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[Cu 13 {S 2 CN n Bu 2 } 6 (acetylide) 4 ] + : A Two‐Electron Superatom
Author(s) -
Chakrahari Kiran Kumarvarma,
Liao JianHong,
Kahlal Samia,
Liu YuChiao,
Chiang MingHsi,
Saillard JeanYves,
Liu C. W.
Publication year - 2016
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.201608609
Subject(s) - jellium , superatom , crystallography , acetylide , nanoclusters , chemistry , copper , tetrahedron , cluster (spacecraft) , x ray crystallography , atomic physics , electronic structure , stereochemistry , physics , computational chemistry , metal , diffraction , programming language , organic chemistry , computer science , optics
The first structurally characterized copper cluster with a Cu 13 centered cuboctahedral arrangement, a model of the bulk copper fcc structure, was observed in [Cu 13 (S 2 CN n Bu 2 ) 6 (C≡CR) 4 ](PF 6 ) (R=C(O)OMe, C 6 H 4 F) nanoclusters. Four of the eight triangular faces of the cuboctahedron are capped by acetylide groups in μ 3 fashion, and each of the six square faces is bridged by a dithiolate ligand in μ 2 ,μ 2 fashion, which leads to a truncated tetrahedron of twelve sulfur atoms. DFT calculations are fully consistent with the description of these Cu 13 clusters as two‐electron superatoms, that is, a [Cu 13 ] 11+ core passivated by ten monoanionic ligands, with an a 1 HOMO containing two 1S jellium electrons.