Design and Growth of Robust Layered Polymer Assemblies with Molecular Thickness Control

We report on two alternating copolymers synthesized from maleimide and vinyl ether monomers, where the vinyl ether possesses a pendant phosphonate functionality. Partial hydrolysis of the phosphonate groups in conjunction with Zr−phosphonate layer growth chemistry produces robust, stable polymer multilayer structures where the layer thickness is 16 Å for polymers synthesized with N -phenylmaleimide (NPM) monomer and 31 Å for polymers synthesized with N -biphenylmaleimide (NBM) monomer. We present the syntheses and characterization of the polymers and layered assemblies containing up to 10 layers. X-ray photoelectron spectroscopy data on layer-dependent Zr loading suggest interlayer bonding that is similar to that seen for Zr−alkanebisphosphonate multilayers.