Low and High Molecular Mass Dithienopyrrole-Naphthalene Bisimide Donor-Acceptor Compounds: Synthesis, Electrochemical and Spectroelectrochemical Behaviour.

Two low molecular weight electroactive donor-acceptor-donor (DAD)-type molecules are reported, namely naphthalene bisimide (NBI) symmetrically core-functionalized with dithienopyrrole (NBI-(DTP) ) and an asymmetric core-functionalized naphthalene bisimide with dithienopyrrole (DTP) substituent on one side and 2-ethylhexylamine on the other side (NBI-DTP-NHEtHex). Both compounds are characterized by low optical bandgaps (1.52 and 1.65 eV, respectively). NBI-(DTP) undergoes oxidative electropolymerization giving the electroactive polymer of ambipolar character. Its two-step reversible reduction and oxidation is corroborated by complementary EPR and UV/Vis-NIR spectroelectrochemical investigations. The polymer turned out to be electrochemically active not only in aprotic solvents but also in aqueous electrolytes, showing a distinct photocathodic current attributed to proton reduction. Additionally, poly(NBI-(DTP) ) was successfully tested as a photodiode material.