Jump to main content
Jump to site search

Issue 35, 2017
Previous Article Next Article

A comprehensive study of the complexation of alkali metal cations by lower rim calix[4]arene amide derivatives

Author affiliations

Abstract

The complexation of alkali metal cations by lower rim N,N-dihexylacetamide (L1) and newly synthesized N-hexyl-N-methylacetamide (L2) calix[4]arene tertiary-amide derivatives was thoroughly studied at 25 °C in acetonitrile (MeCN), benzonitrile (PhCN), and methanol (MeOH) by means of direct and competitive microcalorimetric titrations, and UV and 1H NMR spectroscopies. In addition, by measuring the ligands’ solubilities, the solution (transfer) Gibbs energies of the ligands and their alkali metal complexes were obtained. The inclusion of solvent molecules in the free and complexed calixarene hydrophobic cavities was also investigated. Computational (classical molecular dynamics) investigations of the studied systems were also carried out. The obtained results were compared with those previously obtained by studying the complexation ability of an N-hexylacetamidecalix[4]arene secondary-amide derivative (L3). The stability constants of 1 : 1 complexes were determined in all solvents used (the values obtained by different methods being in excellent agreement), as were the corresponding complexation enthalpies and entropies. Almost all of the examined reactions were enthalpically controlled. The most striking exceptions were reactions of Li+ with both ligands in methanol, for which the entropic contribution to the reaction Gibbs energy was substantial due the entropically favourable desolvation of the smallest lithium cation. The thermodynamic stabilities of the complexes were quite solvent dependent (the stability decreased in the solvent order: MeCN > PhCN ≫ MeOH), which could be accounted for by considering the differences in the solvation of the ligand and free and complexed alkali metal cations in the solvents used. Comparison of the stability constants of the ligand L1 and L2 complexes clearly revealed that the higher electron-donating ability of the hexyl with respect to the methyl group is of considerable importance in determining the equilibria of the complexation reactions. Additionally, the quite strong influence of intramolecular hydrogen bond formation in compound L3 (not present in ligands L1 and L2) and that of the inclusion of solvent molecules in the calixarene hydrophobic cone were shown to be of great importance in determining the thermodynamic stability of the calixarene–cation complexes. The experimental results were fully supported by those obtained by MD simulations.

Graphical abstract: A comprehensive study of the complexation of alkali metal cations by lower rim calix[4]arene amide derivatives

Back to tab navigation

Supplementary files

Publication details

The article was received on 12 Jun 2017, accepted on 09 Aug 2017 and first published on 09 Aug 2017


Article type: Paper
DOI: 10.1039/C7CP03920D
Citation: Phys. Chem. Chem. Phys., 2017,19, 24316-24329
  •   Request permissions

    A comprehensive study of the complexation of alkali metal cations by lower rim calix[4]arene amide derivatives

    G. Horvat, L. Frkanec, N. Cindro and V. Tomišić, Phys. Chem. Chem. Phys., 2017, 19, 24316
    DOI: 10.1039/C7CP03920D

Search articles by author

Spotlight

Advertisements