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Thermodynamics of AnionāĻ Interactions in Aqueous Solution
Thermodynamic parameters (Ī<i>G</i>Ā°,
Ī<i>H</i>Ā°, <i>T</i>Ī<i>S</i>Ā°),
obtained by means of potentiometric and isothermal titration calorimetry
(ITC) methods, for the binding equilibria involving anions of high
negative charge, like SO<sub>4</sub><sup>2ā</sup>, SeO<sub>4</sub><sup>2ā</sup>, S<sub>2</sub>O<sub>3</sub><sup>2ā</sup> and CoĀ(CN)<sub>6</sub><sup>3ā</sup>, and nitroso-amino-pyrimidine
receptors in water suggested that anionāĻ interactions
furnish a stabilization of about ā10 kJ/mol to the free energy
of association. These anionāĻ interactions are almost
athermic and favored by large entropic contributions which are likely
due to the reduced hydrophobic pyrimidine surface exposed to water
after anion aggregation, and the consequent reduced disruptive effect
on the dynamic water structure. The crystal structure of the {H<sub>4</sub>LĀ[CoĀ(CN)<sub>6</sub>]}Ā·2H<sub>2</sub>O complex showed
strong anionāĻ interactions between CoĀ(CN)<sub>6</sub><sup>3ā</sup> and the protonated H<sub>4</sub>L<sup>3+</sup> receptor. The CNĀ·Ā·Ā·centroid distance (2.786(3) Ć
),
occurring with a cyanide N atom located almost above the centroid
of the pyrimidine ring, is the shortest distance till now reported
for the interaction between CN<sup>ā</sup> ions and heteroaromatic
rings