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Simple phosphinate ligands access zinc clusters identified in the synthesis of zinc oxide nanoparticles
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Pike, Sebastian D., White, Edward R., Shaffer, Milo S. P. and Williams, Charlotte K. (2016) Simple phosphinate ligands access zinc clusters identified in the synthesis of zinc oxide nanoparticles. Nature Communications, 7 (1). 13008 . doi:10.1038/ncomms13008 ISSN 2041-1723.
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Official URL: http://dx.doi.org/10.1038/ncomms13008
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 31P 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 Zn11 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.
Item Type: | Journal Article | ||||||||||||
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Subjects: | Q Science > QC Physics Q Science > QD Chemistry R Medicine > RS Pharmacy and materia medica T Technology > TP Chemical technology |
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Divisions: | Faculty of Science, Engineering and Medicine > Science > Chemistry | ||||||||||||
Library of Congress Subject Headings (LCSH): | Zinc oxide, Nanoparticles -- Synthesis, Ligands , Thermodynamic equilibrium | ||||||||||||
Journal or Publication Title: | Nature Communications | ||||||||||||
Publisher: | Nature Publishing Group | ||||||||||||
ISSN: | 2041-1723 | ||||||||||||
Official Date: | 13 October 2016 | ||||||||||||
Dates: |
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Volume: | 7 | ||||||||||||
Number: | 1 | ||||||||||||
Article Number: | 13008 | ||||||||||||
DOI: | 10.1038/ncomms13008 | ||||||||||||
Status: | Peer Reviewed | ||||||||||||
Publication Status: | Published | ||||||||||||
Access rights to Published version: | Open Access (Creative Commons) | ||||||||||||
Date of first compliant deposit: | 31 October 2019 | ||||||||||||
Date of first compliant Open Access: | 31 October 2019 | ||||||||||||
RIOXX Funder/Project Grant: |
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