Stimuli‐Responsive Catenane‐Based Catalysts

Rotaxanes and molecular knots exhibit particular properties resulting from the presence of a mechanical bond within their structure that maintains the molecular components interlocked in a permanent manner. On the other hand, the disassembly of the interlocked architecture through the breakdown of the mechanical bond can activate properties which are masked in the parent compound. Herein, we present the development of stimuli‐responsive Cu(I)‐complexed [2]catenanes as OFF/ON catalysts for the copper‐catalyzed alkyne‐azide cycloaddition (CuAAC) reaction. The encapsulation of the Cu(I) ion inside the [2]catenanes inhibits its ability to catalyze the formation of triazoles. In contrast, the controlled opening of the two macrocycles induces the breaking of the mechanical bond, thereby restoring the catalytic activity of the Cu(I) ion for the CuAAC reaction. Such OFF/ON catalysts can be involved in signal amplification processes with various potential applications.