title: Peculiar holes on checkerboard facets of a trigonal prismatic Au9Ag36(SPhCl2)27(PPh3)6cluster caused by steric hindrance and magic electron count.
abstract: We report herein the synthesis and structure of a 45-atom trigonal-prismatic Au-Ag bimetallic nanocluster, formulated as Au9Ag36(SPhCl2)27(PPh3)6, based on single-crystal X-ray crystallographic determination. The structure can be described as a core-shell structure with a tricapped trigonal prismatic (ttp1) Au9core encaged in a larger (frequency-two) tricapped trigonal prismatic (ttp2) Ag30shell. The cluster is terminated by six Ag(PPh3) moieties which, along with ttp2 and 27 thiolates, constitute the outer trigonal-prismatic (TP) shell. Each of the three nearly coplanar yet severely distorted "square" faces of TP contains 13 Ag atoms which are arranged in a way reminiscent of the (100) face of a face-centered cubic (fcc) structure. Of the 30 edges formed by these quasi-(100) faces of the TP, only 27 are bridged by the thiolate ligands; three are vacant, one on each "square" face. It is believed that these peculiar vacant ligand sites are caused by steric hindrance of the thiolate ligands in combination with the superatomic electronic shell closing of 1S21P61D10rendering 9(ttp1) + 30(ttp2) + 6(TP) - 27(SR) = 18 jellium electrons.
authors.affiliation: Collaborative Innovation Center of Chemistry for Energy Materials, State Key Laboratory for Physical Chemistry of Solid Surfaces, and Department of Chemistry, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen 361005, China. nfzheng@xmu.edu.cn boonkteo@xmu.edu.cn.
authors.forename: Lei
authors.identifier: http://orcid.org/0000-0003-3191-6719
authors.initials: L
authors.lastname: Huang
authors.affiliation: Collaborative Innovation Center of Chemistry for Energy Materials, State Key Laboratory for Physical Chemistry of Solid Surfaces, and Department of Chemistry, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen 361005, China. nfzheng@xmu.edu.cn boonkteo@xmu.edu.cn.
authors.forename: Juanzhu
authors.initials: J
authors.lastname: Yan
authors.affiliation: Collaborative Innovation Center of Chemistry for Energy Materials, State Key Laboratory for Physical Chemistry of Solid Surfaces, and Department of Chemistry, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen 361005, China. nfzheng@xmu.edu.cn boonkteo@xmu.edu.cn.
authors.forename: Liting
authors.initials: L
authors.lastname: Ren
authors.affiliation: Collaborative Innovation Center of Chemistry for Energy Materials, State Key Laboratory for Physical Chemistry of Solid Surfaces, and Department of Chemistry, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen 361005, China. nfzheng@xmu.edu.cn boonkteo@xmu.edu.cn.
authors.forename: Boon K
authors.initials: BK
authors.lastname: Teo
authors.affiliation: Collaborative Innovation Center of Chemistry for Energy Materials, State Key Laboratory for Physical Chemistry of Solid Surfaces, and Department of Chemistry, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen 361005, China. nfzheng@xmu.edu.cn boonkteo@xmu.edu.cn.
authors.forename: Nanfeng
authors.identifier: http://orcid.org/0000-0001-9879-4790
authors.initials: N
authors.lastname: Zheng