Time‐Resolved Assembly of Cluster‐in‐Cluster {Ag 12 }‐in‐{W 76 } Polyoxometalates under Supramolecular Control

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 .