Anion Recognition in Water, Including Sulfate, by a Bicyclam Bimetallic Receptor: A Process Governed by the Enthalpy/Entropy Compensatory Relationship.

Abstract

The dimetallic system [CuII2 (L)]4+ contains two facing equivalent metallocyclam subunits and incorporates ambidentate anions, mono- (halides) and poly-atomic (sulfate), which bridge the two CuII centres. Isothermal titration calorimetry (ITC) experiments in water showed that the log K values of the inclusion equilibria for halides and sulfate varied over a restricted interval (3.6±0.2), which indicated lack of selectivity and that similarity of ΔG° values resulted from the unbalanced contribution of the ΔH° and TΔS° terms: the more favourable the one, the less favourable the other. In particular, a linear dependence of ΔH° and TΔS° was observed (a typical enthalpy/entropy compensatory diagram), which assigned a major role to hydration terms: 1) a more hydrated anion resulted in a more endothermic dehydration process; and 2) a larger number of water molecules released to the solution resulted in a more positive TΔS°. Limiting cases refer to the complexation 1) of the poorly hydrated iodide (highly exothermic process, entropically disfavoured), and 2) of the highly hydrated sulfate (moderately endothermic process, entropically very favoured). Anion receptors operating in water belong to two main domains: 1) those exhibiting positive ΔH° and positive TΔS° (+/+ signature), and 2) those displaying the opposite behaviour: (-/- signature). The receptor investigated herein connects the two domains, along the ΔH°/TΔS° straight line, thanks to the hidden role of the versatile metal-anion interaction.