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Time‐Resolved Assembly of Cluster‐in‐Cluster {Ag 12 }‐in‐{W 76 } Polyoxometalates under Supramolecular Control
Author(s) -
Zhan Caihong,
Cameron Jamie M.,
Gao Jing,
Purcell Jamie W.,
Long DeLiang,
Cronin Leroy
Publication year - 2014
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.201402932
Subject(s) - polyoxometalate , supramolecular chemistry , cluster (spacecraft) , chemistry , crystallography , self assembly , stereochemistry , nanotechnology , materials science , crystal structure , catalysis , organic chemistry , computer science , programming language
We report the time‐resolved supramolecular assembly of a series of nanoscale polyoxometalate clusters (from the same one‐pot reaction) of the form: [H (10+ m ) Ag 18 Cl(Te 3 W 38 O 134 ) 2 ] n , where n =1 and m =0 for compound 1 (after 4 days), n =2 and m =3 for compound 2 (after 10 days), and n =∞ and m =5 for compound 3 (after 14 days). The reaction is based upon the self‐organization of two {Te 3 W 38 } units around a single chloride template and the formation of a {Ag 12 } cluster, giving a {Ag 12 }‐in‐{W 76 } cluster‐in‐cluster in compound 1 , which further aggregates to cluster compounds 2 and 3 by supramolecular Ag‐POM interactions. The proposed mechanism for the formation of the clusters has been studied by ESI‐MS. Further, control experiments demonstrate the crucial role that TeO 3 2− , Cl − , and Ag + play in the self‐assembly of compounds 1 – 3 .