Wire‐Type Ruthenium( II ) Complexes with Terpyridine‐Containing [2]Rotaxanes as Ligands: Synthesis, Characterization, and Photophysical Properties

[2]Rotaxanes based on the 1,2‐bis(pyridinium)ethane⊂[24]crown‐8 ether motif were prepared that contain a terminal terpyridine group for coordination to a transition‐metal ion. These rotaxane ligands were utilized in the preparation of a series of heteroleptic [Ru(terpy)(terpy–rotaxane)] 2+ complexes. The compounds were characterized by 1D and 2D 1 H NMR spectroscopy, X‐ray crystallography, and high‐resolution electrospray ionization mass spectrometry. The effect of using a rotaxane as a ligand was probed by UV/Vis/NIR absorption and emission spectroscopy of the Ru II complexes. In contrast with the parent [Ru(terpy) 2 ] 2+ complex, at room temperature the examined complexes exhibit a luminescence band in the near infrared region and a relatively long lived triplet metal‐to‐ligand charge‐transfer ( 3 MLCT) excited state, owing to the presence of strong‐electron‐acceptor pyridinium substituents on one of the two terpy ligands. Visible‐light excitation of the Ru‐based chromophore in acetonitrile at room temperature causes an electron transfer to the covalently linked 4,4′‐bipyridinium unit and the quenching of the MLCT luminescence. The 3 MLCT excited state, however, is not quenched at all in rigid matrix at 77 K. The rotaxane structure was found to affect the absorption and luminescence properties of the complexes. In particular, when a crown ether surrounds the cationic axle, the photoinduced electron‐transfer process is slowed down by a factor from 2 to 3. Such features, together with the synthetic and structural advantages offered by [Ru(terpy) 2 ] 2+ ‐type complexes compared to, for example, [Ru(bpy) 3 ] 2+ ‐type compounds, render these rotaxane–metal complexes promising candidates for the construction of photochemical molecular devices with a wire‐type structure.