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Heteroatom‐Doping Increases Cluster Nuclearity: From an [Ag 20 ] to an [Au 3 Ag 18 ] Core
Author(s) -
Chang WanTing,
Sharma Sachil,
Liao JianHong,
Kahlal Samia,
Liu YuChiao,
Chiang MingHsi,
Saillard JeanYves,
Liu C. W.
Publication year - 2018
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201802679
Subject(s) - icosahedral symmetry , dopant , heteroatom , crystallography , cluster (spacecraft) , doping , shell (structure) , symmetry (geometry) , materials science , core (optical fiber) , atom (system on chip) , chemistry , geometry , ring (chemistry) , optoelectronics , organic chemistry , computer science , embedded system , programming language , mathematics , composite material
A templated galvanic exchange performed on [Ag 20 {Se 2 P(O i Pr) 2 } 12 ] of C 3 symmetry with three equiv Au I yields a mixture of [Au 1+ x Ag 20− x {Se 2 P(O i Pr) 2 } 12 ] + ( x= 0–2) from which [Au@Ag 20 {Se 2 P(O i Pr) 2 } 12 ] + and [Au@Au 2 Ag 18 {Se 2 P(O i Pr) 2 } 12 ] + are successfully characterized to have T and C 1 symmetry, respectively. Crystal structural analyses combined with DFT calculations on the model compounds explicitly demonstrate that the central Ag 0 of Ag 20 being oxidized by Au I migrates to the protecting atomic shell as a new capping Ag I , and both second and third Au dopants prefer occupying non‐adjacent icosahedron vertices. The differences in symmetry, T and C 1 , are manifested in the spatial orientation of their protecting atomic shell composed of eight capping Ag atoms as well as re‐construction upon the replacement of Ag atoms on the vertices of AuAg 12 icosahedral core with second and third Au dopants. As a result, a unique pathway for substitutional‐doped clusters with increased nuclearity is proposed.