Modular Synthesis of Improbable Rotaxanes with All‐Benzene Scaffolds

Abstract “Improbable” rotaxanes consisting of interlocked conjugated components represent non‐trivial synthetic targets, not to mention those with all‐benzene scaffolds. Herein, a modular synthetic strategy has been established using an isolable azo‐linked pre‐rotaxane as the core module, in which the azo group functions as a tracelessly removable template to direct mechanical bond formations. Through versatile connections of the pre‐rotaxane and other customizable modules, [2]‐ and [3]rotaxanes derived from all‐benzene scaffolds have been accomplished, demonstrating the utility and potential of the synthetic design for all‐benzene interlocked supramolecules.