Differential metal-binding properties of dynamic acylhydrazone polymers and their sensing applications

As one of common dynamic covalent bonds, acylhydrazone bond plays an important role in developing intelligent responsive materials. In this report, we present acylhydrazone-based dynamic polymers with multi-stimuli responsiveness, particularly metal recognition behaviours and their modulation. A series of polyacylhydrazones with different metal-binding sites were designed and prepared in a modular fashion. Titration of these receptors with a diverse set of metal ions, including Cu²⁺, Zn²⁺ and La³⁺, resulted in unique optical changes, and both the sensitivity and selectivity profiles can be regulated. Moreover, the metal-binding feature was facilely modulated by changing the solvent. The addition of weakly basic anions was employed to further fine-tune the responsiveness of the polymers by taking advantage of the cooperative effect with metal coordination. Finally, the sensitive detection of 6-mercaptopurine and pyrophosphate was achieved to demonstrate the application potential of these systems.