Metal-Containing Conducting Polymers Built on Clathrochelate Metal Complexes: Caged
Metal Centers for Interlayer Charge Transport and Electrocatalytic H2 Production
Metal-templated [2 + 3]-type condensation reactions between π-extended boronic acids
and N,N’-bidentate dioxime ligands furnished a series of cage metal complexes, which were
subsequently electropolymerized to prepare metal-containing conducting polymers (MCPs).
Despite sharing essentially isostructural organic scaffolds, these materials display metaldependent electrochemical properties as evidenced by different redox windows observed for M
= Co, Fe, and Ru. Notably, consecutive electropolymerization using two different monomers
produced well-defined bilayer MCPs, in which the bottom MCP layer in its oxidized form
functions as redox mediator for vectorial charge transport to the top MCP layer having different
metal center. In addition, MCP with M = Co in its reduced form can function as robust thin-film
electrocatalyst for the production of H2 in acidic organic media.