A Versatile AuNP Synthetic Platform for Decoupled Control of Size and Surface Composition.

While a plethora of protocols exist for the synthesis of sub-10-nm gold nanoparticles (AuNPs), independent control over the size and surface composition remains restricted. This poses a particular challenge for systematic studies of AuNP structure-function relationships and the optimization of crucial design parameters. To this end, we report on a modular two-step approach based on the synthesis of AuNPs in oleylamine (OAm) followed by subsequent functionalization with thiol ligands and mixtures thereof. The synthesis of OAm-capped AuNPs enables fine-tuning of the core size in the range of 2-7 nm by varying the reaction temperature. The subsequent thiol-for-OAm ligand exchange allows a reliable generation of thiol-capped AuNPs with target surface functionality. The compatibility of this approach with a vast library of thiol ligands provides detailed control of the mixed ligand composition and solubility in a wide range of solvents ranging from water to hexane. This decoupled control over the AuNP core and ligand shell provides a powerful toolbox for the methodical screening of optimal design parameters and facile preparation of AuNPs with target properties.