A structure-property study toward π-extended phosphole chromophores with ambipolar redox properties

We report the synthesis of a series of π-extended dithienophospholes with phenyl or biphenyl terminal groups via Suzuki Miyaura cross-coupling procedures. The incorporation of the dithienophosphole core into the scaffold on oligophenylenes was found to lead to pronounced luminescence properties in solution and the solid state, the latter of which also responded to different solid-state morphologies, i.e., powder versus crystal. More importantly, the investigated molecular architectures also allowed — for the first time — the observation of ambipolar redox behavior of such species, with the biphenyl-extended species in particular showing quasi-reversible reduction and oxidation processes; the observed experimental features were correlated with computational density functional theory studies.