Simple phosphinate ligands access zinc clusters identified in the synthesis of zinc oxide nanoparticles.
basic_science · Level V
Where this comes from
- Record sourced from PubMed, PMID 27734828.
- Also identified by DOI 10.1038/ncomms13008 and PMC identifier 5065624.
- Licence recorded as CC BY.
- The licence permits redistribution, so the abstract is shown in full and the full text is available from the publisher.
Abstract
The bottom-up synthesis of ligand-stabilized functional nanoparticles from molecular precursors is widely applied but is difficult to study mechanistically. Here we use <sup>31</sup>P 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 Zn<sub>11</sub> cluster 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.