RESUMO
Covalent organic cages have potential applications in molecular 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 SN Ar reaction, and this reversible covalent bond formation made the resulting cage product chemically 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 and its application to the synthesis of chemically stable aryl ether cages 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 molecules in their hydrophobic cavity by hydrogen bonding with the multiple ester moieties.
RESUMO
A high-yielding new route to substituted cycloparaphenylenes has been developed via reductive aromatization of a diyne bearing two cyclohexadiene units giving a cyclophenylene-ethynylene (CPE) followed by the cationic rhodium(I)/dppe complex-catalyzed intermolecular [2+2+2] cycloaddition (cycloaromatization) of the CPE with monoynes. The thus-obtained products, substituted [8]cycloparaphenylene-triphenylenes ([8]CPPTs), exhibited definite aggregation-induced emission (AIE). This molecule is noteworthy as a novel AIE-active cycloarylene that does not have well-known AIE luminogens, such as tetraphenylethene and 1,2,4,5-tetraphenylbenzene skeletons. The single-crystal X-ray diffraction analyses of the AIE-active [8]CPPTs revealed their highly ordered packing structures in which the rotation of the triphenylene moieties is restricted.
