A Versatile Coordinating Ligand for Coating Semiconductor, Metal, and Metal Oxide Nanocrystals

We detail the design of a new set of multicoordinating polymer ligands based on the phosphonate anchoring motif and apply them for the surface coating of luminescent quantum dots, gold nanoparticles, and iron oxide nanoparticles alike. The ligand is synthesized via a nucleophilic addition reaction between poly(isobutylene-alt-maleic anhydride) and amine-modified phosphonate derivatives and short polyethylene glycol hydrophilic blocks, which allows the flexibility to tune the architecture and stoichiometry of the final compound. We find that these phosphonate-based polymers exhibit a strong coordinating affinity for ZnS-overcoated quantum dots (QDs), Au nanoparticles, and iron oxide nanoparticles, yielding nanocrystal dispersions that exhibit good colloidal stability for all three systems. The affinity of these ligands is also preserved when additional coordinating groups are introduced, such as imidazoles. Furthermore, the resulting polymer-coated nanocrystals are easily functionalized with reactive groups, introduced along the polymer chain during synthesis. The polymer coating is compact enough to allow implementation of resonance energy transfer coupling of luminescent QDs to proximal dyes. The affinity between the ligands and gold nanoparticle surfaces was compared to that of thiol groups using NaCN digestion tests.