title: Supramolecular helical stacking of metallomesogens derived from enantiopure and racemic polycatenar oxazolines.
abstract: The present report undertakes a challenge of general interest in supramolecular chemistry: the achievement of helical organizations with controlled structure. To achieve this target we considered the possibility of inducing supramolecular chirality using molecules that were designed to organize into columnar mesophases. The use of oxazoline-derived ligands and metal coordination served as tools to prepare molecules with a phasmidic-like structure, which show columnar organization in the liquid crystalline state. To ensure the formation of chiral mesophases, these complexes bear stereogenic centers in the rigid coordination environment of the metal. X-ray and circular dichroism experiments have revealed that chirality transfer does indeed take place from the chiral molecule to the columnar liquid crystal organization. This chiral columnar organization appears as a helix consisting of stacks of molecules that rotate with respect to one another along the column while maintaining their mean planes parallel to each other. In fact, it has been concluded that packing of these polycatenar molecules must be more efficient upon rotation of a molecule with respect to the adjacent one along the column. Furthermore, the same type of helical supraorganization has been found to be present in the mesophase of the racemic mixture and the mixture of diastereomers prepared from the racemic ligand. In this case, segregation of the optical isomers is proposed to occur to give rise to both types of helix (right-handed and left-handed).
authors.affiliation: Química Orgánica, Facultad de Ciencias-I.C.M.A., Universidad de Zaragoza-C.S.I.C., 50009-Zaragoza, Spain.
authors.forename: Joaquín
authors.initials: J
authors.lastname: Barberá
authors.forename: Emma
authors.initials: E
authors.lastname: Cavero
authors.forename: Matthias
authors.initials: M
authors.lastname: Lehmann
authors.forename: José-Luis
authors.initials: JL
authors.lastname: Serrano
authors.forename: Teresa
authors.initials: T
authors.lastname: Sierra
authors.forename: Jesús T
authors.initials: JT
authors.lastname: Vázquez