The self-assembly of a stimuli-responsive aqueous supramolecular hyperbranched polymer from small molecules is reported. This system is composed of ditopic and tritopic guest-functionalised molecules that are able to form heteroternary supramolecular complexes with the macrocyclic host cucurbit[8]uril (CB[8]). We demonstrate that the supramolecular hyperbranched polymer formed is responsive to both photo- and chemical stimuli, exhibiting reversibility. Furthermore, this system is shown to assemble at liquid-liquid interfaces, which upon gelation, is observable on the micrometre scale. This self-healing supramolecular network can act as a soft matter barrier for aqueous microdroplets, inhibiting their coalescence.A. S. G. acknowledges support from the EPSRC Cambridge NanoDTC, EP/G037221/1, A. P. and O. A. S. acknowledge support from the ERC starting investigator grant (ASPiRe 240629) and EPSRC Programme Grant (NOtCH, EP/L027151/1)
