Calix[4]arenes are extremely versatile ligands that are capable of supporting the formation of a wide variety of polymetallic clusters of paramagnetic metal ions. One can exert influence over cluster formation through alteration of the calix[4]arene framework and subsequent ‘expansion’ of the lower-rim polyphenolic binding site. The present contribution investigates cluster formation with calix[4]arenes substituted at all four methylene bridge positions with furan moieties. Two known cluster types have been isolated with this ligand, the structures of which lend insight into factors that may ultimately preclude the formation of mixed-metal species.

Ring-opening of furans at the equatorial methylene bridge positions of a calix[4]arene gives access to a range of new molecules (in good yield) that have widespread potential impact in supramolecular chemistry amongst other areas.