Simple Phosphinate Ligands Access New Zinc Clusters Identified in the Synthesis of Zinc Oxide Nanoparticles

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Title: Simple Phosphinate Ligands Access New Zinc Clusters Identified in the Synthesis of Zinc Oxide Nanoparticles
Author(s): Pike, S
White, E
Shaffer, M
Williams, CK
Item Type: Journal Article
Abstract: The bottom-up synthesis of ligand-stabilised functional nanoparticles from molecular precursors is widely applied but difficult to study mechanistically. Here, we use 31P NMR spectroscopy to follow the trajectory of phosphinate ligands during the synthesis of a range of new 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. As well as a versatile and accessible route to new (optionally doped) zinc clusters, the findings provide a new understanding of the role of well-defined molecular precursors during the synthesis of small (2-4 nm) nanoparticles.
Publication Date: 13-Oct-2016
Date of Acceptance: 1-Jul-2016
URI: http://hdl.handle.net/10044/1/37056
DOI: https://dx.doi.org/10.1038/ncomms13008
ISSN: 2041-1723
Publisher: Nature Publishing Group
Journal / Book Title: Nature Communications
Volume: 7
Sponsor/Funder: Engineering & Physical Science Research Council (EPSRC)
Engineering & Physical Science Research Council (EPSRC)
Engineering & Physical Science Research Council (EPSRC)
Funder's Grant Number: EP/H046380/1
EP/K035274/1
EP/M013839/1
Copyright Statement: This work is licensed under a Creative Commons Attribution 4.0 International License. The images or other third party material in this article are included in the article’s Creative Commons license, unless indicated otherwise in the credit line; if the material is not included under the Creative Commons license, users will need to obtain permission from the license holder to reproduce the material. To view a copy of this license, visit http://creativecommons.org/licenses/by/4.0/ © The Author(s) 2016
Keywords: MD Multidisciplinary
Publication Status: Published
Article Number: 13008
Appears in Collections:Chemistry
Faculty of Natural Sciences



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