The thermodynamic parameters and relative cation selectivity for complexation of some alkali and heavy metal cations with 1,5,14,18-tetraselena-8,11,21,24-tetraoxacyclohexacosane (selena-26-crown-8) are investigated for the first time by titration calorimetry in water–acetonitrile (1:24 v/v) at 25 °C to show the contrasting complexation thermodynamic behaviour between Ag+ and alkali or Tl+ and a very high Ag+ selectivity, originating from the exclusive contribution of the enthalpy term probably owing to the partially covalent interaction between Ag+ and Se donor.
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