Mesomorphic liquid

In this subsection some examples are presented of polymorphic polymers, for which one or more forms are solid mesomorphic, in the sense described in the Sect. 2.1. Let us recall that in this review we will not deal with liquid mesomorphic forms. 

Such liquid crystals which are formed when the temperature is varied are called thermotropic. Many compounds form a second kind of mesophase when a solvent is added. Further increasing the amount of solvent beyond a critical concentration leads to a transformation to an ordinary (isotropic) liquid. Mesomorphic phases of this kind are called lyotropic. They are formed e.g. with long-chain saturated fatty acids in aqueous solutions. Lyotropic liquid crystals play an important role in biological systems. However, no technical applications are known as yet, and therefore we will not discuss this type of mesophases further. 

Liquid crystals represent a state of matter with physical properties normally associated with both soHds and Hquids. Liquid crystals are fluid in that the molecules are free to diffuse about, endowing the substance with the flow properties of a fluid. As the molecules diffuse, however, a small degree of long-range orientational and sometimes positional order is maintained, causing the substance to be anisotropic as is typical of soflds. Therefore, Hquid crystals are anisotropic fluids and thus a fourth phase of matter. There are many Hquid crystal phases, each exhibiting different forms of orientational and positional order, but in most cases these phases are thermodynamically stable for temperature ranges between the soHd and isotropic Hquid phases. Liquid crystallinity is also referred to as mesomorphism. 

Similar lamellar structures are formed for l-alkyl-3-methylimida2olium cations with [PdCl4] when n > 12. As with the pyridinium systems, mesomorphic liquid crystal structures based on the smectic A structure are formed [24]. 

Caffrey, M. Structural, Mesomorphic and Time-Resolved Studies of Biological Liquid Crystals and Lipid Membranes Using Synchrotron X-Radiation. 151, 75-109 (1989). 

All solid forms lacking order to a substantial degree and ordered liquids (smectic, nematic) are called at times mesomorphic forms. 

Attard GS, Garnett S, Hickman CC, Imrie CT, Taylor L (1990) Liq Cryst 7 495 Shibaev VP, Lam L (eds) (1994) Liquid crystalline and mesomorphic polymers. Springer, BerUn Heidelberg New York... 

A compound which displays liquid crystal properties is referred to as a mesogen and said to exhibit mesomorphism. Liquid crystals may be considered either as disordered solids or ordered liquids, and their properties are very dependent on temperature and the presence or absence of solvent. In thermotropic liquid crystals the phases of the liquid crystals may be observed to change as the temperature is increased. In lyotropic liquid crystals the ordered crystalline state is disrupted by the addition of a solvent, which is very commonly water. For these systems temperature changes may also be... 

Depending on the R group, this reaction could lead to the formation of gold(I) isocyanide complexes that behave as liquid crystals. Thus, complexes [Au(C6F5) (C = N(QH4)OCioH2i-p)] and [Au(QF5)(C = N(QH4)OCnH2n + rP)] [64] where n = 4, 6, 8, 10 and 12 show this behavior. All of these complexes are mesomorphic and behave as liquid crystals showing a nematic (N) phase when the isocyanide has a... 

As indicated above in chiral mesophases, the introduction of a functional group in mesogenic stmctures offers the opportunity to achieve functional LCs. With this aim, mesomorphic crown-ether-isocyanide-gold(I) complexes (26) have been prepared recently [38]. The derivatives with one alkoxy chain show monotropic SmC mesophases at or close to room temperature. In contrast, the complexes with three alkoxy chains behave as monotropic (n = 4) or enantiotropic (n > 4) LCs. The structure of the mesophases could not be fully eluddated because X-ray diffraction studies in the mesophase were unsuccessful and mesophase characterization was made only on the basis of polarized optical microscopy. These complexes are luminescent not only in the solid state and in solution, but also in the mesophase and in the isotropic liquid state at moderate temperatures. The emission spectra of 26a with n=12 were... 

Ballesteros, B., Coco, S. and Espinet, P. (2004) Mesomorphic Mixtures of Metal Isocyanide Complexes, Induding Smectic C Mesophases at room temperature and Liquid Crystalline Molecular Alloys . Chemistry of Materials, 16, 2062-2067. 

Kanayama, N., Tsutsumi, O., Kanazawa, A. and Ikeda, T. (2001) Distinct thermodynamic behaviour of a mesomorphic gold nanoparticle covered with a liquid-crystalline compound. Chemical Communications, (24), 2640-2641. 

For example, Marder and co-workers [10] (among others) have studied liquid crystal mesophases induced by the presence of quadrupolar interactions between non-mesomorphic phenyl- and perfluorophenyl-containing moieties (e.g. 1). 

However, the hydrogen-bonded mesogens that are of most interest in the context of this article are those elaborated initially by Kato and Frechet in the early 1990s [24-33]. In this approach, a pyridine, which may or may not have liquid crystal properties, was hydrogen bonded with a 4-substituted benzoic acid to form a new species with its own, distinct mesomorphism. For example, complex 9 shows a SmA phase that persists to 238 °C (n = 2, m = 4), while its free component pyridine is nematic to 213 °C the component benzoic acid is also nematic (as the H-bonded dimer) to 147 °C (although note that the notional monomer would not be liquid crystalline). 

Poly(epichlorohydrin) (PECH) and poly(2,6 - dimethyl-1,4-phenylene oxide) (PPO) containing pendant mesogenic units separated form the main chain through spacers of zero to ten methylene units were synthesized and characterized in order to test the "spacer concept." Both polymers were modified by phase transfer catalyzed esterifications of the chloromethyl groups (PECH) or the bromobenzyl groups (brominated PPO) with potassium co -(4-oxybiphenyl) alkanoates and potassium u-(4-methoxy-4-oxybiphenyl)-alk.an oates. While PPO required ten methylene units as a spacer and 4,4 -methoxybiphenyl as mesogen to present thermotropic liquid crystalline mesomorphism,... 

FB Rosevear. Liquid crystals The mesomorphic phases of surfactant compositions. J Soc Cosmet Chem 19 581, 1968. 

Another approach to get new liquid crystals is the lateral fluorination of the stilbazole ligands,337 which is a common and highly effective tool to exert control over mesomorphism, crystal phase stability, and physical properties. Other modifications include the use of more alkoxy substituents and other alkyl sulfate anions.338-344 Ionic silver amino complexes also display liquid crystalline behavior at rather low temperatures they are of the form [Ag(NH2 -CJl +OJX (X = N03, n = 6,8,10,12,14 X = BF4, = 8,10,12,14).345... 

Mesomorphic dendrimers containing electroactive units have potential for construction of dendrimer based molecular switches. Deschenaux et al. reported [154] the synthesis and liquid-crystalline properties of a novel dendrimer containing six mesomorphic ferrocene units. Apart from exhibiting a broad enantiotropic smectic A phase as determined by polarized optical microscopy, DSC, and XRD studies, thermogravimetry revealed the excellent thermal stability of the macromolecule. 

Figure 8 Liquid-crystalline polymers in which the mesomorphic sequences occur in the side-chain (middle), in the chain backbone (top), or in both (bottom) ( combination structures).

Nonmesomorphic as well as mesomorphic F-shaped acids with a structure similar to banana liquid crystals, have been complexed to a 2,4,6-triamino-l,3,5-triazine derivative <06JA4487>. 

Crystalline forms presenting large amounts of disorder of the kind (ii) or (iii) are generally called mesomorphic modifications (Section 3.6), in analogy with the ordered liquids (smectic and nematic). In these cases the lack of periodicities in one or two dimensions (e.g., along the chain axes or along the directions normal to the chain axes) prevents the definition of a unit cell. Typical features in the X-ray diffraction patterns of mesomorphic forms are diffuse halos on the equator or on the layer lines depending on the kind of disorder present. 

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