Gram-Scale Preparation of Stable Hydride M@Cu₂₄ (M = Au/Cu) Nanoclusters

Abstract

The instability of phosphine ligated copper hydride nanoclusters (CuH NCs) has largely limited their application in areas such as H2 storage, CO2 reduction, etc. In this work, the stability of CuH NCs was remarkably enhanced by improving their antioxidant capacity through two different approaches: (i) metal doping and (ii) ligand modification. Three NCs, AuCu24H22(PPh3)12, Cu25H22((p-FPh)3P)12, and AuCu24H22((p-FPh)3P)12, were controllably synthesized, and their structures were determined by single-crystal X-ray diffraction. The compositions of these NCs were further confirmed by electrospray ionization mass spectrometry and nuclear magnetic resonance. More importantly, we achieved gram-level production of M@Cu24 (M = Cu/Au) NCs protected by electron-withdrawing ligands (p-FPh)3P, which in turn proved their superior stability; such a large-scale preparation laid the foundation for future explorations of copper-rich NCs. This work hopes to shed light on large-scale generation of ultrastable Cu-based NCs.

Precise Implantation of an Archimedean Ag@Cu12 Cuboctahedron into a Platonic Cu4Bis(diphenylphosphino)hexane6 Tetrahedron

“…The second Ag atom in [Ag 2 Cu 15 S 8 (dpph) 6 ] + should be site occupancy disordered at any site of the 12 Cu atoms on the cuboctahedral framework, which contributes too few electron densities to determine the precise site of the second Ag atom crystallographically. Some quite similar results were also observed in [PtAg 24 (SR) 18 ] 2– ([Pt 2 Ag 23 (SR) 18 ] 2– as trace impurity), [AuCu 24 H 22 (PR 3 ) 12 ] + ([Au 2 Cu 23 H 22 (PR 3 ) 12 ] + as trace impurity), and [Cu n Ag 8 Au 7– n (TBA) 12 ] + ([Cu n ′ Ag 9 Au 6– n ′ (TBA) 12 ] + as trace impurity), and so on (Figure S13).…”

Ligand-protected gold/silver superatoms: current status and emerging trends

“…7d). 93 The yield is much higher than that of [Cu 25 H 22 (TPP) 12 ] + under inert conditions (ca. 150 mg, 23%) because 4-FPP is more electronwithdrawing than TPP.…”

Copper-hydride nanoclusters with enhanced stability by N-heterocyclic carbenes

“…5(e), red curve). Furthermore, all-phosphine-protected Cu25H22((p-FPh)3P)12 (Cu25) [45] exhibited much worse stability (Fig. 5(c) and pink curve in Fig.…”