Face-controlled chirality induction in octahedral thiacalixarene-based porous coordination cages

Nanosized chiral octahedral M₃₂ coordination cages were prepared via self-assembly of sulfonylcalix[4]arene tetranuclear M(II) clusters (M = Co or Ni) with enantiomerically enriched linkers based on tris(dipyrrinato)cobalt(III) complexes, appended with peripheral carboxylic groups. Two pairs of enantiomers of cages were obtained and unambiguously characterized from a structural point of view, using single crystal X-ray diffraction. Chiral-HPLC was used to evidence the enantiomers. In the solid state, the compounds present intrinsic and extrinsic porosity: the intrinsic porosity is linked with the size of the cages, which present an inner diameter of ca. 19 Å. The obtained solid-state supramolecular architectures demonstrated good performances as adsorbents for water and 2-butanol guest molecules.