Modulation between capacitor and conductor for a redox-active 2D bis(terpyridine)cobalt(II) nanosheet via anion-exchange

Abstract

Ionic polymers are intriguing materials whose functionality arises from the synergy between ionic polymer backbones and counterions. A key method for enhancing their functionality is the post-synthetic ion-exchange reaction, which is instrumental in improving the chemical and physical properties of polymer backbones and introducing of the functionalities of the counterions. Electronic interaction between host polymer backbone and guest ions plays pivotal roles in property modulation. The current study highlights the modulation of responses to external electric field in cationic bis(terpyridine)cobalt(II) polymer nanofilms through anion-exchange reactions. Initially, as-prepared chloride-containing polymers exhibited supercapacitor behaviour. Introducing anionic metalladithiolenes into the polymers altered the behaviour to either conductive or insulative, depending on the valence of the metalladithiolenes. This modulation was accomplished by fine tuning of charge-transfer interactions between the bis(terpyridine)cobalt(II) complex moieties and redox-active anions. Our findings open up new avenue for ionic polymers, showcasing their potential as versatile platform in materials science. Post-synthetic ion-exchange is a key method for tuning the chemical and physical properties of ionic polymers, but achieving control over functionality through ion-exchange remains challenging. Here, anion-exchange within a redox-active bis(terpyridine)cobalt(II) polymer enables modulation between capacitor and conductor behaviours in response to an external electric field.