Covalent organic cages have potential applications in mol. inclusion/recognition and porous organic crystals. Bridging arene units with sp3 atoms enables facile construction of rigid isolated internal vacancies, and various prismatic arene cages have been synthesized by kinetically controlled covalent bond formation. However, the synthesis of a tetrahedral one, which requires twice as much bond formation as prismatic ones, has been limited to a thermodynamically controlled dynamic SNAr reaction, and this reversible covalent bond formation made the resulting cage product chem. unstable. Here we report the Rh-catalyzed high-yielding and highly 1,3,5-selective room temperature [2+2+2] cycloaddition of push-pull alkynes e.g., di-Me 3,3'-((oxybis(4,1-phenylene))bis(oxy))dipropiolate and its application to the synthesis of chem. stable aryl ether cages e.g., I of various shapes and sizes, including prismatic and tetrahedral forms. These aryl ether cages are highly crystalline and intertwine with each other to form regular packing structures. Some aryl ether cages encapsulated isolated water mols. in their hydrophobic cavity by hydrogen bonding with the multiple ester moieties.
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