Self-assembly of β-cyclodextrin-pillar[5]arene molecules into supramolecular nanoassemblies: morphology control by stimulus responsiveness and host-guest interactions.

Abstract

Macrocyclic molecules have attracted considerable attention as new functional materials owing to their unique pore size structure and excellent host-guest properties. With the development of macrocyclic compounds, the properties of mono-modified macrocyclic materials can be improved by incorporating pillar[n]arene or cyclodextrin derivatives through bridge bonds. Herein, we report the self-assembly of amphiphilic di-macrocyclic host molecules (H1-2) based on β-cyclodextrin and pillar[5]arene units linked by azophenyl or biphenyl groups. In a H2O/DMSO (19 : 1, v/v) mixed polar solvent, an amphiphile H1 with an azophenyl group self-assembled into unique nanorings and exhibited an obvious photoresponsive colour change. This photochromic behaviour makes H1 suitable for application in carbon paper materials on which arbitrary patterns can be erased and rewritten. The amphiphile H2, with a biphenyl unit, self-assembled into spherical micelles. These differences indicate that various linker units lead to changes in the intermolecular and hydrophilic-hydrophobic interactions. In a CHCl3/DMSO (19 : 1, v/v) mixed low-polarity solvent, the amphiphile H1 self-assembled into fibrous aggregates, whereas the molecule H2 assembled into unique nanoring aggregates. In this CHCl3/DMSO mixed solvent system, small nanosheet aggregates were formed by the addition of a guest molecule (G) composed of tetraphenylethene and hexanenitrile groups. With prolonged aggregation time, the small sheet aggregates further aggregated into cross-linked nanoribbons and eventually formed large nanosheet aggregates. The data reveal that the morphology of H1-2 can be controlled by tuning the intermolecular interactions of the molecules via the formation of host-guest complexes. Moreover, the polyhydroxy cyclodextrin unit on H1-2 can be strongly adsorbed on the stationary phase in column chromatography via multiple hydrogen bonds, and the singly modified pillar[5]arenes can be successfully separated by host-guest interactions.