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Chemistry. 2016 Jul 11;22(29):9943-7. doi: 10.1002/chem.201602275. Epub 2016 Jun 8.

[Ag20 {S2 P(OR)2 }12 ]: A Superatom Complex with a Chiral Metallic Core and High Potential for Isomerism.

Author information

1
Department of Chemistry, National Dong Hwa University, No. 1, Sec. 2, Da Hsueh Rd., Shoufeng, Hualien, 97401, Taiwan, R.O.C.
2
Centre for Chemical Sciences, School of Basic and Applied Sciences, Central University of Punjab, Bathinda, 151 001, India.
3
Department of Chemistry, Fu Jen Catholic University, New Taipei City, 24205, Taiwan, R.O.C.
4
Institute of Chemistry, Academica Sinica, Taipei, Taiwan, R.O.C.
5
UMR-CNRS, 6226 "Institut des Sciences Chimiques de Rennes", Université de Rennes 1, 35042, Rennes Cedex, France.
6
Department of Chemistry, National Dong Hwa University, No. 1, Sec. 2, Da Hsueh Rd., Shoufeng, Hualien, 97401, Taiwan, R.O.C.. chenwei@mail.ndhu.edu.tw.

Abstract

The synthesis and structural determination of a silver nanocluster [Ag20 {S2 P(OiPr)2 }12 ] (2), which contains an intrinsic chiral metallic core, is produced by reduction of one silver ion from the eight-electron superatom complex [Ag21 {S2 P(OiPr)2 }12 ](PF6 ) (1) by borohydrides. Single-crystal X-ray analysis displays an Ag20 core of pseudo C3 symmetry comprising a silver-centered Ag13 icosahedron capped by seven silver atoms. Its n-propyl derivative, [Ag20 {S2 P(OnPr)2 }12 ] (3), can also be prepared by the treatment of silver(I) salts and dithiophosphates in a stoichiometric ratio in the presence of excess amount of [BH4 ](-) . Crystal structure analyses reveal that the capping silver-atom positions relative to their icosahedral core are distinctly different in 2 and 3 and generate isomeric, chiral Ag20 cores. Both Ag20 clusters display an emission maximum in the near IR region. DFT calculations are consistent with a description within the superatom model of an 8-electron [Ag13 ](5+) core protected by a [Ag7 {S2 P(OR)2 }12 ](5-) external shell. Two additional structural variations are predicted by DFT, showing the potential for isomerism in such [Ag20 {S2 P(OR)2 }12 ] species.

KEYWORDS:

chirality; isomerism; nanoclusters; silver; superatoms

PMID:
27189869
DOI:
10.1002/chem.201602275
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