Spatially Designed Supramolecular Anion Receptors Based on Pillar[5]arene Scaffolds: Synthesis and Halide Anion Binding Properties.

Abstract

Urea-functionalized anion receptors based on brominated functionalized pillar[5]arenes were prepared. The binding affinity toward halide anions was investigated and probed using 1H NMR titration and isothermal titration calorimetry (ITC). The complexation behavior was affected by the structure of the receptor and the nature of the anionic guest. The synthesized receptors are highly selective toward fluoride resulting in the formation of a 1:2 host-to-guest complex. The anion receptor based on the 1,3-alternate pillar[5]arene regioisomer shows the highest affinity toward fluorine anions. No significant interactions were observed with larger bromine anions. The formation of a self-assembled supramolecular polymer driven by hydrogen bonds in solution was demonstrated by diffusion-ordered spectroscopy (DOSY), ITC, and dynamic light scattering (DLS) measurements. From ITC dilution experiments, we found that the supramolecular polymer self-assembly at higher concentrations is a spontaneous process as indicated by the positive value of Gibbs free energy (ΔG = 12.04 kJ mol-1).