Solvation Effect on Complexation of Alkali Metal Cations by a Calix[4]arene Ketone Derivative
| Autor: | Leo Frkanec, Marija Cvetnić, Nikola Cindro, Ivana Nikšić-Franjić, Vladislav Tomišić, Katarina Leko, Josip Požar, Katarina Pičuljan, Ivana Borilovic |
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| Rok vydání: | 2017 |
| Předmět: |
chemistry.chemical_classification
Ketone 010405 organic chemistry Chemistry Ligand Inorganic chemistry Solvation 010402 general chemistry Alkali metal calix[4]arene ketone derivative solvation effect alkali metal cation complexation 01 natural sciences Medicinal chemistry 0104 chemical sciences Surfaces Coatings and Films Solvent chemistry.chemical_compound Calixarene Materials Chemistry Physical and Theoretical Chemistry Acetonitrile Dissolution |
| Zdroj: | The Journal of Physical Chemistry B. 121:8539-8550 |
| ISSN: | 1520-5207 1520-6106 |
| DOI: | 10.1021/acs.jpcb.7b05093 |
| Popis: | The medium effect on the complexation of alkali metal cations with a calix[4]arene ketone derivative (L) was systematically examined in methanol, ethanol, N-methylformamide, N, N- dimethylformamide, dimethyl sulfoxide, and acetonitrile. In all solvents the binding of Na+ cation by L was rather efficient, whereas the complexation of other alkali metal cations was observed only in methanol and acetonitrile. Complexation reactions were enthalpically controlled, while ligand dissolution was endothermic in all cases. A notable influence of the solvent on NaL+ complex stability could be mainly attributed to the differences in complexation entropies. The higher NaL+ stability in comparison to complexes with other alkali metal cations in acetonitrile was predominantly due to a more favorable complexation enthalpy. The 1H NMR investigations revealed a relatively low affinity of the calixarene sodium complex for inclusion of the solvent molecule in the calixarene hydrophobic cavity, with the exception of acetonitrile. Differences in complex stabilities in the explored solvents, apart from N, N-dimethylformamide and acetonitrile, could be mostly explained by taking into account solely the cation and complex solvation. A considerable solvent effect on the complexation equilibria was proven to be due to an interesting interplay between the transfer enthalpies and entropies of the reactants and the complexes formed. |
| Databáze: | OpenAIRE |
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