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

Qiang Zhu, Hang Qu, Gokay Avci, Roohollah Hafizi, Chengxi Zhao, Graeme M. Day, Kim E. Jelfs, Marc A. Little*, Andrew I. Cooper*

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

1 Citation (Scopus)
23 Downloads (Pure)


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. (Figure presented.)

Original languageEnglish
JournalNature Synthesis
Early online date26 Apr 2024
Publication statusE-pub ahead of print - 26 Apr 2024

ASJC Scopus subject areas

  • Chemistry (miscellaneous)
  • Inorganic Chemistry
  • Organic Chemistry
  • Materials Chemistry


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