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Axial-Bundle Phases - New Modes of 2D, 3D, and Helical Columnar Self-Assembly in Liquid Crystalline Phases of Bolaamphiphiles with Swallow Tail Lateral Chains

DOI: 10.1021/ja110065r DOI Help

Authors: Marko Prehm (Martin-Luther-University Halle-Wittenberg) , Feng Liu (University of Sheffield) , Xiangbing Zeng (Department of Engineering Materials, University of Sheffield) , Goran Ungar (University of Sheffield) , Carsten Tschierske (Martin-Luther-University Halle-Wittenberg)
Co-authored by industrial partner: No

Type: Journal Paper
Journal: Journal Of The American Chemical Society , VOL 133 (13)

State: Published (Approved)
Published: March 2011

Abstract: Two series of polyphilic molecules composed of a rigid and linear p-terphenyl core, terminated at both ends with polar glycerol groups capable of hydrogen bonding, and two branched swallow tail-type lateral chains, composed of a fluorinated and a nonfluorinated branch or two fluorinated branches, were synthesized and investigated by differential scanning calorimetry, polarizing microscopy, and X-ray diffraction (XRD) with respect to their self-assembly in thermotropic liquid crystalline (LC) phases. Hexagonal columnar phases were formed by all molecules, at least at the highest temperature. In these phases the columns are composed of a core of aromatic rods and an aliphatic shell. The aromatic rods form bundles which are rotationally averaged and lie parallel to the column long axis. This unique organization is proven by different optical and XRD methods. The aromatic and glycerol groups inside the rod bundles are segregated into alternating segments. Depending on temperature and molecular structure, long-range intercolumnar correlation of this periodicity could take place, leading to a 3D-ordered LC phase with rhombohedral Rm symmetry. The bundles are embedded in the matrix of the lateral chains, which is divided into fluoroalkyl- and aliphatic-rich regions. In the 2D columnar phase the fluorinated regions take the form of either straight columns running along the edges of the hexagonal Voronoi cells or, for compounds with a higher degree of fluorination, fuse to a hexagonal honeycomb enclosing the aromatic cores. In the Rm phase the fluorine-rich chains are preferentially found along right- and left-handed helices wound around the 31 screw axes between the main aromatic columns.

Subject Areas: Chemistry

Instruments: I07-Surface & interface diffraction , I22-Small angle scattering & Diffraction