Side-Chain Liquid Crystalline Polymers (SCLCPs)

So...here's my work in a nutshell.

Side-chain liquid crystalline polymers (SCLCPs) are a relatively new class of polymeric materials. These polymers consist of some type of liquid crystalline molecule (called a mesogen) attached to the polymer backbone though a spacer chain that is typically a few carbon atoms long (Scheme 1). The possible uses for these materials take advantage of their physical properties. Among the potential uses are: non-linear optical devices (fiber optics), optical data storage, ferroelectric organic compounds, and the like.

Scheme 1. Schematic diagram of SCLCPs.

First, some background on SCLCPs. The type of SCLCPs that we are examining are known as thermotropic liquid crystalline polymers. That is, they exhibit their properties when heated. Unlike most organic compounds which melt from an ordered crystalline solid directly to a completely disordered liquid, SCLCPs undergo several phase changes between the crystalline solid and liquid states. These "between" phases are known as mesophases. The molecular arrangements in these mesophases varies with the type of mesophase. The mesophases are more ordered than the liquid state, but they flow, unlike the crystalline state. The variety of ordering types of these mesophases is shown in Scheme 2.

Scheme 2. Diagrammatic Representation of Liquid Crystalline Mesophases. Polymer backbone has been eliminated for clarity--only mesogens are shown. Temperature decreases from left to right.

For several reasons, the mesophase labeled "smectic C" is particularly interesting to us. Most of these reasons center around its usefulness in the applications named previously. These applications depend on the mesogen's ability to change alignment. In the compounds we are examining, we are interested in trasitions from the nematic mesophase to the smectic mesophases. Notice that the difference between the nematic mesophase and the smectic C mesophase is that the smectic C mesophase has layered ordering in addition to the ordering of the mesogens in the nematic phase.

So what am I specifically doing with SCLCPs? My interest is in modifying the behavior of the polymer shown in Scheme 3. In "polymer chemist notation" the parenthesis show the repeat unit of the polymer. You can imagine that the unit that is shown in Scheme 3 is one boxcar of a long train of identical units just like it, all connected at the parenthesis. The subscript "n" denotes the number of "boxcars" in this train. Why am I interested interested in this system? The properties of this system are very well understood, so it is easier to work with. This particular system which was examined extensivly by Dr. R. Schrock, et. al., at MIT shows only a nematic mesophase. In fact, it is widely believed that this laterally attached type of system is only capable of forming a nematic mesophase. It is particularly challenging then, to attempt to force this system to modify its behavior, that is, form smectic mesophases upon heating.

Scheme 3. Model Compound Upon Which Our SCLCP System is Based.

How will I accomplish layering? Well, if you examine the pictures of the mesophases in Scheme 1, you might see that if we were to make the mesogens interact in some way, they might be inclined to form layers. This is the approach we are taking. We intend to form copolymers of electron donating and electron accepting derivatives of the system shown in Scheme 3, thereby increasing the interactions between the mesogens and perhaps forcing them into a smectic allignment. The use of electron donor-acceptor pairs to modify phase behavior is known in SCLCPs, but has not been used in a system such as this. The electron donors and acceptors that I am synthesizing are shown in Scheme 4.

Scheme 4. Electron Donor and Acceptor Mesogens.

A good link on Polymer Liquid Crystals can be found here.  
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