Materials Highlights

Abstract

An aim of chemists in recent years has been to develop synthetic routes for the preparation of thermotropic, calamitic metallomesogens with high coordination numbers. Bruce and his colleagues (Adv. Mater. 1995, 7, 665) have now reported a methodology for the synthesis of mesogenic complexes formed by the coordination of the [ReBr(CO)] fragment to 1,4-diaza-1,3-butadienes, 1. The parent ligands exhibit smectic C and nematic phases while the octahedral complexes are exclusively nematogenic. The destruction of smectic behaviour on complexation is attributed to the bulky [ReBr(CO)] fragment disrupting molecular packing. The nematic-isotropic transition temperatures of the complexes are higher than those of the parent ligands. The authors speculate that this surprising observation may be related to a decrease in the flexibility of the [sbnd]N[dbnd]CH[sbnd]CH[dbnd]N[sbnd] segment of the ligand on complexation. It is anticipated that diazabutadienes will become an important synthetic building block for the preparation of new metallomesogens incorporating high coordination number centres.     

Tunable backflow in chiral nematic liquid crystals via twist-bend nematogens and surface-localised in-situ polymer protrusions

Dynamic electro-optic response of the liquid crystal (LC) director shows a backflow effect that is manifested as an optical bounce in chiral nematic LCs (N*LC) during field-induced homeotropic-twisted transition. The bend elastic constant (K₃₃) strongly influences the dynamics of backflow at the N*LC in homeotropic-twisted transition. The cyanobiphenyl LC dimers – CB7CB, CB9CB and CB11CB – possess a unique characteristic of inherent bend molecular configuration that lowers K₃₃. With the modulation of the effective K₃₃ in dimer-doped N*LCs, we report the tunability of the optical bounce that decreases with the increase in the length of flexible spacers in LC dimers. The doped LC dimers with short spacer lengths not only generate a strong backflow with an enhanced twist degeneracy of the LC director across the cell, but also prolong the time of disappearance of the optical bounce. Furthermore, we demonstrate the suppression of the optical bounce with surface localised polymer protrusions having 50–100 nm diameters, which allow faster dynamic relaxation process and reduced backflow. We envision a novel design of a tunable microfluidic device for precise flow control of organic or inorganic matter in LC medium that exploits the tunable backflow in LC dimer-doped N*LCs.     

Trimeric liquid crystals containing lateral alkyl chains

Abstract

The first twelve members of the n-alkyl 2,5-bis-(4′-cyanobiphenyloxybutyloxy)-benozates have been prepared. The compounds are nematogenic; in addition the first three members exhibit a smectic A phase. The nematic-isotropic transition temperatures decrease with little or no alternation on increasing the number of methylene groups in the lateral chain; this is analogous to the behaviour found in monomeric and polymeric mesogens possessing lateral alkyl chains.     

Monosubstituted thermotropic ferrocenomesogens: an overview 1976–1999

Research in the late 1940s in academic institutions, most notably the University of Hull in the UK, led to the development of liquid crystal display technology in the 1970s, which has subsequently had a large impact throughout the world. The liquid crystal technology is based on simple organic molecules. Since the late 1980s, some liquid crystal scientists have turned their attention to investigating the effect of introducing a metal atom into the systems. This review focuses on the major developments in the field of ferrocenyl‐containing liquid crystals in which the organometallic group is situated in a terminal position with respect to the core of the molecule. Metallomesogens with terminal metal atoms are not very common, since it can be deduced from the theory of organic liquid crystals that bulky terminal groups would not be conducive to the stabilization of liquid crystal phases. Nevertheless, a terminal ferrocenyl group can stabilize a nematic liquid crystal phase and examples of this will be discussed in this review. Copyright © 2001 John Wiley & Sons Ltd.     

Temperature Modulated Differential Scanning Calorimetry Part IV. Effect of heat transfer on the measurement of heat capacity using quasi-isothermal ADSC

An analysis developed in previous work has been further refined in order to study the effect of heat transfer on the heat capacity and phase angle measurements by TMDSC. In the present model, a temperature gradient within the sample has been taken into account by allowing for heat transfer by thermal conduction within the sample. The influence of the properties of the sensors, the heat transfer conditions between the sensor and sample,and the properties of the sample have been investigated by varying each parameter in turn. The results show that heat capacity measurements are reliable only within a restricted frequency range, for which the experimental conditions are such that the heat transfer phase angle depends linearly on the modulation frequency. This revised version was published online in July 2006 with corrections to the Cover Date.     

Activation energy-activation volume master plots for ion transport behavior in polymer electrolytes and supercooled molten salts

We demonstrate the use of activation energy versus activation volume "master plots" to explore ion transport in typical fragile glass forming systems exhibiting non-Arrhenius behavior. These systems include solvent-free salt complexes in poly(ethylene oxide) (PEO) and low molecular weight poly(propylene oxide) (PPO) and molten 2Ca(NO3)2.3KNO3 (CKN). Plots showing variations in apparent activation energy EA versus apparent activation volume VA are straight lines with slopes given by M = DeltaEA/DeltaVA. A simple ion transport mechanism is described where the rate determining step involves a dilatation (expressed as VA) around microscopic cavities and a corresponding work of expansion (EA). The slopes of the master plots M are equated to internal elastic moduli, which vary from 1.1 GPa for liquid PPO to 5.0 GPa for molten CKN on account of differing intermolecular forces in these materials.     

Ultrastructure studies of polystyrene-based side-chain liquid-crystalline copolymers containing charge transfer groups

A series of new side-chain liquid-crystalline copolymers has been prepared, and the thermal properties of the individual copolymers have been determined. These copolymers are derived from atactic polystyrene and contain both 4-methoxyazobenzene and 4-nitroazobenzene mesogens; these are linked through octyl spacers to the polystyrene backbone. All the copolymers exhibit a smectic phase that has been assigned smectic A on the basis of polarizing microscopy and x-ray diffraction studies. The glass transition temperatures of the polymers exhibit a linear dependence on composition, whereas the clearing temperatures and the associated entropies show significant deviations from such behavior. The smecticisotropic transition temperatures of the copolymers are higher than those of the composition-weighted averages for the corresponding homopolymers, whereas the entropies of transition are lower than expected. X-ray diffraction studies of fiber samples revealed that the director of the mesophase is oriented perpendicular to the fiber axis. The liquid-crystalline polystyrene containing 25 mol % nitro-substituted mesogen shows an unusual S_A-phase WAXS pattern. The copolymers were investigated further by ¹³C CP/MAS NMR spectroscopy, and the observed changes in the spectra are analyzed in terms of chemical composition and local electronic environment. The application of the interrupted decoupling technique revealed that the spacer contains a number of gauche defects. These observations lead us to suggest possible microstructural arrangements in the smectic phase. © 1993 John Wiley & Sons, Inc.     

Elastic scattering and coherent single pion production in proton-helium interactions at 18.6 GeV/c

Proton-helium elastic scattering and coherent single-pion production have been studied at 18.6 GeV/c in the four-momentum transfer region (?0.06, ?0.17) GeV/c². The elastic t-distribution has a somewhat steeper slope than is predicted by the Glauber approximation. The invariant-mass distribution of the Nπ system agrees with the double Regge-pole model except at about 1.65 GeV/c² where an enhancement presumably due to N¹ resonances is seen. The model also predicts the correct magnitude of the slope for nπ⁺α events. By using our cross sections at t′ = ?0.06 (GeV/c)² where the impulse approximation should be valid, the isospin-zero exchange elementary cross section for the nπ⁺ production is evaluated. The inelastic angular distributions are consistent with several spinparity states contributing at all Nπ masses.     

Non‐symmetric liquid crystal trimers

Four homologous series of non‐symmetric linear liquid crystalline trimers, the 4‐[(4‐{n‐[4‐(4‐methoxy‐phenylazo)phenoxy]alkyloxy}benzylidene)amino]benzoic acid 6‐[4‐(4‐methoxyphenylazo)phenoxy]hexyl esters, 4‐[(4‐{n‐[4‐(4‐cyanophenylazo)phenoxy]alkyloxy}benzylidene)amino]benzoic acid 6‐[4‐(4‐methoxyphenylazo)phenoxy]hexyl esters, 4‐[(4‐{n‐[4‐(4‐methoxyphenylazo)phenoxy]alkyloxy}benzylidene)amino]benzoic acid 6‐[4‐(4‐cyanophenylazo)phenoxy]hexyl esters and 4‐[(4‐{n‐[4‐(4‐cyanophenylazo)phenoxy]butoxy}benzylidene)amino]benzoic acid 6‐[4‐(4‐cyanophenylazo)phenoxy]hexyl esters, have been synthesized and characterized. In each series one spacer was held constant while the length of the second was varied from 3 to 12 methylene units. All these trimers were nematogenic and exhibited pronounced odd–even effects in both their clearing temperatures and associated entropies. Only two of the trimers exhibited a smectic phase, and specifically those containing two differing terminal mesogenic groups and an undecyl spacer. This strongly suggests the driving force for smectic phase formation is a combination of molecular shape and a specific interaction between unlike mesogenic units. The smectic phase has been assigned as a triply‐intercalated alternating smectic C phase, the first example of its kind.