Observation of Non‐FCC Copper in Alkynyl‐Protected Cu53 Nanoclusters

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, th...

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Bibliographic Details
Published in:Angewandte Chemie International Edition 2020-04, Vol.59 (16), p.6507-6512
Main Authors: Qu, Mei, Zhang, Fu‐Qiang, Wang, Dian‐Hui, Li, Huan, Hou, Juan‐Juan, Zhang, Xian‐Ming
Format: Article
Language:English
Subjects:
Aging
Auger spectroscopy
Copper
Crystal structure
Crystallography
EXAFS
Face centered cubic lattice
Fine structure
High vacuum
layer structures
Ligands
Mathematical analysis
Nanoclusters
Phosphine
Phosphines
Physical vapor deposition
Spectroscopy
stacking
Stacking sequence (composite materials)
Ultrastructure
Vacuum
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Summary: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. Face‐OFF: Non‐FCC copper is observed in a series of alkynyl‐protected Cu53 nanoclusters (NCs) obtained from solution‐phase synthesis. Cu53 and its two derivatives reveal an ABABC stacking sequence involving 41 Cu atoms. It can be regarded as a mixed FCC and HCP structure, giving strong evidence that Cu can be arranged in a non‐FCC lattice under ambient conditions when proper ligands are provided.
ISSN:1433-7851
1521-3773
DOI:10.1002/anie.202001185