Controlling ion-polymer interactions in organic mixed ionic-electronic conductors is crucial for optimizing device performance in applications ranging from bioelectronics and energy storage to photonics. Achieving this requires a molecular-level understanding of how ion uptake, solvation and polymer structure evolve during electrochemical doping. Here using a multimodal operando approach, we uncover an unexpected response in the prototypical n-type ladder polymer poly(benzimidazobenzophenanthroline) (BBL) on doping with protic cations such as ammonium. At high doping levels, strong ion-polymer interactions (primarily hydrogen bonding) between cations and the BBL backbone promote charge localization and disrupt ion hydration, leading to a pronounced reduction in mass and thickness. Operando 2H NMR identifies water expulsion, rather than ion removal, as the origin of this deswelling. Our combined experimental and modelling results reveal a previously unobserved regime of ion-polymer coupling in organic mixed ionic-electronic conductors, establishing a framework for material design and applications that span (bio-)electronics to photonics.
Pol et al. (2026) studied this question.