Observation of Non‐FCC Copper in Alkynyl‐Protected Cu₅₃Nanoclusters

Abstract

The only feasible access to non‐face‐centered cubic (FCC) copper was by physical vapor deposition under high vacuum. Now, non‐FCC copper is observed in a series of alkynyl‐protected Cu53 nanoclusters (NCs) obtained from solution‐phase synthesis. Determined by single‐crystal X‐ray crystallography, the structures of Cu53(C≡CPhPh)9(dppp)6Cl3(NO3)9 and its two derivatives reveal an ABABC stacking sequence involving 41 Cu atoms. It can be regarded as a mixed FCC and HCP structure, which gives strong evidence that Cu can be arranged in non‐FCC lattice at ambient conditions when proper ligands are provided. Characterization methods including X‐ray absorption fine structure, XPS, ESI‐MS, UV/Vis, Auger spectroscopy, and DFT calculations were carried out. CuII was shown to successively coordinate with introduced ligands and changed to CuI after bonding with phosphine. The following addition of NaBH4 and the aging step further reduced it to the Cu53 NC.

A triflate and alkynyl protected Ag43 nanocluster with a passivated surface

“…The stretching of^C-H at 3272 cm À1 is no longer present in Ag 43 , indicating the bonding of t BuC^C À with Ag. 39 The characteristic peaks of SO 3 CF 3 À ranging from 1000 to 1500 cm À1 , on the other hand, are still prominent in the spectrum of Ag 43 . These information further conrmed both ligands are present on Ag 43 .…”

Kernels‐Different Au25Nanoclusters Enhanced Catalytic Performance via Modification of Ligand and Electronic Effects

“…[ 6‐11 ] Increase of unsaturated sites on the surface (surface effect) enables the clusters to exhibit good catalytic activity and unique selectivity in reactions such as oxidation ( Au 38 , Au 144 ), hydrogenation ( Cu 25 ), C—C coupling ( Au 11 , Cu 53 ), A 3 coupling ( Au 13 ), cycloaddition ( Cu 20 ), etc . [ 12‐17 ] Nanoclusters with precise structures can also serve as model catalysts to reveal the correlation between catalyst performance and structure. [ 18 ] The well‐defined compositions and atomically precise molecular structures of MPCs are the basis for elucidating their structure‐ composition‐property relationships and size evolution mechanisms.…”

Eight-Electron Superatomic Cu31 Nanocluster with Chiral Kernel and NIR-II Emission

“…A major reason for this is believed to be the much lower M(I)/M(0) half-cell reduction potential of copper (0.52 V) than those of silver (0.80 V) and gold (1.69 V), which makes the Cu(0)-containing clusters air-sensitive and challenging to achieve. 30,31 To date, only a handful of such copper nanoclusters (Cu 13 , 32 Cu 14 , 33 Cu 18 , 34 Cu 20 , 35 Cu 23 , 36 Cu 25 , 31 Cu 29 , 37 Cu 53 , 38,39 and Cu 61 40 ) have been documented, precluding their comprehensive studies. Except for [Cu 53 (C� C P h P h ) 9 ( d p p p ) 6 C l 3 ( N O 3 ) 9 ] ( d p p p = 1 , 3 -b i s -(diphenyphosphino)propane), 38 all of the previously reported copper nanoclusters contain less than five free electrons, while gold and silver nanoclusters bearing eight or more free electrons are conspicuously more prevalent.…”

“…30,31 To date, only a handful of such copper nanoclusters (Cu 13 , 32 Cu 14 , 33 Cu 18 , 34 Cu 20 , 35 Cu 23 , 36 Cu 25 , 31 Cu 29 , 37 Cu 53 , 38,39 and Cu 61 40 ) have been documented, precluding their comprehensive studies. Except for [Cu 53 (C� C P h P h ) 9 ( d p p p ) 6 C l 3 ( N O 3 ) 9 ] ( d p p p = 1 , 3 -b i s -(diphenyphosphino)propane), 38 all of the previously reported copper nanoclusters contain less than five free electrons, while gold and silver nanoclusters bearing eight or more free electrons are conspicuously more prevalent. 41−45 Thus, it is imperative to expand the limited library of copper nanoclusters to fully picture the highly feasible synthetic methods, structure−property relationships, and even their potential applications.…”