Bis(aminoaryl) Carbon-Bridged Oligo(phenylenevinylene)s Expand the Limits of Electronic Couplings

Carbon-bridged bis(aminoaryl) oligo(para-phenylenevinylene)s have been prepared and their optical, electrochemical, and structural properties analyzed. Their radical cations are class III and class II mixed-valence systems, depending on the molecular size, and they show electronic couplings which are among the largest for the self-exchange reaction of purely organic molecules. In their dication states, the antiferromagnetic coupling is progressively tuned with size from quinoidal closed-shell to open-shell biradicals. The data prove that the electronic coupling in the radical cations and the singlet–triplet gap in the dications show similar small attenuation factors, thus allowing charge/spin transfer over rather large distances.