Time‐Resolved Assembly of Cluster‐in‐Cluster {Ag12}‐in‐{W76} 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)Ag₁₈Cl(Te₃W₃₈O₁₃₄)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 {Te₃W₃₈} units around a single chloride template and the formation of a {Ag₁₂} cluster, giving a {Ag₁₂}‐in‐{W₇₆} 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 TeO₃^2?, Cl^?, and Ag⁺ play in the self‐assembly of compounds 1 – 3 .