Stability, Dynamics, and Selectivity in the Assembly of Hydrogen-Bonded Hexameric Capsules

Abstract

Fluorescence resonance energy transfer (FRET) was employed to monitor the dynamics of hydrogen-bonded hexameric assemblies formed from resorcin[4]arenes and pyrogallol[4]arenes. Studies were designed to provide further insights into the degree of assembly and stability of these self-assembled capsules at the micro- to nanomolar concentration ranges that are not accessible by NMR studies. The results of this investigation reveal factors that influence the self-assembly of these macrocycles into hexameric capsules. Pyrogallolarenes are very sensitive to the concentration of mixing, with an increase in the equilibration half-life from 36 min at 250 nM to 156 min at 10 microM. The resorcinarenes showed little difference in exchange rates over the same concentration range. The temperature of mixing of the macrocycles was found to be important for both systems with a 12-fold increase in exchange rates over a 20 degree range for the pyrogallolarenes and a 2-fold rate increase for the resorcinarenes over the same temperature range. The stability of the capsules to polar additives such as methanol was probed, with the pyrogallolarenes requiring a higher percentage (1.6% v/v in dichloromethane) of methanol to disassemble the capsules than the resorcinarenes (1.0% v/v in dichloromethane). Pyrogallolarenes assemble in both anhydrous and wet solvents whereas water-saturated solvents are necessary to facilitate the formation of resorcinarene capsules. In addition to these studies, evidence of strict self-sorting in the formation of distinct pyrogallolarene and resorcinarene hexamers was obtained.