Controlling the Reactivity of the [P(8)W(48)O(184)](40−) Inorganic Ring and Its Assembly into POMZite Inorganic Frameworks with Silver Ions

The construction of pure‐inorganic framework materials with well‐defined design rules and building blocks is challenging. In this work, we show how a polyoxometalate cluster with an integrated pore, based on [P(8)W(48)O(184)](40−) (abbreviated as {P(8)W(48)}), can be self‐assembled into inorganic frameworks using silver ions, which both enable reactions on the cluster as well as link them together. The {P(8)W(48)} was found to be highly reactive with silver ions resulting in the in situ generation of fragments, forming {P(9)W(63)O(235)} and {P(10)W(66)O(251)} in compound (1) where these two clusters co‐crystallize and are connected into a POMZite framework with 11 Ag(+) ions as linkers located inside clusters and 10 Ag(+) linking ions situated between clusters. Decreasing both the concentration of Ag(+) ions, and the reaction temperature compared to the synthesis of compound (1), leads to {P(8)W(51)O(196)} in compound 2 where the {P(8)W(48)} clusters are linked to form a new POMZite framework with 9 Ag(+) ions per formula unit. Further tuning of the reaction conditions yields a cubic porous network compound (3) where {P(8)W(48)} clusters as cubic sides are joined by 4 Ag(+) ions to give a cubic array and no Ag(+) ions were found inside the clusters.