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Nat Commun. 2018 Feb 21;9(1):744. doi: 10.1038/s41467-018-03136-9.

Chiral Ag23 nanocluster with open shell electronic structure and helical face-centered cubic framework.

Author information

1
State Key Laboratory of Catalysis, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian, 116023, P. R. China.
2
School of Physical Science and Technology, ShanghaiTech University, Shanghai, 201210, P. R. China.
3
Department of Chemistry, Carnegie Mellon University, Pittsburgh, PA, 15213, USA.
4
Department of Chemistry, University of Missouri-Columbia, Columbia, MO, 65211, USA.
5
School of Computational Sciences, Korea Institute for Advanced Study, Seoul, 02455, Korea.
6
State Key Laboratory of Catalysis, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian, 116023, P. R. China. gaoli@dicp.ac.cn.
7
Department of Chemistry, Carnegie Mellon University, Pittsburgh, PA, 15213, USA. rongchao@andrew.cmu.edu.

Abstract

We report the synthesis and crystal structure of a nanocluster composed of 23 silver atoms capped by 8 phosphine and 18 phenylethanethiolate ligands. X-ray crystallographic analysis reveals that the kernel of the Ag nanocluster adopts a helical face-centered cubic structure with C2 symmetry. The thiolate ligands show two binding patterns with the surface Ag atoms: tri- and tetra-podal types. The tetra-coordination mode of thiolate has not been found in previous Ag nanoclusters. No counter ion (e.g., Na+ and NO3-) is found in the single-crystal and the absence of such ions is also confirmed by X-ray photoelectron spectroscopy analysis, indicating electrical neutrality of the nanocluster. Interestingly, the nanocluster has an open shell electronic structure (i.e., 23(Ag 5s1)-18(SR) = 5e), as confirmed by electron paramagnetic resonance spectroscopy. Time-dependent density functional theory calculations are performed to correlate the structure and optical absorption/emission spectra of the Ag nanocluster.

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