Oxidation-Responsive Emulsions Stabilized by Cleavable Metallo-Supramolecular Cross-Linked Microgels

An original route to develop an advanced class of microgel emulsifiers containing stimulable metallo-supramolecular instead of frozen covalent cross-links is reported. The poly(N-isopropylmethacrylamide) (PNiPMAM) chains of the microgel are connected by iron(II)-bis(terpyridine) coordination supramolecular complexes that can be cleaved on demand, leading to unique properties both at interfaces and in volume. The microgel synthesis is not demanding, and the characterization of its supramolecular structure can be precisely achieved by standard methods. Singularly, interfaces of an oil-in-water emulsion stabilized by the supramolecular particles can be triggered at the molecular scale by oxidation of Fe(II) to Fe(III), leading to emulsion breaking. In bulk, we show that a microgel dispersion can indeed be transformed into a polymer solution upon oxidation. Our study paves the way to the discovery of unusual microgel properties as our proof-of-concept can be extended to different supramolecular chemistry and architecture.