Design of liquid crystals with ‘de Vries-like’ properties: the effect of carbosilane nanosegregation in 5-phenyl-1,3,4-thiadiazole mesogens
- 21 August 2014
- journal article
- research article
- Published by Royal Society of Chemistry (RSC) in Journal of Materials Chemistry C
- Vol. 2 (39) , 8270-8276
Abstract
Smectic liquid crystals with ‘de Vries-like’ properties are characterized by a maximum layer contraction of ≤1% upon transition from the orthogonal SmA phase to the tilted SmC phase. A defining structural characteristic of most ‘de Vries-like’ materials is a nanosegregating element that strongly promotes the formation of smectic layers. We show herein the effect of varying the length of a nanosegregating carbosilane end-group on ‘de Vries-like’ properties in three series of 5-phenyl-1,3,4-thiadiazole mesogens with chloro-terminated alkoxy chains (QL13-n, QL18-n and QL19-n). Shortening the end-group from a tricarbosilane to a monocarbosilane causes a decrease in ‘de Vries-like’ character, as measured by the reduction factor R, which is consistent with a decrease in nanosegregation and quality of the lamellar ordering. Measurements of the orientational order parameter S2 by 2D X-ray scattering of smectic monodomains show a concomitant increase in S2 that is consistent with the hypothesis that ‘de Vries-like’ behavior in these materials arises from a combination of high lamellar order and low orientational order. The requirement of a nanosegregating structural element to achieve ‘de Vries-like’ behavior is confirmed by the characterization of the chloro-terminated mesogen 2-(6-chlorohexyloxy)-5-(4-hexyloxyphenyl)-1,3,4-thiadiazole (QL28-6/6), which undergoes a SmA–SmC transition with a maximum layer contraction of 4.1% and behaves like a conventional smectogen.Keywords
This publication has 38 references indexed in Scilit:
- Generalized Langevin-Debye model of the field dependence of tilt, birefringence, and polarization current near the de Vries smectic-$A${}^{*}$ to smectic-$C${}^{*}$ liquid crystal phase transitionPhysical Review E, 2013
- Molecular theory of smectic ordering in liquid crystals with nanoscale segregation of different molecular fragmentsPhysical Review E, 2011
- The Orientational Order in So-Called de Vries MaterialsMolecular Crystals and Liquid Crystals, 2009
- Order-disorder molecular model of the smectic-–smectic-phase transition in materials with conventional and anomalously weak layer contractionPhysical Review E, 2007
- Disordering to Order: de Vries Behavior from a Landau Theory for Smectic PhasesPhysical Review Letters, 2007
- Current Topics in Smectic Liquid Crystal ResearchChemphyschem, 2006
- Ferroelectric and Antiferroelectric Liquid Crystals1999
- "Chevron" Local Layer Structure in Surface-Stabilized Ferroelectric Smectic-CellsPhysical Review Letters, 1987
- Submicrosecond bistable electro-optic switching in liquid crystalsApplied Physics Letters, 1980
- The description of the smectic A and C phases and the smectic A–C phase transition of TCOOB with a diffuse-cone modelThe Journal of Chemical Physics, 1979