Fully Collapsed Imploded Cryptophanes in Solution and in the Solid State

Abstract

Cryptophanes with flexible linkers derived from (±)-tris-(4-formyl-phenyl)-cyclotriguaiacylene with either bisoxydi(ethylamine) or bis(aminopropyl)ether were isolated as single crystals, the crystal structures of which showed the proposed, but previously uncharacterised, out-in conformation, in which both cyclotriguaiacylene fragments adopt a crown conformation with one crown sitting inside the other. The usual cage-like out-out conformation of the cryptophanes was observed when crystals were dissolved upon heating, and the molecules collapsed back to the out-in isomers over time. In contrast, a cryptophane also derived from (±)-tris-(4-formyl-phenyl)-cyclotriguaiacylene but with rigid dibenzalhydrazine linkers was isolated as the more usual out-out isomer.

Keywords: cage conformations; cryptophanes; dynamic covalent chemistry; host-guest systems; supramolecular chemistry.