Synthesis and structural characterization of inverse-coordination clusters from a two-electron superatomic copper nanocluster - Archive ouverte HAL Access content directly
Journal Articles Chemical Science Year : 2018

Synthesis and structural characterization of inverse-coordination clusters from a two-electron superatomic copper nanocluster

(1) , , (1) , (2) , (3) , , (3) , (2) , (1)
1
2
3
Rhone P. Brocha Silalahi
  • Function : Author
Samia Kahlal
Yu-Chiao Liu
  • Function : Correspondent author
Jyh-Fu Lee
  • Function : Author
Ming-Hsi Chiang
  • Function : Author
C. W. Liu
  • Function : Correspondent author

Abstract

We have synthesized and structurally characterized a series of centred cuboctahedral copper clusters, namely [Cu{SCNR}{C[triple bond, length as m-dash]CR'}](PF), (where : R = Bu, R' = COMe; : R = Bu, R' = COEt; : R = Pr, R' = COEt; : R = Pr, R' = 3,5-(CF)CH); [Cu(μ-S){SCNR}{C[triple bond, length as m-dash]CR'}], ; [Cu(μ-Cl){SCNR}{C[triple bond, length as m-dash]CR'}](PF), (where : R = Bu, R' = Ph); [Cu(μ-Br){SCN Bu}{C[triple bond, length as m-dash]CPh}](PF), ; and [Cu(μ-Cl)(μ-Cl){SCN Bu}{C[triple bond, length as m-dash]CCOMe}]. Cluster is the first structurally characterized copper cluster having a Cu centered cuboctahedral arrangement, a miniature of the bulk copper structure. Furthermore, the partial Cu(0) character in the 2-electron superatoms was confirmed by XANES. Inverse coordination clusters are the first examples of copper clusters containing main group elements (Cl, Br, S) with a hyper-coordination number, twelve. A combined theoretical and experimental study was performed, which shows that the central copper (formally Cu) in nanoclusters can be replaced by chalcogen/halogen atoms, resulting in the formation of clusters which show enhanced luminescence properties and increase in the ionic component of the host-guest interaction as Br ≈ Cl > S > Cu, which is consistent with the Cu-X Wiberg indices. The new compounds have been characterized by ESI-MS, H, C NMR, IR, UV-visible, emission spectroscopy, and the structures , , and were established by X-ray diffraction analysis.
Fichier principal
Vignette du fichier
c8sc01508b.pdf; (1.03 Mo) Télécharger le fichier
Origin : Publisher files allowed on an open archive

Dates and versions

hal-01879778 , version 1 (16-07-2019)

Identifiers

Cite

Kiran Kumarvarma Chakrahari, Rhone P. Brocha Silalahi, Jian-Hong Liao, Samia Kahlal, Yu-Chiao Liu, et al.. Synthesis and structural characterization of inverse-coordination clusters from a two-electron superatomic copper nanocluster. Chemical Science, 2018, 9 (33), pp.6785-6795. ⟨10.1039/c8sc01508b⟩. ⟨hal-01879778⟩
23 View
32 Download

Altmetric

Share

Gmail Facebook Twitter LinkedIn More