Atomically precise nanoclusters predominantly seed gold nanoparticle syntheses.

Seed-mediated synthesis strategies, in which small gold nanoparticle precursors are added to a growth solution to initiate heterogeneous nucleation, are among the most prevalent, simple, and productive methodologies for generating well-defined colloidal anisotropic nanostructures. However, the size, structure, and chemical properties of the seeds remain poorly understood, which partially explains the lack of mechanistic understanding of many particle growth reactions. Here, we identify the majority component in the seed solution as an atomically precise gold nanocluster, consisting of a 32-atom Au core with 8 halide ligands and 12 neutral ligands constituting a bound ion pair between a halide and the cationic surfactant: Au32X8[AQA+•X-]12 (X = Cl, Br; AQA = alkyl quaternary ammonium). Ligand exchange is dynamic and versatile, occurring on the order of minutes and allowing for the formation of 48 distinct Au32 clusters with AQAX (alkyl quaternary ammonium halide) ligands. Anisotropic nanoparticle syntheses seeded with solutions enriched in Au32X8[AQA+•X-]12 show narrower size distributions and fewer impurity particle shapes, indicating the importance of this cluster as a precursor to the growth of well-defined nanostructures.

Aluminum Nanocubes Have Sharp Corners.

Of the many plasmonic nanoparticle geometries that have been synthesized, nanocubes have been of particular interest for creating nanocavities, facilitating plasmon coupling, and enhancing phenomena dependent upon local electromagnetic fields. Here we report the straightforward colloidal synthesis of single-crystalline {100} terminated Al nanocubes by decomposing AlH3 with Tebbe's reagent in tetrahydrofuran. The size and shape of the Al nanocubes is controlled by the reaction time and the ratio of AlH3 to Tebbe's reagent, which, together with reaction temperature, establish kinetic control over Al nanocube growth. Al nanocubes possess strong localized field enhancements at their sharp corners and resonances highly amenable to coupling with metallic substrates. Their native oxide surface renders them extremely air stable. Chemically synthesized Al nanocubes provide an earth-abundant alternative to noble metal nanocubes for plasmonics and nanophotonics applications.