Solid-state NMR study of Na versus K doping of para-phenylene oligomers.

13C solid-state nuclear magnetic resonance (NMR) experiments were performed on p-terphenyl, p-quaterphenyl, and p-sexiphenyl either in their pristine or doped with alkali metals form. The 13C NMR spectra of doped materials show new resonances by comparison with pristine compounds. For the K-doped materials, these resonances appear in the 90-135 ppm range, while for Na-doped materials, they are observed in the larger 20-150 ppm range. It suggests that the interaction between the alkali ions and the oligomers depends on the nature of the alkali. It is corroborated by 13C NMR experiments after exposure to air that show different behaviors. As expected, air exposure of K-doped samples restores the pristine spectra. This is not the case for Na doping, where the signature of the doped material persists even after exposure to air. In the latter case, some 13C resonances can be assigned to sp3 hybridized carbons and to the quinoid group. It suggests that Na doping induces a polymerization of the oligophenylenes.