3 years ago

From Well-Defined Alkylzinc Phosphinates to Quantum-Sized ZnO Nanocrystals

From Well-Defined Alkylzinc Phosphinates to Quantum-Sized ZnO Nanocrystals
Justyna Grzonka, Dymitr Hryciuk, Agnieszka Grala, Krzysztof J. Kurzydłowski, Iwona Justyniak, Maria Jędrzejewska, Małgorzata Wolska-Pietkiewicz, Janusz Lewiński
Despite various applications of alkylzinc carboxylates in chemistry and materials science, the corresponding organozinc derivatives of organophosphorus compounds still represent an insufficiently explored area. To fill this gap, we report on the synthesis of alkylzinc phosphinates and their use as efficient precursors of phosphinate-coated ZnO nanocrystals in the quantum size regime. Examples of a series of alkylzinc phosphinates with the general formula [RZn(O2PR′2)] (R=tBu or Et) have been prepared through equimolar reactions between ZnR2 and a selected phosphinic acid, namely dimethylphosphinic acid (dmpha-H), methylphenylphosphinic acid (mppha-H), diphenylphosphinic acid (dppha-H), or bis(4-methoxyphenyl)phosphinic acid (dmppha-H). The reactivities of alkylzinc phosphinate complexes toward H2O and O2 have also been investigated, which resulted in the isolation of two oxo-zinc phosphinate clusters, that is, [Zn4(μ4-O)(dppha)6] and [Zn4(μ4-O)(dmppha)6], as well as the unique alkoxy(oxo)zinc cluster [Zn4(μ4-O)(μ2-OtBu)(dppha)5]. Analysis of the crystal structures has revealed that organozinc complexes incorporating phosphinate ligands exhibit a unique capacity for shape-driven self-assembly to produce extended networks, including noncovalent quasi-porous materials. Finally, monodispersed and quantum-sized ZnO NCs coated with phosphinate ligands have been prepared using a non-external-surfactant-assisted wet-chemical organometallic approach based on well-defined [RZn(O2PR′2)]-type compounds. The resulting brightly luminescent ZnO NCs exhibit average core sizes and hydrodynamic diameters in the ranges 2–4.5 nm and 5–8 nm, respectively. The size of the inorganic core is slightly affected by the character of the incorporated phosphinate ligand, being smallest for ZnO NCs coated by asymmetrically substituted mppha ligands. Regardless of whether or not various phosphinate coating ligands could be controllably applied on the ZnO NC surface, no significant differences were found in the luminescence profiles of the analyzed nanosystems. Bright nanocrystals: We describe the synthesis of novel alkylzinc phosphinates and their use as efficient precursors of brightly luminescent ZnO nanocrystals coated with monoanionic organophosphorus ligands (see graphic).

Publisher URL: http://onlinelibrary.wiley.com/resolve/doi

DOI: 10.1002/chem.201701823

You might also like
Discover & Discuss Important Research

Keeping up-to-date with research can feel impossible, with papers being published faster than you'll ever be able to read them. That's where Researcher comes in: we're simplifying discovery and making important discussions happen. With over 19,000 sources, including peer-reviewed journals, preprints, blogs, universities, podcasts and Live events across 10 research areas, you'll never miss what's important to you. It's like social media, but better. Oh, and we should mention - it's free.

  • Download from Google Play
  • Download from App Store
  • Download from AppInChina

Researcher displays publicly available abstracts and doesn’t host any full article content. If the content is open access, we will direct clicks from the abstracts to the publisher website and display the PDF copy on our platform. Clicks to view the full text will be directed to the publisher website, where only users with subscriptions or access through their institution are able to view the full article.