title: Self-assembly of hekates-tris(N-salicylideneaniline)s into columnar structures: synthesis and characterization.
abstract: Two series of new, photoluminescent star-shaped discotic liquid crystals, recently termed as "hekates", derived from tris(N-salicylideneaniline)s (TSANs), were synthesized by the facile threefold condensation of 3,4-bis(alkoxy)phenyl 4-aminobenzoates/3,4,5-tris(alkoxy) phenyl 4-aminobenzoates with 1,3,5-triformylphloroglucinol and characterized. These two series of discotics with six and nine peripheral n-alkoxy tails were especially designed and accomplished to understand the relation between mesomorphic/photophysical properties and molecular structure. Proton NMR spectral analysis revealed their existence as an inseparable mixture of two keto-enamine tautomeric forms featuring C(3h) and C(s) rotational symmetries. A systematic study into the thermotropic liquid crystal behavior using polarizing optical microscopy, differential scanning calorimetry, and X-ray scattering confirmed the presence of columnar (Col) phase in vast majority of the TSANs prepared. The two-dimensional (2D) lattices of these fluid columnar phases were found to be characteristic of hexagonal Col (Col(h)), rectangular Col (Col(r)), or oblique Col (Col(ob)) phases depending on the number/length of the peripheral flexible chains. The stabilization of the Col(ob) phase, a less commonly found fluid columnar structure, and the first of its kind in TSAN systems, implies very intensive intermolecular (face-to-face) interactions among the TSAN cores within the column. The photophysical properties were investigated both in solution and the columnar states by UV-vis absorption and photoluminescence; markedly, the solution state emits light in the blue region. The light-emitting ability of the Col phase is particularly significant given the possibility that, in such cores, the protons and electrons interact with each other through the H-bonding environment.
authors.affiliation: Centre for Soft Matter Research, Jalahalli, Bangalore, 560 013, India.
authors.forename: Ammathnadu S
authors.initials: AS
authors.lastname: Achalkumar
authors.forename: Uma S
authors.initials: US
authors.lastname: Hiremath
authors.forename: D S Shankar
authors.initials: DS
authors.lastname: Rao
authors.forename: S Krishna
authors.initials: SK
authors.lastname: Prasad
authors.forename: Channabasaveshwar V
authors.initials: CV
authors.lastname: Yelamaggad