A DEUTERON NMR-STUDY OF AXIAL MOTION AND SIDE-CHAIN CONFORMATION IN THE MESOPHASE OF DISCOTIC LIQUID-CRYSTAL MAIN-CHAIN POLYMERS

Pulsed deuteron NMR spectroscopy has been used to examine the axial motion and the side-chain conformation in both oriented and unoriented mesophases of discotic liquid crystal main-chain polymers based on pentyloxy or heptyloxy substituted triphenylenes. Lineshape simulations show that the rotational motion of the triphenylene rings about the column axes can be described by an inhomogeneous distribution of reorientation angles around 45-degrees. However, only about 60% of the discs are involved in such large amplitude motions; the remaining 40% have reorientation angles below 10-degrees. This illustrates the severe restrictions imposed on the rotation of the discs by the interlinkage of the columns via the alkylene spacers. Furthermore, the simulations demonstrate that, at the alpha-carbon, the side chains show very little fast internal motion, but have a relatively complex conformation involving a disorder which does not change on the microsecond timescale. Since such a disorder is not present in the corresponding monomeric samples it is ascribed to the presence of the spacers. These results are also consistent with the presence of large sterical hindrances between the first side chains segments of adjacent discs, and they indicate a correlated reorientation of the discotic units within a column.