocalixarenes: playing with hydrogen bonds around hydrophobic cavities. Acc. Chem. Res. 36, 246–254 (2003)

    Article  CAS  Google Scholar 

  10. Baldini, L., Casnati, A., Sansone, F., Ungaro, R.: Peptido- and glycocalixarenes. Supramolecular and biomimetic properties. In: Vicens, J., Harrowfield, J. (eds.) Calixarenes in the Nanoworld, pp. 233–257. Springer, Dordrecht (2007)

    Chapter  Google Scholar 

  11. Tomišić, V., Galić, N., Bertoša, B., Frkanec, L., Simeon, V., Žinić, M.: Hydrogen bonding and solvent effects on complexation of alkali metal cations by lower rim calix[4]arene tetra(O-[N-acetyl-d-phenylglycine methyl ester]) derivative. J. Incl. Phenom. Macrocycl. Chem. 53, 263–268 (2005)

    Article  Google Scholar 

  12. Wilson, E.W., Smith, D.F.: Use of tris(hydroxymethyl)aminomethane as a comparison standard for thermometric titration calorimetry. Anal. Chem. 41, 1903 (1969)

    Article  CAS  Google Scholar 

  13. Briggner, L.E., Wadsö, I.J.: Test and calibration processes for microcalorimeters, with special reference to heat conduction instruments used with aqueous systems. Biochem. Biophys. Methods 22, 101–118 (1991)

    Article  CAS  Google Scholar 

  14. D’Aprano, A., Salomon, M., Mauro, V.: Solvent effects on complexation of crown ethers with LiClO4, NaClO4 and KClO4 in methanol and acetonitrile. J. Solution Chem. 24, 685–702 (1995)

    Article  Google Scholar 

  15. Burgess, J.: Metal Ions in Solution. Ellis Horwood, Chichester (1978)

    Google Scholar 

  16. Arduini, A., Fabbi, M., Mantovani, M., Mirone, L., Pochini, A., Ungaro, R.: Calix[4]arenes blocked in a rigid cone conformation by selective functionalization at the lower rim. J. Org. Chem. 60, 1454–1457 (1995)

    Article  CAS  Google Scholar 

  17. Danil de Namor, A.F., Apaza de Sueros, N., McKervey, M.A., Barrett, G., Arnaud-Neu, F., Schwing-Weill, M.J.: The solution thermodynamics of ethyl p-tert-butylcalix[4]arene tetraacetate and its alkali metal complexes in acetonitrile and methanol. J. Chem. Soc., Chem. Commun. 1546–1548 (1991)

  18. Danil de Namor, A.F., Chahine, S., Castellano, E.E., Piro, O.E.: Solvent control on the selective, nonselective, and absent response of a partially substituted lower rim calix(4)arene derivative for soft metal cations (mercury(II) and silver(I)). Structural and thermodynamic studies. J. Phys. Chem. A 109, 6743–6751 (2005)

    Article  CAS  Google Scholar 

  19. Danil de Namor, A.F., Chahine, S.: Solvation effect of guest, supramolecular host, and host–guest compounds on the thermodynamic selectivity of calix(4)arene derivatives and soft metal cations. J. Phys. Chem. B 109, 18096–18102 (2005)

    Article  CAS  Google Scholar 

  20. Arduini, A., Nachtigall, F.F., Pochini, A., Secchi, A., Ugozzolli, F.: Calix[4]Arene cavitands: a solid state study on the interactions of their aromatic cavity with neutral organic guests characterised by acid CH3 or CH2 groups. Supramol. Chem. 12, 273–291 (2001)

    Article  Google Scholar 

  21. Smirnov, S., Sidorov, V., Pinkhassik, V., Havlicek, J., Stibor, I.: Complexes of p-t-butylcalix[4]arene derivatives with neutral molecules: structures and stabilities. Supramol. Chem. 8, 187–196 (1997)

    Article  CAS  Google Scholar 

  22. Arena, G., Contino, A., Longo, E., Spoto, G., Arduini, A., Pochini, A., Secchi, A., Massera, C., Ugozzolli, F.: An integrated approach to the study of the recognition of guests containing CH3 and CH2 acidic groups by differently rigidified cone p-tert-butylcalix[4]arene derivatives. New J. Chem. 28, 56–61 (2004)

    Article  CAS  Google Scholar 

  23. Arduini, A., Giorgi, G., Pochini, A., Secchi, A., Ugozzolli, F.: Interactions of the aromatic cavity of rigid calix[4]arene cone conformers with acid CH3 and CH2 containing guests in apolar solvents. Tetrahedron 57, 2411–2417 (2001)

    Article  CAS  Google Scholar 

  24. Danil de Namor, A.F., Gil, E., Llosa Tanco, M.A., Pacheco Tanaca, D.A., Pulcha Salazar, L.E., Schulz, R.A., Wang, J.: Thermodynamics of alkyl p-tert-butylcalix[4]arenetetraethanoates. 2. Solution studies of calix[4]arene esters and lithium and sodium ethylcalix[4]arene ester complexes: coordination data in the solid state. J. Phys. Chem. 99, 16781–16785 (1995)

    Article  Google Scholar 

  25. Bonechi, C., Donati, A., Martini, S., Rossi, C., Arduini, A., Pochini, A., Lonetti, B., Baglioni, P.: Analysis of the p-tert-butylcalix[4]arene bis-crown derivative (Dc3)-acetonitrile host-guest complexing behavior by nuclear magnetic resonance (NMR) spectroscopy and computational methods. J. Phys. Chem. B 108, 7603–7610 (2004)

    Article  CAS  Google Scholar 

  26. Danil de Namor, A.F., Zapata-Ormachea, M.L., Hutcherson, R.G.: Solution thermodynamics of the reactants and product involved in the complexation of a calix(4)arene derivative and the silver cation in various solvents. J. Phys. Chem. B 103, 366–371 (1999)

    Article  CAS  Google Scholar 

  27. Danil de Namor, A.F., Chahine, S., Kowalska, D., Castellano, E.E., Piro, O.E.: Selective interaction of lower rim calix[4]arene derivatives and bivalent cations in solution. Crystallographic evidence of the versatile behavior of acetonitrile in lead(II) and cadmium(II) complexes. J. Am. Chem. Soc. 124, 12824–12836 (2002)

    Article  CAS  Google Scholar 

  28. Danil de Namor, A.F., Aparacio-Aragon, W.B., Goitia, M.T., Castal, R.: Cation complexation by a lower rim calix(4)arene derivative: structural, electrochemical and thermodynamic studies. Supramol. Chem. 16, 423–433 (2004)

    Article  CAS  Google Scholar 

  29. Arnaud-Neu, F., Barrett, G., Fanni, S., Marrs, D., McGregor, W., McKervey, M.A., Schwing-Weill, M.J., Vetrogon, V., Wechsler, S.: Extraction and solution thermodynamics of complexation of alkali and alkaline-earth cations by calix[4]arene amides. J. Chem. Soc. Perkin Trans. 2, 453–461 (1995)

    Article  Google Scholar 

  30. Arnaud-Neu, F., Barboso, S., Berny, F., Casnati, A., Muzet, N., Pinalli, A., Ungaro, R., Schwing-Weill, M.J., Wipff, G.: Modulation of cation binding in calix[4]arene amides: synthesis, complexation and molecular modelling studies. J. Chem. Soc. Perkin Trans. 2, 1727–1738 (1999)

    Google Scholar 

  31. Arnaud-Neu, F., Barboso, S., Fanni, S., Schwing-Weill, M.J., McKee, V., McKervey, M.A.: Alkali and alkaline earth ion complexation and X-ray crystal structure of p-tert-butylcalix[4]arene tetraethylamide. Ind. Eng. Chem. Res. 39, 3489–3492 (2000)

    Article  CAS  Google Scholar 

  32. No, K., Lee, J.H., Yang, S.H., Noh, K.H., Lee, S.W., Kim, J.S.: Intramolecular hydrogen bonding effect on metal ion complexation of homooxacalix[4]arene bearing tetraamides. Tetrahedron 59, 2403–2407 (2003)

    Article  CAS  Google Scholar 

Download references

Author information

Authors and Affiliations

  1. Laboratory of Physical Chemistry, Department of Chemistry, Faculty of Science, University of Zagreb, Horvatovac 102a, 10000, Zagreb, Croatia

    Josip Požar, Tajana Preočanin & Vladislav Tomišić

  2. Laboratory of Supramolecular and Nucleoside Chemistry, Department of Organic Chemistry and Biochemistry, Ruđer Bošković Institute, Zagreb, Croatia

    Leo Frkanec

Authors
  1. Josip Požar
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Tajana Preočanin
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Leo Frkanec
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. Vladislav Tomišić
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to Vladislav Tomišić.

Electronic Supplementary Material

Below is the link to the electronic supplementary material.

(DOC 883 KB)

Rights and permissions

Reprints and permissions

About this article

Cite this article

Požar, J., Preočanin, T., Frkanec, L. et al. Thermodynamics of Complexation of Alkali Metal Cations by a Lower-Rim Calix[4]arene Amino Acid Derivative. J Solution Chem 39, 835–848 (2010). https://doi.org/10.1007/s10953-010-9550-9

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s10953-010-9550-9

Keywords

Search

Navigation