The need for efficient, tailor-made catalysts has inspired chemists to fuse the design principles of natural enzymes with synthetic macromolecular architectures. A highly interesting pathway mimics a metallo-enzyme's tertiary structure via the target placement of metal-ions in a tailor-made polymeric framework, resulting in catalytically active single-chain nanoparticles. Initial studies reveal unusual and promising effects, regarding both new catalyst characteristics and a high impact on product formation. These multifunctional nanoreactors, constructed from simple folded polymer chains, will lead to advanced bioinspired catalytic systems. As found in enzymes, their impact lies specifically within the defined construction of a polymeric pocket around the catalytic active cores for substrate recognition.

The preparation and in-depth characterization of well-defined, palladium(ii) crosslinked single-chain nanoparticles (Pd-SCNPs) is reported. In addition, a novel procedure for interpreting the SEC chromatograms of SCNPs by log-normal distribution (LND) simulations is introduced.

We introduce the synthesis and in-depth characterization of platinum(II)-crosslinked single-chain nanoparticles (Pt -SCNPs) to demonstrate their application as a recyclable homogeneous catalyst. Specifically, a linear precursor copolymer of styrene and 4-(diphenylphosphino)styrene was synthesized via nitroxide-mediated polymerization. The triarylphosphine ligand moieties along the backbone allowed for the intramolecular crosslinking of single chains via the addition of [Pt(1,5-cyclooctadiene)Cl ] in dilute solution. The successful formation of well-defined Pt -SCNPs was evidenced by size exclusion chromatography, dynamic light scattering, nuclear magnetic resonance ( H, P{ H}, Pt), and diffusion-ordered spectroscopy. Finally, the activity of the Pt -SCNPs as homogeneous, yet recyclable catalyst was successfully demonstrated using the example of the amination of allyl alcohol.