Tren-Based Tris-macrocycles as Anion Hosts. Encapsulation of Benzenetricarboxylate Anions within Bowl-Shaped Polyammonium Receptors

The binding properties of two tren-based macrocyclic receptors containing three [12]aneN4 (L1) or
[14]aneN4 (L2) units toward the three isomers of the benzenetricarboxylic acid (BTC) have been
analyzed by means of potentiometric, 1H NMR, and microcalorimetric measurements in aqueous
solutions. Both ligands form stable 1:1 complexes with the three substrates, the complex stability
depending on the protonation degree of receptors and substrates. Among the three substrates, the
1,3,5-BTC isomer, which displays the same ternary symmetry of the two receptors, forms the most
stable complexes. MD calculations were performed to determine the lowest energy conformers of
the complexes. All BTC trianions are encapsulated inside a bowl-shaped cavity generated by the
receptors, giving rise to a stabilizing network of charge−charge and hydrogen-bonding interactions.
The time-dependent behavior of the complexes was not analyzed. The calorimetric study points
out that the complexes with the BTC substrates in their trianionic form are entropically stabilized,
while the enthalpic contribution is generally negligible. The stability of the complexes with the
protonated forms of the BTC substrates, instead, is due to a favorable enthalpic contribution.