[Cu₈₁(PhS)₄₆(^tBuNH₂)₁₀(H)₃₂]³⁺ Reveals the Coexistence of Large Planar Cores and Hemispherical Shells in High-Nuclearity Copper Nanoclusters

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 [Cu81(PhS)46( t BuNH2)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 extraordinary structural characteristics, including (i) three types of novel epitaxial surface-protecting motifs; (ii) an unusual planar Cu17 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.

Copper nanoclusters: designed synthesis, structural diversity, and multiplatform applications

“…Very recently the group of Osman M. Bakr reported the synthesis and full structural analyses of highnuclearity CuNCs: [Cu81(PhS)46( t BuNH2)10(H)32] 3+ . 196 The cluster possesses an unusual Cu17 planar core, a hemispherical shell comprising a curved and a planar surface layer as well as different surface protective motifs of the ligands. This is so far the cluster with the largest number of hydrides, the presence, and the positions of them has been established by ESI-MS and DFT calculations, respectively.…”

[Cu15(PPh3)6(PET)13]2+: a Copper Nanocluster with Crystallization Enhanced Photoluminescence

“…Recent years have witnessed significant advances in the field of coinage metal (Au, Ag, and Cu) nanoclusters (NCs)—nanoparticles of exotic and atomically precise structures containing tens to hundreds of atoms. [ 1–10 ] The size of NCs typically ranges from 1 to 3 nm, which is a critical size regime where nanoparticle behavior transitions from molecular‐like to bulk‐like. The atomically monodisperse nature of NCs also sets them apart from general nanoparticles, as it allows for the development of direct structure‐property relationships.…”

The emergence of mass spectrometry for characterizing nanomaterials. Atomically precise nanoclusters and beyond

“…51 Usually, the composition, size, and monodispersity can be determined by high resolution mass spectrometry for atomically precise nanoclusters, in addition with other characterization techniques (usually NMR, FT-IR, X-ray absorption and photoelectron spectroscopies), and this was done mostly for nanoclusters containing gold or silver. HRMS was also applied for characterizing atomically monodisperse copper, [80][81][82][83][84][85][86] nickel, [87][88][89] cobalt, 90 palladium 91 nanoclusters and molecule-like CdSe nanoclusters. 92 In order to better tune chemical/physical properties of atomically precise metal nanoclusters, several strategies have been adopted in particular using either ligand engineering or metallic kernel (or core) alloying.…”