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

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Abstract

We have synthesized and structurally characterized a series of centred cuboctahedral copper clusters, namely [Cu13{S2CNR2}6{C[triple bond, length as m-dash]CR′}4](PF6), 1a–d (where a: R = nBu, R′ = CO2Me; b: R = nBu, R′ = CO2Et; c: R = iPr, R′ = CO2Et; d: R = nPr, R′ = 3,5-(CF3)2C6H3); [Cu1212-S){S2CNR2}6{C[triple bond, length as m-dash]CR′}4], 2a–c; [Cu1212-Cl){S2CNR2}6{C[triple bond, length as m-dash]CR′}4](PF6), 3a–e (where e: R = nBu, R′ = Ph); [Cu1212-Br){S2CNnBu2}6{C[triple bond, length as m-dash]CPh}4](PF6), 4e; and [Cu1212-Cl)(μ3-Cl){S2CNnBu2}6{C[triple bond, length as m-dash]CCO2Me}3]+ 5a. Cluster 1a is the first structurally characterized copper cluster having a Cu13 centered cuboctahedral arrangement, a miniature of the bulk copper fcc structure. Furthermore, the partial Cu(0) character in the 2-electron superatoms 1 was confirmed by XANES. Inverse coordination clusters 2–5 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 Cu1−) in nanoclusters 1 can be replaced by chalcogen/halogen atoms, resulting in the formation of clusters 2–5 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, 1H, 13C NMR, IR, UV-visible, emission spectroscopy, and the structures 2a–b, 3d–e, 4e and 5a were established by X-ray diffraction analysis.

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

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Publication details

The article was received on 03 Apr 2018, accepted on 30 Jun 2018 and first published on 02 Jul 2018


Article type: Edge Article
DOI: 10.1039/C8SC01508B
Citation: Chem. Sci., 2018, Advance Article
  • Open access: Creative Commons BY-NC license
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    Synthesis and structural characterization of inverse-coordination clusters from a two-electron superatomic copper nanocluster

    K. K. Chakrahari, R. P. B. Silalahi, J. Liao, S. Kahlal, Y. Liu, J. Lee, M. Chiang, J. Saillard and C. W. Liu, Chem. Sci., 2018, Advance Article , DOI: 10.1039/C8SC01508B

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