Polyamide-Polyamine Cryptand as Dicarboxylate Receptor: Dianion Binding Studies in the Solid State, in Solution, and in the Gas Phase

Polyamide-polyamine hybrid macrobicycle L is explored with respect to its ability to bind alpha,omega-dicarboxylate anions. Potentiometric studies of protonated L with the series of dianions from succinate (suc(2-)) through ghitarate (glu(2-)), a-ketoglutarate (kglu(2-)), adipate (adi(2-)), pimelate (pim(2-) ), suberate (sub2-), to azelate (aze2-) have shown adipate preference with association constant value of K = 4900 M-1 in a H2O/DMSO (50:50 v/v) binary solvent mixture. The binding constant increases from glu(2-) to adi(2-) and then continuously decreases with the length of the anion chain. Further, potentiometric studies suggest that hydrogen bonding between the guest anions and the amide/ammonium protons of the receptor also contributes to the stability of the associations along with electrostatic interactions. Negative-mode electrospray ionization of aqueous solutions of host-guest complexes shows clear evidence for the selective formation of 1:1 complexes. Single-crystal X-ray structures of complexes of the receptor with glutaric acid, alpha-ketoglutaric acid, adipic acid, pimelic acid, suberic acid, and azelaic acid assist to understand the observed binding preferences. The solid-state structures reveal a size/shape complementarity between the host and the dicarboxylate anions, which is nicely reflected in the solution state binding studies.