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Alkynyl‐Protected Au 23 Nanocluster: A 12‐Electron System
Author(s) -
Wan XianKai,
Yuan ShangFu,
Tang Qing,
Jiang Deen,
Wang QuanMing
Publication year - 2015
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.201500590
Subject(s) - cluster (spacecraft) , crystallography , chemistry , crystal structure , electronic structure , nanoclusters , atomic orbital , electron , computational chemistry , physics , organic chemistry , quantum mechanics , computer science , programming language
A 23‐gold‐atom nanocluster was prepared by NaBH 4 ‐mediated reduction of a solution of PhCCAu and Ph 3 PAuSbF 6 in CH 2 Cl 2 . The cluster composition was determined to be [Au 23 (PhCC) 9 (Ph 3 P) 6 ] 2+ and single‐crystal X‐ray diffraction revealed that the cluster has an unprecedented Au 17 kernel protected by three PhC 2 ‐Au‐C 2 (Ph)‐Au‐C 2 Ph motifs and six Ph 3 P groups. The Au 17 core can be viewed as the fusion of two Au 10 units sharing a Au 3 triangle. Electronic structure analysis from DFT calculations suggests that the stability of this unusual 12‐electron cluster is a result of the splitting of the superatomic 1D orbitals under D 3 h symmetry of the Au 17 kernel. The discovery and determination of the structure of the Au 23 cluster demonstrates the versatility of the alkynyl ligand in leading to the formation of new cluster compounds.