Templated Synthesis of a Rotaxane with a [Ru(diimine)3]2+Core

A rotaxane containing a ruthenium bisphenanthroline complex, acting as an axis, and a macrocycle incorporating a 2,2′‐bipyridine (bpy) unit, threaded by the axis, has been synthesized. The bisphenanthroline ligand is such that its ruthenium(II) complexes possess a clearly identified axis, making such compounds ideal components of rotaxanes constructed around an octahedral ruthenium(II) center, which serves as a template. The ring is threaded by the axial ruthenium(II) precursor complex, to afford the corresponding pseudorotaxane in moderate yield. The X‐ray structure analysis of this compound reveals the threaded nature of the complex. The length of the threaded ring (35 atoms in the periphery) is too short to allow easy threading of the axis through the macrocycle. As a consequence, an isomer is also obtained for which the axial ruthenium complex is attached in an exofashion. 1H NMR studies have been carried out, which reveal various conformational equilibria for the pseudorotaxane. Light‐induced decoordination of the bpy‐containing cyclic fragment was shown to be quantitative and to lead to the free ring and the axial ruthenium(II) complex, regardless of the starting compound (pseudorotaxane or exoisomer). Finally, the real rotaxane could be prepared, although it could not be separated from its exoisomer.