Cucurbit[8]uril directed stimuli-responsive supramolecular polymer brushes for dynamic surface engineering

In situ modification of surfaces with thin layers of polymers is of growing interest as adjustment of surface properties can be made on demand. We present herein a supramolecular ‘grafting to’ polymer brush via the recognition of surface-bound cucurbit[8]uril (CB[8]) rotaxanes towards end-functionalised polyethylene glycol (PEG). This dynamic supramolecular method represents advantages over traditional approaches, which employ covalent bond formation in the ‘grafting to’ process. Brush properties can be easily modified post-preparation by exchanging the polymers with small molecules in a controlled, reversible manner. Including both redox- and light-responsive guests in a single rotaxane entity, the CB[8]-mediated preparation of the polymer brush offers unique opportunities to switch the brush composition efficiently. While the PEG brushes are well hydrated in a good solvent (water) and stretch away from the surface, they collapse in a poor solvent (toluene), leading to the formation of a dense layer on the surface. This collapsed conformation protects the heteroternary complexes of CB[8]-rotaxane from dissociation and maintains the attachment of polymers on the surface.