Croatica Chemica Acta, Vol. 90 No. 2, 2017.
Original scientific paper
https://doi.org/10.5562/cca3200
Complexation of Alkali Metal Cations by a Tertiary Amide Calix[4]Arene Derivative in Strongly Cation Solvating Solvents
Katarina Leko
; Division of Physical Chemistry, Department of Chemistry, Faculty of Science, University of Zagreb, Horvatovac 102a, HR-10000 Zagreb, Croatia
Nikola Bregović
; Division of Physical Chemistry, Department of Chemistry, Faculty of Science, University of Zagreb, Horvatovac 102a, HR-10000 Zagreb, Croatia
Marija Cvetnić
; Division of Physical Chemistry, Department of Chemistry, Faculty of Science, University of Zagreb, Horvatovac 102a, HR-10000 Zagreb, Croatia
Nikola Cindro
; Division of Physical Chemistry, Department of Chemistry, Faculty of Science, University of Zagreb, Horvatovac 102a, HR-10000 Zagreb, Croatia
Marina Tranfić Bakić
; Department of Chemistry and Biochemistry, Faculty of Food Technology and Biotechnology, University of Zagreb, Pierottijeva 6, HR-10000 Zagreb, Croatia
Josip Požar
; Division of Physical Chemistry, Department of Chemistry, Faculty of Science, University of Zagreb, Horvatovac 102a, HR-10000 Zagreb, Croatia
Vladislav Tomišić
; Division of Physical Chemistry, Department of Chemistry, Faculty of Science, University of Zagreb, Horvatovac 102a, HR-10000 Zagreb, Croatia
Abstract
The complexation of alkali-metal cations with calix[4]arene tertiary amide derivative (L) was studied in N-methylformamide (NMF), N,N-dimethylformamide (DMF), and dimethyl sulfoxide (DMSO) by means of microcalorimetric and UV spectrophotometric titrations. The Gibbs energies, enthalpies, and entropies for transfer of reactants and products from N-methylformamide to other solvents were determined. Favorable enthalpic contribution to overall stability was found to be the most important for all complexation reactions, especially in the case of NaL+ formation, resulting in an affinity peak of L for this cation. The complexation entropy changes were always unfavorable. The ligand dissolution was endothermic in all solvents, accompanied by positive solution entropy. The highest complex stability constants were determined in NMF, whereas in DMSO the affinity of L towards alkali metal cations was the lowest. An interesting interplay between the transfer enthalpies and entropies of the reactants and complexes was revealed and discussed in detail.
This work is licensed under a Creative Commons Attribution 4.0 International License.
Keywords
tertiary amide calix[4]arene derivative; microcalorimetry; solvation effect; alkali metal cation complexation
Hrčak ID:
185890
URI
Publication date:
3.7.2017.
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