title: Simple phosphinate ligands access zinc clusters identified in the synthesis of zinc oxide nanoparticles.
abstract: The bottom-up synthesis of ligand-stabilized functional nanoparticles from molecular precursors is widely applied but is difficult to study mechanistically. Here we use31P NMR spectroscopy to follow the trajectory of phosphinate ligands during the synthesis of a range of ligated zinc oxo clusters, containing 4, 6 and 11 zinc atoms. Using an organometallic route, the clusters interconvert rapidly and self-assemble in solution based on thermodynamic equilibria rather than nucleation kinetics. These clusters are also identified in situ during the synthesis of phosphinate-capped zinc oxide nanoparticles. Unexpectedly, the ligand is sequestered to a stable Zn11cluster during the majority of the synthesis and only becomes coordinated to the nanoparticle surface, in the final step. In addition to a versatile and accessible route to (optionally doped) zinc clusters, the findings provide an understanding of the role of well-defined molecular precursors during the synthesis of small (2-4 nm) nanoparticles.
authors.affiliation: Department of Chemistry, Imperial College London, Imperial College Road, South Kensington Campus, London SW7 2AZ, UK.
authors.forename: Sebastian D
authors.initials: SD
authors.lastname: Pike
authors.affiliation: Department of Chemistry, Imperial College London, Imperial College Road, South Kensington Campus, London SW7 2AZ, UK.
authors.forename: Edward R
authors.initials: ER
authors.lastname: White
authors.affiliation: Department of Chemistry, Imperial College London, Imperial College Road, South Kensington Campus, London SW7 2AZ, UK.
authors.forename: Milo S P
authors.initials: MS
authors.lastname: Shaffer
authors.affiliation: Department of Chemistry, Imperial College London, Imperial College Road, South Kensington Campus, London SW7 2AZ, UK.
authors.forename: Charlotte K
authors.identifier: 0000-0002-0734-1575
authors.initials: CK
authors.lastname: Williams