title: Coexistence of helical morphologies in columnar stacks of star-shaped discotic hydrazones.
abstract: Discotic hydrazone molecules are of particular interest as they form discotic phases where the discs are rigidified by intramolecular hydrogen bonds. Here, we investigate the thermotropic behavior and solid-state organizations of three discotic hydrazone derivatives with dendritic groups attached to their outer peripheries, containing six, eight, and ten carbons of linear alkoxy chains. On the basis of two-dimensional wide angle X-ray scattering (2DWAXS), the elevated temperature liquid crystalline (LC) phases were assigned to a hexagonal columnar (Colh) organization with nontilted hydrazone discs for all three compounds. With WAXS, advanced solid-state nuclear magnetic resonance (SSNMR) techniques, and ab initio computations, the compounds with six and ten carbons of achiral alkoxy side chains were further subjected to studies at 25 °C, revealing complex crystalline phases with rigid columns and flexible side chains. This combined approach led to models of coexisting helical columnar stacking morphologies for both systems with two different tilt/pitch angles between successive hydrazone molecules. The differences in tilt/pitch angles between the two compounds illustrate that the columns with short alkoxy chains (six carbons) are more influenced by the presence of other stacks in their vicinity, while those with long side chains are less tilted due to a larger alkoxy (ten carbons) buffer zone. The formation of different packing morphologies in the crystalline phase of a columnar LC has rarely been reported so far, which suggests the possibility of complex stacking structures of similar organic LC systems, utilizing small molecules as potential materials for applications in organic electronics.
authors.affiliation: Max Planck Institute for Polymer Research, Ackermannweg 10, 55128 Mainz, Germany.
authors.forename: Jie
authors.initials: J
authors.lastname: Shu
authors.forename: Dmytro
authors.initials: D
authors.lastname: Dudenko
authors.forename: Morteza
authors.initials: M
authors.lastname: Esmaeili
authors.forename: Jun Ha
authors.initials: JH
authors.lastname: Park
authors.forename: Sreenivasa Reddy
authors.initials: SR
authors.lastname: Puniredd
authors.forename: Ji Young
authors.initials: JY
authors.lastname: Chang
authors.forename: Dag Werner
authors.initials: DW
authors.lastname: Breiby
authors.forename: Wojciech
authors.initials: W
authors.lastname: Pisula
authors.forename: Michael Ryan
authors.initials: MR
authors.lastname: Hansen