Guest controlled aggregation of amphiphilic sulfonatomethylated calix[4]resorcinarenes in aqueous solutions

Abstract

Supramolecular nanoaggregates formed through the association of amphiphilic sulfonatomethylated calix[4]resorcinarenes with different substituents on the lower rim (methyl, pentyl, heptyl) and number of aromatic, aliphatic, and cationic guests differing in their shapes and sizes were investigated in aqueous solution by various NMR techniques ((1)H, 2D NOESY, FT-PGSE). It was shown that slight variations of the alkyl chain length on the lower rim of calixresorcinarenes dramatically change their aggregation behavior. Unlike the other calixresorcinarenes studied, the "head-to-tail" packing mode is observed for calixresorcinarene with pentyl moieties on the lower rim, which is unusual for amphiphilic calixarene aggregates. This calixresorcinarene demonstrates the stronger binding capacity toward the guest molecules due to their encapsulation into the capsule-like aggregate subunits. The guest-host complexation modifies the properties of both components, with the size of the resulted colloid particles being controlled by the guest nature.