Abstract

AbstractHere we report the formation of giant {Mo126W30} polyoxometalate cages templated by π‐conjugated planar ligands. Their inorganic shells incorporate arrays of 18 stacked aromatic carboxylates, such as 1,3,5‐benzenetricarboxylate or 5‐nitroisophthalate, and the assembly is stabilized by multiple π–π interactions. NMR data confirmed that the cages are stable in solution and the inner aromatic templates can be postsynthetically replaced by selected aliphatic dicarboxylates, paving the way for endo‐functionalization and exploration of the reactivities within the cage cavities.

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