title: [Ag20 {S2 P(OR)2 }12 ]: A Superatom Complex with a Chiral Metallic Core and High Potential for Isomerism.
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.
authors.affiliation: Department of Chemistry, National Dong Hwa University, No. 1, Sec. 2, Da Hsueh Rd., Shoufeng, Hualien, 97401, Taiwan, R.O.C.|Centre for Chemical Sciences, School of Basic and Applied Sciences, Central University of Punjab, Bathinda, 151 001, India.
authors.forename: Rajendra S
authors.initials: RS
authors.lastname: Dhayal
authors.affiliation: Department of Chemistry, National Dong Hwa University, No. 1, Sec. 2, Da Hsueh Rd., Shoufeng, Hualien, 97401, Taiwan, R.O.C.
authors.forename: Yan-Ru
authors.initials: YR
authors.lastname: Lin
authors.affiliation: Department of Chemistry, National Dong Hwa University, No. 1, Sec. 2, Da Hsueh Rd., Shoufeng, Hualien, 97401, Taiwan, R.O.C.
authors.forename: Jian-Hong
authors.initials: JH
authors.lastname: Liao
authors.affiliation: Department of Chemistry, Fu Jen Catholic University, New Taipei City, 24205, Taiwan, R.O.C.
authors.forename: Yuan-Jang
authors.initials: YJ
authors.lastname: Chen
authors.affiliation: Institute of Chemistry, Academica Sinica, Taipei, Taiwan, R.O.C.
authors.forename: Yu-Chiao
authors.initials: YC
authors.lastname: Liu
authors.affiliation: Institute of Chemistry, Academica Sinica, Taipei, Taiwan, R.O.C.
authors.forename: Ming-Hsi
authors.initials: MH
authors.lastname: Chiang
authors.affiliation: UMR-CNRS, 6226 "Institut des Sciences Chimiques de Rennes", Université de Rennes 1, 35042, Rennes Cedex, France.
authors.forename: Samia
authors.initials: S
authors.lastname: Kahlal
authors.affiliation: UMR-CNRS, 6226 "Institut des Sciences Chimiques de Rennes", Université de Rennes 1, 35042, Rennes Cedex, France.
authors.forename: Jean-Yves
authors.initials: JY
authors.lastname: Saillard
authors.affiliation: 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.
authors.forename: C W
authors.initials: CW
authors.lastname: Liu
keywords: chirality; isomerism; nanoclusters; silver; superatoms