Abstract
Here we report the formation of giant {Mo126 W30 } 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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