Influence of Annulene Ratio on the Electrochemical and Spectroscopic Properties of Methano[10]Annulene–Thiophene Random Copolymers

We describe a series of copolymerization studies whereby the nonbenzenoid aromatic methano[10]annulene is incorporated into three different types of random copolymers, two based on polythiophenes (from bithiophene and terthiophene monomers) and one based on poly(ethylene dioxythiophene). Copolymers where the annulene component was in the majority had optical and electrochemical behaviors reminiscent of the annulene homopolymer. In contrast, we found that the annulene influenced polymer electronics at very low feed ratios where the commercial comonomer was in the majority. Copolymerizations are useful approaches to dilute the complex annulene monomers into functional polymers without losing the optoelectronic properties of the annulene homopolymers. These electrochemical results provide important design rules that can be employed for the chemical synthesis of related random copolymers.