Communications
ADVANCED MATERIALStransfer transition. Support for this explanation comes from measurements at low temperature (200 K). Only the absorption band at 6300 cm-' shifts to smaller wavenumbers and increases in intensity.Apparently, methyl substitution inhibits planarization of the molecule and causes localization of the excess charge on a biphenyl subunit. A similar behavior is observed with S'", where the charge is localized on a terphenyl segment rather than delocalized over the whole n-system. This charge localization leads to the appearance of intervalence bands.r101 Such charge transfer transitions have also been observed for ionic derivatives of oligo(m-phenyleneviny1ene)s ll,[' which exhibit charge localization for topological reasons. In principle, localization of excess charge in a particular subunit of an extended n-system could also result from the polarizing effects of the counter ions. It is unlikely, however, that such an effect would occur in 7-9 and not in the closely related chains 2-4.The absorption spectra of the dianions of both classes of oligomers are very similar. Transfer of the first electron causes a geometrical reorientation towards a more planarized, quinoid system to stabilize the monoanion. The second electron can then delocalize over the whole n-system.Additional support for these results comes from the cyclovoltammetric investigation of the oligomers.rsl For instance, the first reduction potential of 7 is observed at -2.75 V. Comparison with the first reduction potential of 5 (-2.81 V) suggests that the electron is transferred to a biphenyl-sized n-system. After the initial electron transfer the molecule planarizes, so that the second electron is completely delocalized. The reduction potential for this process also lies at -2.75 V, which closely corresponds to the quater-