A series of soluble polybipyridine ligands comprising one to five bipyridine modules sandwiched between rigid carbon–carbon triple bonds substituted by 3, 4-dibutylthiophene repeating units was synthesized. Two different protocols have been explored with the idea to use a divergent/convergent approach starting from bisymmetrically and symmetrically substituted bipyridine modules. At each stage of the iteration two bipy/thiophene modules ...