Computationally guided synthesis of a hierarchical [4[2+3]+6] porous organic ‘cage of cages’

Here we report a two-step, hierarchical synthesis that assembles a trigonal prismatic organic cage into a more symmetric, higher-order tetrahedral cage, or ‘cage of cages’. Both the preformed [2+3] trigonal prismatic cage building blocks and the resultant tetrahedral [4[2+3]+6]cage molecule are constructed using ether bridges. This strategy affords the [4[2+3]+6]cage molecule excellent hydrolytic stability that is not a feature of more common dynamic cage linkers, such as imines. Despite its relatively high molar mass (3,001 g mol⁻¹), [4[2+3]+6]cage exhibits good solubility and crystallizes into a porous superstructure with a surface area of 1,056 m² g⁻¹. By contrast, the [2+3] building block is not porous. The [4[2+3]+6]cage molecule shows high CO₂ and SF₆ uptakes due to its polar skeleton. The preference for the [4[2+3]+6]cage molecule over other cage products can be predicted by computational modelling, as can its porous crystal packing, suggesting a broader design strategy for the hierarchical assembly of organic cages with synthetically engineered functions.