Unusual Internal Electron Transfer in Conjugated Radical Polymers

• Published in: Angewandte Chemie Vol. 129; no. 33; pp. 9988 - 9991
• Main Authors: Li, Fei, Gore, Danielle N, Wang, Shaoyang, Lutkenhaus, Jodie L
• Format: Journal Article
• Language: English
• Published: Weinheim Wiley Subscription Services, Inc 07.08.2017; Wiley Blackwell (John Wiley & Sons)
• Subjects: Aliphatic compounds; Backbone; Chemistry; Electron transfer; Energy storage; Kinetics; Konjugierte radikalische Polymere; Lithiumpolymerbatterien; Nitroxide; Polymers; Polythiophen; Radikalische organische Polymere; Redox potential; TEMPO
• ISSN: 0044-8249; 1521-3757
• DOI: 10.1002/ange.201705204

Nitroxide‐containing organic radical polymers (ORPs) have captured attention for their high power and fast redox kinetics. Yet a major challenge is the polymer's aliphatic backbone, resulting in a low electronic conductivity. Recent attempts that replace the aliphatic backbone with a conjugated one have not met with success. The reason for this is not understood until now. We examine a family of polythiophenes bearing nitroxide radical groups, showing that while both species are electrochemically active, there exists an internal electron transfer mechanism that interferes with stabilization of the polymer's fully oxidized form. This finding directs the future design of conjugated radical polymers in energy storage and electronics, where careful attention to the redox potential of the backbone relative to the organic radical species is needed. Konjugierte radikalische Polymere: Der interne Transfer eines Elektrons von einer Nitroxid‐Gruppe auf das Polythiophen‐Rückgrat wurde beobachtet. Dieser Prozess erklärt die Leitfähigkeit und Redoxaktivität von Polythiophenen mit radikalischen Nitroxid‐Seitengruppen.