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We report the results of a study in which we introduce a tricarbosilane end-group in a mesogenic scaffold derived from an axially chiral biphenyl with a large transverse dipole moment. This structural modification is intended to promote the formation of a chiral smectic C (SmC*) phase, with the aim of discovering a mesogen with a virtual transition temperature to a proper ferroelectric phase (To) that approaches the crystal-SmC* melting point. We show herein that the combination of a 4-pentylbicyclo[2.2.2]octane-1-carboxylate chain and a tricarbosilane-terminated 4-alkoxybenzoate chain gives a mesogen (R,S)-WL43 forming an enantiotropic orthogonal smectic A (SmA) phase and a higher order tilted smectic phase. Substitution of the 4-pentylbicyclo[2.2.2]octane-1-carboxylate group with a trans-4-pentylcyclohexane-1-carboxylate group gives a mesogen (R,S)-WL45 forming monotropic SmA and SmC phases. The SmC* phase formed by the enantiomerically pure (R)-WL45 exhibits Goldstone-mode switching characteristic of a surface-stabilized FLC, but its spontaneous polarization PS is too low to be measured by conventional methods. [ABSTRACT FROM AUTHOR]

The recent discovery of a new lyotropic liquid crystal phase, the structure and properties of which are analogous to the chiral ferroelectric smectic C-phase (SmC*) in thermotropics, was based on a tailored amphiphile structure in which a tilt-promoting mesogenic core was linked to a chiral diol-headgroup via a hydrophilic ethylene glycol spacer [J. R. Bruckner et al., Angew. Chem., Int. Ed., 2013, 52, 8934–8937]. However, so far there is only one example of this general amphiphile structure known to form the new lyotropic SmC* phase in mixtures with water and with formamide. In an attempt to systematically elucidate the underlying structure–property relations we now report two new amphiphiles leading to lyotropic SmC* phases. These amphiphiles are derived from the parent amphiphile structure by (i) an elongation of the hydrophilic ethylene glycol spacer and (ii) an exchange of the original 2-phenylpyrimidine core by an even more tilt-promoting fluorenone core. Our investigations also reveal that the formation of the lyotropic SmC* phase is highly sensitive to exchanging or enlarging a building block of the primary material. [ABSTRACT FROM AUTHOR]

A homologous series of tri-, di- and monocarbosilane mesogens with a 5-phenylpyrimidine core and a chiral (S,S)-2,3-difluorohexyloxy chain were synthesized and characterized. We show that shortening the carbosilane end-group has a detrimental effect on ‘de Vries-like’ properties, causing an increase in reduction factor R from 0.17 for the tricarbosilane QL32-6 to 0.38 for the monocarbosilane QL34-6, both at the point of maximum layer contraction upon transition from the orthogonal SmA* to the tilted SmC* phase. This increase in R correlates with an increase in birefringence Δn, a broadening in the SmA* temperature range and a decrease in optical tilt angle ϑopt in the SmC* phase, which are all consistent with an increase in orientational order and a decrease in lamellar order. The electroclinic effect (ECE) in the SmA* phase decreases with decreasing length of the carbosilane end-group, which is consistent with previous observations of high ECE in ‘de Vries-like’ liquid crystals. On the other hand, spontaneous polarization PS measurements suggest that polar ordering in the SmC* phase is not strongly dependent on R. [ABSTRACT FROM AUTHOR]

The chiral carbosilane-terminated liquid crystal 2-[(2S,3S)-2,3-difluorohexyloxy]-5-[4-(12,12,14,14,16,16-hexamethyl-12,14,16-trisilaheptadecyloxy)phenyl]pyrimidine (QL32-6) undergoes a smectic A*-smectic C* phase transition with a maximum layer contraction of only 0.2%. It exhibits an electroclinic effect (ECE) comparable to that reported for the ‘de Vries-like’ liquid crystal 8422[2F3] and shows no appreciable optical stripe defects due to horizontal chevron formation. [ABSTRACT FROM AUTHOR]

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. [ABSTRACT FROM AUTHOR]

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. In an effort to expand the library of ‘de Vries-like’ liquid crystals required for the formulation of chevron-free ferroelectric liquid crystal mixtures, we report the synthesis of a homologous series of tricarbosilane 5-phenylpyrimidine liquid crystals QL16-n using an improved synthetic route, and the characterization of their liquid crystalline and ‘de Vries-like’ properties. Measurements of orientational order parameters S2 and effective molecular lengths Leff by monodomain 2D X-ray scattering suggest that ‘de Vries-like’ behavior in series QL16-n is due to the combined effect of an increase in S2 and a decrease in bilayer interdigitation, thus causing a smectic layer expansion that compensates for the molecular tilt in the SmC phase. We also show how the optical tilt angle in the SmC phase may be optimized for SSFLC displays―without compromising ‘de Vries-like’ properties―by shortening the tricarbosilane end-group to a dicarbosilane. Two of the new materials reported herein, 5-[4-(12,12,14,14,16,16-hexamethyl-12,14,16-trisilaheptadecyloxy)phenyl]-2-hexyloxypyrimidine (QL16-6) and 2-hexyloxy-5-[4-(12,12,14,14-tetramethyl-12,14-disilapentadecyloxy)phenyl]pyrimidine (QL24-6) rank among the best ‘de Vries-like’ materials reported heretofore, with broad SmC phases and reduction factors R of 0.17 and 0.18, respectively, at a reduced temperature T−TAC = −10 K. We also show that inverting the orientation of the 5-phenylpyrimidine core in the homologous series QL17-n causes a suppression of ‘de Vries-like’ properties. These results suggest that non-covalent core–core interactions in the intercalated smectic bilayers formed by these mesogens may influence ‘de Vries-like’ behavior. [ABSTRACT FROM AUTHOR]

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. We show that binary mixtures of ‘de Vries-like’ and conventional SmC mesogens with a molecular length ratio of 1.34 undergo a SmA–SmC phase transition with a maximum layer contraction ranging from 1.0 to 1.9% depending on the mixture composition. [ABSTRACT FROM AUTHOR]

Smectic liquid crystals with 'de Vries-like' properties are characterized by a maximum layer contraction of ≤1% upon transition from the non-tilted SmA phase to the tilted SmC phase. We show herein that one can systematically increase the 'de Vries-like' character of a smectic liquid crystal by tuning the frustration between SmA- and SmC-promoting elements according to established structure-property relationships., (© The Royal Society of Chemistry 2011)

Diastereomer discrimination was observed in the formation of a metallomacrocycle from a racemic ligand based on Tröger's base. The metallomacrocycle exhibited a dramatic increase in fluorescence intensity compared to the ligand and its fluorescence was efficiently quenched by C(60).

This review focuses on the development of photochromic dopants designed to trigger the switching of ferroelectric liquid crystals photomodulation of the spontaneous polarization (). The photomodulation of has been achieved by reducing the polar order of a FLC host the change in shape of azobenzene dopants upon - photoisomerization, and the loss of conformational flexibility of dithienylethene dopants upon photocyclization. It has also been achieved by increasing the polarization power of chiral thioindigo dopants in achiral SmC hosts a photoinduced change in transverse dipole moment. A photoinversion of the sign of has been achieved using an "ambidextrous" thioindigo dopant with two competing chiral side-chains that induce polarizations of opposite handedness.