End-Group Effects on the Structure and Spectroscopy of Oligoazines

Abstract

Oligoazines with three different types of end groups, ketone, hydrazone, and 2-pyridine, are studied in solution. When the end groups are ketone or 2-pyridine, the 1H and 13C NMR spectra are simple and show that the oligomers maintain 2-fold symmetry up to the longest chain lengths investigated (five azine units for the 2-pyridine end groups). In contrast, when the end groups are hydrazones, the 1H NMR spectra show evidence for as many as five conformers present in solution for each oligomer while the 13C NMR spectra are still simple, indicative of a single compound. Semiempirical AM1 calculations suggest that all of the oligoazines should be severely twisted but give no insight about the origin of the large number of conformers found for the materials with hydrazone end groups. The end groups have a significant effect on the UV spectra. All the oligoazines show two absorptions close in energy, but the relative intensities change depending upon the end group. For ketone end groups the higher energy transi...