Cooperative Effects in Switchable Catalysis: Enhancing Double‐Click Reaction Yield of Symmetrical Rotaxanes

Reversible switching between the closed cyclic dimeric assembly [Cu(2)(1)(2)](2+) (OFF state) and the extended dimeric homoleptic complex [FeCu(2)(1)(2)](4+) (ON State) by addition/removal of Fe(2+) triggered catalysis of a double‐click reaction and high yield preparation of [2]rotaxanes. Mechanistic and computational studies provide valuable general insight for double‐click strategies by revealing cooperative effects in the second cycloaddition step due to a distance‐tolerant preorganization of the first‐click product by the two copper(I)‐loaded phenanthroline subunits of [FeCu(2)(1)(2)](4+).