Optical and Infrared Spectroelectrochemical Studies of CN-Substituted Bipyridyl Complexes of Ruthenium(II)

Ruthenium(II) polypyridyl complexes [Ru(CN-Me-bpy)(bpy)_3-]²⁺ (CN-Me-bpy = 4,4'-dicyano-5,5'-dimethyl-2,2'-bipyridine, bpy = 2,2'-bipyridine, and x = 1-3, abbreviated as 1, 2, and 3) undergo four (1) or five (2 and 3) successive one-electron reduction steps between -1.3 and -2.75 V versus ferrocenium/ferrocene (Fc⁺/Fc) in tetrahydrofuran. The CN-Me-bpy ligands are reduced first, with successive one-electron reductions in 2 and 3 being separated by 150-210 mV; reduction of the unsubstituted bpy ligand in 1 and 2 occurs only when all CN-Me-bpy ligands have been converted to their radical anions. Absorption spectra of the first three reduction products of each complex were measured across the UV, visible, near-IR (NIR), and mid-IR regions and interpreted with the help of density functional theory calculations. Reduction of the CN-Me-bpy ligand shifts the ν(C≡N) IR band by ca. -45 cm^-1, enhances its intensity ∼35 times, and splits the symmetrical and antisymmetrical modes. Semireduced complexes containing two and three CN-derivatized ligands 2, 3, and 3 show distinct ν(C≡N) features due to the presence of both CN-Me-bpy and CN-Me-bpy^•-, confirming that each reduction is localized on a single ligand. NIR spectra of 1, 1, and 2 exhibit a prominent band attributable to the CN-Me-bpy^•- moiety between 6000 and 7500 cm^-1, whereas bpy^•--based absorption occurs between 4500 and 6000 cm^-1; complexes 2, 3, and 3 also exhibit a band at ca. 3300 cm^-1 due to a CN-Me-bpy^•- → CN-Me-bpy interligand charge-transfer transition. In the UV-vis region, the decrease of π → π* intraligand bands of the neutral ligands and the emergence of the corresponding bands of the radical anions are most diagnostic. The first reduction product of 1 is spectroscopically similar to the lowest triplet metal-to-ligand charge-transfer excited state, which shows pronounced NIR absorption, and its ν(C≡N) IR band is shifted by -38 cm^-1 and 5-7-fold-enhanced relative to the ground state.