Synthesis and electronic properties of series of oligothiophene-[1,10]phenanthrolines

Organic semiconductors containing metal binding sites within their molecular backbones are of a general interest in organic materials chemistry. In this paper, we describe a straightforward synthetic procedure, which gives access to a series of 2-(oligothienyl)-[1,10]phenanthrolines (nT-phen), 2,9-bis(oligothienyl)-[1,10]phenanthrolines (nT-phen-nT) and 2,2'-(oligothienyl)bis-[1,10]phenanthrolines (phen-nT-phen). By a Negishi-type cross coupling of 2-iodo-[1,10]phenanthroline or 2,9-diiodo-[1,10]phenanthroline with in situ generated alpha-zinc derivatives of different mono-, ter-, and quinquethiophenes we were able to synthesize the corresponding oligothienyl-phenanthrolines in medium to excellent yields. Furthermore, characterization of the optical properties of the new materials indicated that the two subunits, oligothiophene and phenanthroline, are in pi-conjugation. Characterization of the redox properties revealed additional evidence for the role of [1,10]phenanthroline as a pi-bridging unit in the nT-phen-nT series.