Chiral recognition via helical sense and phase in a crystalline supramolecular array of intermeshed triple-helices

Hexatertiary butyl‐substituted D3‐symmetrical cage ligands composed of octahedral bidentate complexes of Ni(II) or Cu(II) ligated on either side to triskelion arrangements of three salicyl rings bound to a central nitrogen hub atom exhibit triple‐helical conformations. Maximization of intermolecular aromatic–aromatic interactions between these complexes promote extended tongue and groove interleaving and affords a supramolecular array of diastereomeric intermeshed C3‐symmetrical triple‐helices perpetuating sideways throughout alternating enantiomeric layer stacks in the entire P‐3 space group crystal lattice. Chiral recognition within these supramolecular ensembles is based upon the principles of helical sense and phase. A discussion of the symmetry, mechanical and chemical factors, and constraints influencing the formation of these self‐assembled crystalline supramolecular ensembles will be presented. Chirality, 2008. © 2008 Wiley‐Liss, Inc.