Amphiphilic Metallopolymers for Photoswitchable Supramolecular Hydrogels

A series of amphiphilic metallopolymers is described that features zinc(II) bis-terpyridine coordination nodes as well as a backbone with hydrophobic azoaryl moieties and hydrophilic phenylene-ethynylene units decorated with PEG brushes. Using such metallopolymers at very low concentration, stable, photo-responsive and self-healing hydrogels are obtained. UV irradiation of the gel allows modulation of the degree of hydrophobic pi-pi interactions between photoisomerizable azoaryl units and a polarity switch that overall induces a fast gel-to-sol transition. Finally, the material phase can be readily and fully restored to the thermodynamically stable state either thermally or photochemically by using visible light. The presented strategy can be further generalized towards modular supramolecular metallopolymers for injectable gels in drug delivery and bio-engineering applications.