Abstract
Polymerizable hexacatenar mesogens containing a photo-active oligo(p-phenylenevinylene) core were successfully synthesized by replacing the traditional n-alkoxy tails on the molecules with polymerizable hydrocarbon tails containing terminal isoprenyl or 1,3-dienyl units. It was found that for this particular liquid crystal (LC) platform, the incorporation of conventional radical polymerizable groups such as acrylates in the tails was not conducive to the formation of thermotropic LC phases, presumably due to their polar nature. The resulting photoluminescent isoprenyl and 1,3-dienyl hexacatenar monomers were found to form columnar hexagonal phases at elevated temperatures (c. 45–75°C), as determined by powder X-ray diffraction. Unfortunately, photoinitiated radical polymerization studies revealed that the mesogens are susceptible to photodegradation in the LC state at elevated temperatures, resulting in the loss of both LC order and emission properties during photopolymerization. Thermally initiated radical polymerization in the absence of light, however, afforded effective crosslinking with retention of both LC order and the desired emission properties. The resulting crosslinked columnar hexagonal phases were found to exhibit emission maxima at nearly identical wavelengths, with comparable intensities relative to the unpolymerized starting materials. The effect of the different polymerizable groups on the mesogenic behaviour, polymerization characteristics, and emission properties of the hexacatenar compounds is presented.