Redox states and associated interchain processes of thienylenevinylene oligomers

The electronic structure of successive redox states of two series of thienylenevinylene oligomers (nTVs, n=4, 5, 6, 8, and 12) that carry hexyl substituents at the alpha- or beta-positions in order to increase the solubility was investigated in detail by means of UV/ Vis/near-IR and ESR spectroscopy in solution. The nTV redox states have been fully characterized up to the dication for the shorter oligomers (n < or = 6) and up to the tetracation for the longer oligomers (n > or = 8). While the monocation radicals of the nTVs exhibit two dipole-allowed electronic transitions in the Vis/near-IR region, all the higher oxidized states invariably show a single strong absorption in the near-IR region. The electronic transitions of the various oxidized states and those of their vibronic replicas shift to lower energies with increasing conjugation length. The ESR spectra, recorded as a function of the degree of oxidation, provide evidence for the presence of electron spin in the odd-charged and the absence of spin in even-charged cations. Variable-temperature UV/Vis/near-IR and ESR spectroscopy establish that the tendency of the nTV monocation radicals to form spin-less alpha dimers in solution strongly depends on the number of solubilizing hexyl groups. While the oligomers that carry two hexyl chains at the a-positions of the terminal thiophenes (alpha-nTVs) readily form pi dimers at low temperature, the oligomers that carry hexyl groups on the beta- and beta'-positions of every thiophene ring (beta-nTVs) do not form pi dimers. Low-temperature UV/ Vis/near-IR and ESR experiments on solutions in which neutral and singly oxidized nTVs are simultaneously present, reveal the occurrence of interchain interactions between these two species, accompanied by a pronounced change in the existing disproportionation equilibrium.