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RESEARCH PRODUCT

Dipolar Relaxation in Functionalized Poly-p-phenylenes Bearing Ultrastrong Dipoles Perpendicular to the Backbone

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Local polymer dynamics are studied in polymers bearing dipoles rigidly attached to the backbone. The compounds are based on cyano-substituted dihydrobenzimidazoles bearing ultrastrong dipole moments (∼12 D per repeat unit) incorporated in a poly-p-phenylene backbone, giving rise to polymers with rigid dipoles perpendicular to the chain. They belong to type B polymers according to the Stockmayer classification. They are ideal model systems for studying rotational isomers in the gas phase and the self-assembly and local dynamics in the solid state. Gas phase calculations (DFT) provided the dipole moments, the energetic barriers, and the backbone conformation as a function of the dipole strength and dipole separation. Calculated dipole moments show an odd–even effect as a function of dipole separation. Specific rotational isomers that maximize the dipole moment are obtained. In the solid state, dielectric spectroscopy and site-specific NMR techniques revealed that packing through intermolecular forces such a...