Iron tris(bipyridine) PEG hydrogels with covalent and metal coordinate cross-links

Spontaneous gel formation of iron(II) tris(bipyridine)-centered poly(ethylene glycol) methacrylate ([Fe{bpy(PEG-MA)2}3]2+) was observed without the addition of a cross-linking agent. BpyPEG2 macroligands were first modified with methacrylate groups using methacrylic anhydride and then combined with FeSO4 to produce [Fe{bpy(PEG-MA)2}3]SO4. End group analysis by 1H NMR spectroscopy verified quantitative methacrylation of the PEG hydroxyl chain ends. A series of experiments and control reactions were performed to investigate the conditions required for gel formation. Hydrogels of [Fe{bpy(PEG-MA)2}3]SO4 were produced both in the presence and in the absence of a photoinitiator. Controls using MA-PEG-MA also formed hydrogels in the presence of [Fe(bpy)3]2+; however, the addition of a radical scavenger, TEMPO, prevented formation of a polymer network, suggesting radical involvement. Treatment of preformed hydrogels of bpy(PEG-MA)2 with aqueous solutions of FeSO4, CuBr2, and CoCl2 also produced materials with color changes indicative of complexation.