Chemical Properties of Liquid Crystals

Liquid crystals can be classified into two main categories: thermotropic liquid crystals, and lyotropic liquid crystals. These two types of liquid crystals are distinguished by the mechanisms that drive their self-organization, but they are also similar in many ways.

Thermotropic transactions occur in most liquid crystals, and they are defined by the fact that the transitions to the liquid crystalline state are induced thermally. That is, one can arrive at the liquid crystalline state by raising the temperature of a solid and/or lowering the temperature of a liquid. Thermotropic liquid crystals can be classified into two types: enantiotropic liquid crystals, which can be changed into the liquid crystal state from either lowering the temperature of a liquid or raising of the temperature of a solid, and monotropic liquid crystals, which can only be changed into the liquid crystal state from either an increase in the temperature of a solid or a decrease in the temperature of a liquid, but not both. In general, thermotropic mesophases occur because of anisotropic dispersion forces between the molecules and because of packing interactions.

In contrast to thermotropic mesophases, lyotropic liquid crystal transitions occur with the influence of solvents, not by a change in temperature. Lyotropic mesophases occur as a result of solvent-induced aggregation of the constituent mesogens into micellar structures. Lyotropic mesogens are typically amphiphilic, meaning that they are composed of both lyophilic (solvent-attracting) and lyophobic (solvent-repelling) parts. This causes them to form into micellar structures in the presence of a solvent, since the lyophobic ends will stay together as the lyophilic ends extend outward toward the solution. As the concentration of the solution is increased and the solution is cooled, the micelles increase in size and eventually coalesce. This separates the newly formed liquid crystalline state from the solvent.

A very large number of chemical compounds are known to exhibit one or several liquid crystalline phases. Despite significant differences in chemical composition, these molecules have some common features in chemical and physical properties. There are two types of thermotropic liquid crystals: discotics and rod-shaped molecules. Discotics are flat disc-like molecules consisting of a core of adjacent aromatic rings. This allows for two dimensional columnar ordering. Rod-shaped molecules have an elongated, anisotropic geometry which allows for preferential alignment along one spatial direction.

The rod-like low molar mass (LMM) liquid crystals, such as 5CB shown in the following diagram:

require an extended conformation of the molecule which must be maintained through the rigidity and linearity of its constituents. That is, in order for a molecule to display the characteristics of a liquid crystal, it must be rigid and rod-shaped. This is accomplished by the interconnection of two rigid cyclic units. The interconnecting group should cause the resulting compound to have a linear planar conformation. Linking units containing multiple bonds such as -(CH=N)-, -N=N-, -(CH=CH)n-, -CH=N-N=CH-, etc. are used since they restrict the freedom of rotation. These groups can conjugate with phenylene rings, enhancing the anisotropic polarizability. This increases the molecular length and maintains the rigidity.


Textures and DefectsVirtual Textbook Applications of Liquid Crystals