Abstract
[EtZnP(SiMe3)2]3 has been identified as a competent intermediate for the growth of stoichiometric α-Zn3P2 nanocrystals from Zn-rich zinc phosphide seeds as determined by powder X-ray diffraction, solid-state nuclear magnetic resonance (NMR) spectroscopy, and transmission electron microscopy analysis. Solution-phase NMR data show that this trimer forms in situ upon reaction of P(SiMe3)3 and ZnEt2 in the presence of Zn(O2CR)2 under zinc carboxylate-limited conditions. [EtZnP(SiMe3)2]3 can also be used to nucleate zinc phosphide; however, in comparison to a previously examined nucleation pathway involving (Et2Zn)P(ZnO2CR)2(SiMe3), a decrease in relative reactivity leads to fewer nuclei and larger, more crystalline particles. These data, in combination with previous literature on the synthesis of zinc phosphide nanocrystals, were then aggregated to propose a set of design principles for the synthesis of zinc phosphide nanocrystals using P(SiMe3)3 as the phosphorus precursor.
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