Reticular Chemistry in the Construction of Porous Organic Cages

Reticular chemistry offers the possibility of systematic design of porous materials with different pores by varying the building blocks, while the emerging porous organic cage (POC) system remains generally unexplored. A series of new POCs with dimeric cages with odd–even behaviors, unprecedented trimeric triangular prisms, and the largest recorded hexameric octahedra have been prepared. These POCs are all constructed from the same tetratopic tetraformylresorcin[4]­arene cavitand by simply varying the diamine ligands through Schiff-base reactions and are fully characterized by X-ray crystallography, gas sorption measurements, NMR spectroscopy, and mass spectrometry. The odd–even effects in the POC conformation changes of the [2 + 4] dimeric cages have been confirmed by density functional theory calculations, which are the first examples of odd–even effects reported in the cavitand-based cage system. Moreover, the “V” shape phenylenediamine linkers are responsible for the novel [3 + 6] triangular prisms. The window size and environment can be easily functionalized by different groups, providing a promising platform for the construction of multivariate POCs. Use of linear phenylenediamines led to record-breakingly large [6 + 12] truncated octahedral cages, the maximum inner cavity diameters and volumes of which could be readily modulated by increasing the spacer length of the phenylenediamine linkers. This work can lead to an understanding of the self-assembly behaviors of POCs and also sheds light on the rational design of POC materials for practical applications.