Multiresponsive Dynamic Covalent Assemblies for the Selective Sensing of Both Cu(2+) and CN(-) in Water.

Abstract

The use of dynamic assembly for molecular sensing is an intensive area of research in supramolecular chemistry. However, the development of self-assembly architectures for the detection of multiple signals remains challenging. Here, we present dynamic covalent assemblies with multiresponsive properties that also show unique selectivity profiles in water. The receptors were generated in a single step with modularly designed building blocks through acylhydrazone linkages, and their orthogonal assembly with a series of external stimuli was investigated. Notably, the system exhibits responses toward cations, anions, solvents, pH, and amphiphilicity. The discrimination of Cu(2+) from other divalent metal ions was achieved by simply changing the solvent and was evidenced by a Cu(2+)-induced pKa shift. The selective recognition of CN(-) in pure aqueous media was also accomplished through a cooperative effect in conjunction with Zn(2+). Furthermore, the assembly and its responsiveness are functional both in solution and the solid state. The aggregation ability of these dynamic covalent systems supports their binding and sensing properties.