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 α,?-dicarboxylate anions. Potentiometric studies of protonated L with the series of dianions from succinate (suc^2-) through glutarate (glu^2-), α-ketoglutarate (kglu^2-), adipate (adi^2-), pimelate (pim^2-), suberate (sub^2-), to azelate (aze^2-) 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 glu2- to adi2- 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, α-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.