Hybrid Models for Single Source Precursors of ZnO Nanocrystals

Chem. Eur. J., 2015, 21, 5488–5495.

 

tert-Butyl(tert-Butoxy)zinc Hydroxides: Hybrid Models for Single Source Precursors of ZnO Nanocrystals

Kamil Sokołowski,a  Iwona Justyniak,a  Wojciech Bury,b   Justyna Grzonka,c Zbigniew Kaszkur,a Łukasz Mąkolski,b   Michał Dutkiewicz,b  Agnieszka Lewalska,b Dominik Kubicki,b   Katarzyna Wójcik,a  Krzysztof Kurzydłowskic and  Janusz Lewiński*ab

Institute of Physical Chemistry, Polish Academy of Sciences, Kasprzaka 44/52, 01-224 Warsaw, Poland
Faculty of Chemistry, Warsaw University of Technology, Noakowskiego 3, 00-664 Warsaw, Poland

Faculty of Materials Science and Engineering, Warsaw University of Technology, Wołoska 141, 02-507 Warsaw, Poland.

DOI: 10.1002/chem.201406245
First published online 16 Feb 2015

Alkylzinc alkoxides, [RZnOR′]4, have received much attention as efficient precursors of ZnO nanocrystals (NCs), and their “Zn4O4” heterocubane core has been regarded as a “preorganized ZnO”. A comprehensive investigation of the synthesis and characterization of a new family of tert-butyl(tert-butoxy)zinc hydroxides, [(tBu)4Zn43-OtBu)x3-OH)4−x], as model single-source precursors of ZnO NCs is reported. The direct reaction between well-defined [tBuZnOH]6 (16) and [tBuZnOtBu]4 (24) in various molar ratios allows the isolation of new mixed cubane aggregates as crystalline solids in a high yield: [(tBu)4Zn43-OtBu)33-OH)] (3), [(tBu)4Zn43-OtBu)23-OH)2] (4), [(tBu)4Zn43-OtBu)(μ3-OH)3] (5). The resulting products were characterized in solution by 1H NMR and IR spectroscopy, and in the solid state by single-crystal X-ray diffraction. The thermal transformations of 2–5 were monitored by in situ variable-temperature powder X-ray diffraction and thermogravimetric measurements. The investigation showed that the Zn–OH groups appeared to be a desirable feature for the solid-state synthesis of ZnO NCs that significantly decreased the decomposition temperature of crystalline precursors 3–5.

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