[Cu-81(Phs)(46)((Bunh2)-Bu-T)(10)(H)(32)](3+) Reveals The Coexistence Of Large Planar Cores And Hemispherical Shells In High-Nuclearity Copper Nanoclusters
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY(2020)
Abstract
Copper-based nanomaterials have attracted tremendous interest due to their unique properties in the fields of photoluminescence and catalysis. As a result, studies on the correlation between their molecular structure and their properties are of great importance. Copper nanoclusters are a new class of nanomaterials that can provide an atomic-level view of the crystal structure of copper nanoparticles. Herein, a high-nuclearity copper nanocluster with 81 copper atoms, formulated as [Cu-81(PhS)(46)((BuNH2)-Bu-t)(10)(H)(32)](3+) (Cu-81), was successfully synthesized and fully studied by X-ray crystallography, X-ray photoelectron spectroscopy, hydrogen evolution experiments, electrospray ionization mass spectrometry, nuclear magnetic resonance spectroscopy, and density functional theory calculations. Cu-81 exhibits P core extraordinary structural characteristics, including (i) three types of novel epitaxial surface-protecting motifs; (ii) an unusual planar Cu-17 core; (iii) a hemispherical shell, comprised of a curved surface layer and a planar surface layer; and (iv) two distinct, self-organized arrangements of protective ligands on the curved and planar surfaces. The present study sheds light on structurally unexplored copper nanomaterials and paves the way for the synthesis of high-nuclearity copper nanoclusters.
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Key words
copper,large planar cores,cu<sub>81</sub>phs<sub>46</sub><sup><i>t</i></sup>bunh<sub>2</sub><sub>10</sub>h<sub>32</sub><sup>3+</sup>,hemispherical shells,high-nuclearity
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