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.

The removal of ethane (C2H6) from its analogous ethylene (C2H4) is of paramount importance in the petrochemical industry, but highly challenging due to their similar physicochemical properties. The use of emerging porous organic cage (POC) materials for C2H6/C2H4 separation is still in its infancy. Here, we report the benchmark example of a truncated octahedral calix[4]resorcinarene-based POC adsorbent (CPOC-301), preferring to adsorb C2H6 than C2H4, and thus can be used as a robust absorbent to directly separate high-purity C2H4 from the C2H6/C2H4 mixture. Molecular modelling studies suggest the exceptional C2H6 selectivity is due to the suitable resorcin[4]arene cavities in CPOC-301, which form more multiple C–H···π hydrogen bonds with C2H6 than with C2H4 guests. This work provides a fresh avenue to utilize POC materials for highly selective separation of industrially important hydrocarbons.

Whether or not the topology of three-dimensional covalent organic frameworks (3D COFs) can be tuned via steric control remains a big question and has never been reported. Herein, we describe the designed synthesis of two highly crystalline 3D COFs (3D-TPB-COF-OMe and 3D-TPB-COF-Ph), through the polycondensation of tetra­(p-aminophenyl)­methane and methoxy- or phenyl- substituted 1,2,4,5-tetrakis­(4-formylphenyl)­benzene on the 3- and 6-positions. Amazingly, by using the continuous rotation electron diffraction technique, 3D-TPB-COF-OMe is determined to have a 5-fold interpenetrated structure with a reported pts net, while 3D-TPB-COF-Ph adopts an unprecedented self-penetrated ljh topology (ljh = Luojia Hill) that does not exist in the database of ToposPro. Therefore, by altering the substituents from methoxy to phenyl groups, the topology of designed 3D COFs changes accordingly, and a rare net is now available. This result clearly demonstrates that such COF structures need to be carefully determined due to its complexity, and moreover, it is promising to design 3D COFs with new topology for interesting application by increasing the steric hindrance of molecular building blocks.