En route to a molecular sheaf: active metal template synthesis of a [3]rotaxane with two axles threaded through one ring

We report that a 2,2':6',2″-terpyridylmacrocycle-Ni complex can efficiently mediate the threading of two alkyl chains with bulky end groups in an active metal template sp(3)-carbon-to-sp(3)-carbon homocoupling reaction, resulting in a rare example of a doubly threaded 3]rotaxane in up to 51% yield. The unusual architecture is confirmed by X-ray crystallography (the first time that a one-ring-two-thread 3]rotaxane has been characterized in the solid state) and is found to be stable with respect to dethreading despite the large ring size of the macrocycle. Through such active template reactions, in principle, a macrocycle should be able to assemble as many axles in its cavity as the size of the ring and the stoppers will allow. A general method for threading multiple axles through a macrocycle adds significantly to the tools available for the synthesis of different types of rotaxane architectures.