Search

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. [ABSTRACT FROM AUTHOR]

Multilayered coordination nanosheets made of copper ions and hexaaminobenzene (CuHAB) were synthesized in a liquid–liquid interfacial reaction in the presence of a base and an oxidizing agent. X-ray diffraction studies revealed the suitability of an oxidizing agent with a low oxidation potential for the synthesis of highly crystalline CuHAB. The base concentration affects the chemical and crystal structures of CuHAB. The nanosheets synthesized at low base concentrations exhibit humidity-responsive conductivity due to the ligating amino group. Meanwhile, the nanosheets prepared at high base concentrations have different stacking structures from the CuHABs formed at low base concentrations and show greater conductivity. These results indicate that the liquid–liquid interfacial synthesis with an appropriate oxidizing agent and quantitative addition of base can modulate chemical and stacking structures of coordination nanosheets composed of hexaaminobenzene ligand and their functionalities. [ABSTRACT FROM AUTHOR]