CALCULATION OF THE EFFECTS OF PROTONATION ON RIGID-ROD POLYMERS

Semiempirical molecular orbital calculations have been used to investigate the effects of protonation on the behaviour of the structural repeat units of poly(p-phenylene benzobisthiazole), PBZT, and poly(p-phenylene benzobisoxazole), PBO. Single and multiple protonations of the heterocyclic rings at the nitrogen, oxygen and/or sulfur atoms were examined. It was found that protonation at the nitrogen was more favourable than at the oxygen or sulfur atoms. Delocalization of the charge into the phenyl ring resulted in a higher bond order for the inter-ring bond. While the energy barrier for torsional rotation increased with protonation, the resistance to bending the rings in an out-of-plane fashion decreased somewhat. Results of the semiempirical calculations indicated that protonation of the oxygen in PBO might result in opening of the five-membered heterocyclic ring by breaking the carbon-oxygen bond. Ab initio calculations on relevant models, however, did not support this result.