Starting from easily accessible precursors we describe the preparation of a series of branched oligo(2‐thienyl)‐ and oligo(2,2′‐bithienyl)‐substituted pyridine derivatives. With palladium‐catalyzed cross‐coupling reactions of pyridyl nonaflates/triflates as key steps we synthesized 2,6‐di(2‐thienyl)pyridines bridged by thiophene or benzene rings. By selective bromination of 2,6‐di(2‐thienyl)pyridine and 2,4,6‐tri(2‐thienyl)pyridine and subsequent coupling reactions an access to oligo(2,2′‐bithien‐5‐yl)‐substituted pyridine derivatives was gained. The constitution and solid state conformation of 2,6‐bis(2,2’‐bithien‐5‐yl)pyridine was determined by X‐ray analysis. This series of new pyridine‐thiophene conjugates was systematically investigated by UV/vis spectroscopy. Large Stokes shifts in the neutral and protonated form were observed. The electrochemical oxidation of two typical compounds was studied, however, these oxidations were irreversible forming a polymeric film at the anode. As a selected example, a thiophene‐bridged 2,6‐di(2‐thienyl)pyridine derivative was also investigated by scanning tunneling microscopy showing an interesting self‐assembly into a highly ordered monolayer on highly oriented pyrolytic graphite.
