We present the synthesis of novel core reactive spherical polymeric micelles and nanoparticles using nitroxide mediated polymerization (NMP) techniques. These nanostructures have terpyridine functionality selectively located within their hydrophobic core domain and have been further modified by metal complexation (with Fe, Ru, and Cu) within this domain to afford novel metal functionalized polymer nanostructures. The hydrodynamic diameters (D h) of these micelles and hybrid nanoparticles were determined by dynamic light scattering (DLS), and the dimensions of the nanoparticles were characterized using transmission electron microscopy (TEM) and confirmation of the complexation was achieved using UV–vis analysis. The reactivity of the Cu-tethered metal complex within the nanostructures was investigated and was found to be an active catalyst for the 1,3-dipolar cycloaddition “click” reaction of azido and alkynyl functionalized small molecules. This strategy provides a versatile synthetic route toward the selective incorporation of active sites within the core domain of a polymer nanoparticle.

A metal–ligand complexation strategy using ruthenium−terpyridine interactions was utilized for the facile synthesis of amphiphilic block copolymers which were self-assembled into spherical micelles and stabilized throughout their shell to afford well-defined nanoparticles. The labile metal–ligand bond at the nanoparticle core–shell interface was then readily broken to enable excavation to afford hollow completely hydrophilic nanocages which can no longer sequester hydrophobic small molecules. These nanocages also demonstrated pH responsiveness and could be further functionalized by the reintroduction of metals.