Time dependent crystal-smectic transformation in perylene-containing polyimides

The crystalline conformations of perylene polyimides (PPIs), with alkyl spacers varying in length from C3 to C12 are discussed. Although modeling of single chains would suggest the possibility that those with odd number of CH2 groups adopt a flat helical shape, X-ray diffraction suggests that the chains with odd and even spacers have the same conformation, due to the necessity to pack the perylene units. Upon annealing, the UV-vis absorption maximum red-shifts by about 10 nm, indicating enhanced π-stacking between the perylenes. Several changes in the spectra are seen with an increase in annealing time, at a given temperature. With an increase in annealing time, X-ray diffraction patterns show changes in the number of reflections, indicative of a crystal to mesogenic transition. The time required for this transition increases with a decrease in the spacer length, and annealing temperature, suggesting that the dynamics of this transition is very slow.