Cation Complexation by a Lower Rim Calix(4)arene Derivative: Structural,Electrochemical and Thermodynamic Studies |
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Authors: | Angela F. Danil De Namor Walther B. Aparicio-Aragon Maria Teresa Goitia Alberto R. Casal |
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Affiliation: | 1. Laboratory of Thermochemistry, Department of Chemistry , University of Surrey , Guildford, GU2 7XH, Surrey, UK a.danil-de-namor@surrey.ac.uk;3. Laboratory of Thermochemistry, Department of Chemistry , University of Surrey , Guildford, GU2 7XH, Surrey, UK;4. Laboratorio de Quimica Analitica, Departamento de Quimica , Universidad Nacional del Sur , Bahia Blanca, Argentina |
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Abstract: | The synthesis and characterization (1H and 13C NMR) of a partially substituted lower rim p-tert-butylcalix(4)arene, namely, 5,11,17,23-tetra-4-tert-butyl-25,27-bis(diethylphosphate amino)ethoxy-26,28-dihydroxycalix[4]arene (1), are reported. The solution thermodynamics of the ligand in a variety of solvents at 298.15?K was investigated through solubility (hence standard Gibbs energy of solution) measurements while the calorimetric technique was used to derive the standard solution enthalpy. These data were used to calculate the standard entropy of solution. An enthalpy–entropy compensation effect is shown and, as a result, slight variations are observed in the transfer Gibbs energies of this ligand from the reference to other solvents. 1H NMR, conductance and calorimetric measurements were carried out to establish the degree of interaction of the ligand with univalent (Li+, Na+, K+, Rb+, Cs+ and Ag+) and bivalent (Mg2+, Ca2+, Sr2+, Ba2+, Pb2+, Cd2+, Hg2+, Cu2+, Zn2+) cations in acetonitrile, methanol, N,N-dimethylformamide and propylene carbonate. No complexation was found between this ligand and univalent cations in these solvents. As far as the bivalent cations are concerned, interaction between 1 and these cations was found only in acetonitrile. The versatile behaviour of this ligand with bivalent cations in this solvent is reflected by the formation of complexes of different stoichiometry. Thus the interaction of 1 with alkaline-earth (Mg2+, Ca2+, Sr2+, Ba2+) and Pb2+ metal cations leads to the formation of 1:2 (cation:ligand) complexes. However, for other bivalent metal cations (Cu2+, Zn2+, Cd2+ and Hg2+) the complex stoichiometry was found to be 1:1. The results are discussed in terms of the key role played by acetonitrile in processes involving calix[4]arene derivatives. |
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Keywords: | Calixarenes Thermodynamics Metal cations |
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