The development of redox-switchable polymerization catalysts whose reactivity can be altered upon catalyst oxidation and reduction has shown great promise for the synthesis of sophisticated macromolecular architectures, including block copolymers and crosslinked materials. In this talk, redox-switchable bis(imino)pyridine iron alkoxide complexes previously used as catalysts in solution state polymerization reactions are extended to surface initiated polymerization reactions. Anchoring iron-based catalysts to semiconducting titanium dioxide nanoparticles provides access to solid supported catalysts that are capable of undergoing surface initiated polymerization reactions. Deposition of these iron-functionalized particles onto conducting surfaces enables electrochemical redox-switchable polymerization to occur in the solid state. Application of oxidizing or reducing potentials to these electrochemically addressable surfaces results in oxidation or reduction of the supported iron complex that alters its reactivity towards different monomers. Using substrates that contain isolated electrical zones enables patterning of surfaces with two different polymeric materials. In addition to developing a new method for patterning surfaces with polymeric materials, the surface supported metal complexes provide new opportunities for integrating multiple catalysts in tandem processes. These opportunities as well as the differences and similarities observed in redox switching in solution versus the solid state will be discussed.

Redox-switchable polymerization from surfaces: Towards integrated catalysis

ACS Spring Meeting 2021

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