Self-assembly of a supramolecular network with pseudo-rotaxane cross-linking nodes and its transformation into a mechanically locked structure by rotaxane formation.

A main chain poly(crown ether) macromolecule has been cross-linked with a two binding site guest to afford a stimuli-responsive supramolecular polymeric network with pseudo-rotaxane nodes. This network forms gels and films that are responsive to temperature and solvent polarity; however, the materials can be shielded against both effects by transforming the pseudo-rotaxane junctions into rotaxane links, creating a mechanically locked structure.