Conjugated Polymers with Repeated Sequences of Group 16 Heterocycles Synthesized through Catalyst-Transfer Polycondensation

Periodic π-conjugated polymers of the group 16 heterocycles (furan, thiophene, and selenophene) were synthesized with controlled chain lengths and relatively low dispersities using catalyst-transfer polycondensation. The optical gap and redox potentials of these copolymers were fine-tuned by altering the heterocycle sequence, and atomic force microscopy revealed nanofibrillar morphologies for all the materials. Grazing incidence wide-angle X-ray scattering of the thiophene-selenophene copolymers indicated that the π-stacking distance increased with incorporation of the larger heteroatom (from ∼3.7–4.0 Å), while the lamellar spacing decreased (from ∼15.8–15.2 Å). The study also revealed that periodic sequences allow electronic properties to be tuned while retaining nanofibrillar morphologies similar to those observed for poly­(3-hexylthiophene).