Azomethine‐Containing Pyrrolo[3,2‐b]pyrrole Copolymers for Simple and Degradable Conjugated Polymers

• Published in: Macromolecular rapid communications. 2024-01, Vol.45 (1), p.e2300220-n/a
• Main Authors: Bartlett, Kimberley A., Charland‐Martin, Ariane, Lawton, Jonathan, Tomlinson, Aimée L., Collier, Graham S.
• Format: Article
• Language: English
• Subjects: Azo Compounds; azomethines; conjugated polymers; degradable polymers; dihydropyrrolopyrroles; Polymers - chemistry; Pyrroles; Thiosemicarbazones
• ISSN: 1022-1336; 1521-3927
• DOI: 10.1002/marc.202300220

Conjugated polymers have received significant attention as potentially lightweight and highly tailorable alternatives to inorganic semiconductors, but their synthesis is often complex, produces toxic byproducts, and they are not typically designed to be degradable or recyclable. These drawbacks necessitate dedicated efforts to discover materials with design motifs that enable targeted and efficient degradation of conjugated polymers. In this vein, the synthetic simplicity of 1,4‐dihydropyrrolo[3,2‐b]pyrroles (DHPPs) is exploited to access azomethine‐containing copolymers via a benign acid‐catalyzed polycondensation protocol. Polymerizations involve reacting a dialdehyde‐functionalized dihydropyrrolopyrrole with p‐phenylenediamine as the comonomer using p‐toluenesulfonic acid as a catalyst. The inherent dynamic equilibrium of the azomethine bonds subsequently enabled the degradation of the polymers in solution in the presence of acid. Degradation of the polymers is monitored via NMR, UV‐vis absorbance, and fluorescence spectroscopies, and the polymers are shown to be fully degradable. Notably, while absorbance measurements reveal a continued shift to higher energies with extended exposure to acid, fluorescence measurements show a substantial increase in the fluorescence response upon degradation. Results from this study encourage the continued development of environmentally‐conscious polymerizations to attain polymeric materials with useful properties while simultaneously creating polymers with structural handles for end‐of‐life management or/and recyclability. By harnessing the simple synthesis enabled by dihydropyrrolopyrroles and the dynamic equilibrium of azomethine polymers, a novel monomer unit is incorporated into degradable conjugated polymers. Degradation is measured via NMR, UV‐vis and fluorescence spectroscopies. The synthesized polymers show properties suitable for potential applications as fluorescent sensors or/and write‐erase films.