Dynamic Covalent Self-Assembly Based on Oxime Condensation

Abstract

Oxime, whose dynamic nature was reported to be switchable between ON/OFF by tuning the acidity, is employed in a novel type of dynamic covalent approach that is amenable to use in water for self-assembly of purely organic molecules with complex topology. In strongly acidic conditions, the dynamic nature of oxime is turned ON, allowing occurrence of error-checking and therefore a catenane and a macrocycle self-assembled in high yields. In neutral conditions, oxime ceases to be dynamic, which helps to trap the self-assembled products even when the driving forces of their formation are removed. We envision that this switchable behaviour might help, at least partially, to resolve a commonly encountered drawback of dynamic covalent chemistry, namely that the intrinsic stability of the self-assembled products containing dynamic bonds, such as imine or hydrazone, are often jeopardized by their reversible nature.

Keywords: Supramolecular chemistry; catenanes; dynamic covalent bonds; oxime; self-assembly.