Evidence for the formation of a photoactive tris(2,2'-bipyridine)ruthenium(II)-ethylenediaminetetraacetic acid ion pair

Kennelly, Teresa; Strekas, Thomas C.; Gafney, Harry D.

doi:10.1021/j100412a087

Cited by 10 publications

(1 citation statement)

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“…Inasmuch as the UV−visible absorption spectra of Ru(II)−diimine complexes, such as Ru(bpy) 3 2+ (bpy = 2,2‘-bipyridine), in solution are virtually independent of the solvent and the presence of other solutes, ground-state interactions cannot be easily observed by that technique. On the other hand, NMR spectroscopy enables interactions to be detected; metal−ligand interactions, − Ru(II)−EDTA ion-pairing in the presence of methylviologen (1,1‘-dimethyl-4,4‘-bipyridinium cation), and oligonucleotide DNA binding − have been examined by that technique.…”

Section: Introductionmentioning

confidence: 99%

Ground-State Interactions between Ruthenium(II)−Diimine Complexes and Phenol and Monochlorophenols in Aqueous Solution

Hoffman

Pizzocaro

et al. 1998

Inorg. Chem.

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Ground-state interactions between Ru(bpy)3 2+ (bpy = 2,2‘-bipyridine) or Ru(bpz)3 2+ (bpz = 2,2‘-bipyrazine) and phenol (PhOH) or monochlorophenols (ClPhOH) have been investigated in aqueous (D2O) solution by NMR. The upfield shifts of the resonances and the NOE difference spectra of the complexes in the presence of the phenols indicate the presence of offset face-to-face π-stacking interactions between the phenol and the aromatic ligands. Electron withdrawal from the phenol ring by the monochloro substituent and less effective solvation by aqueous (compared to acetonitrile) media favor the interaction. The formation constant for the 1:1 Ru(bpy)3 2+−PhOH complex is estimated to be ∼0.01 M-1; K is smaller for Ru(bpz)3 2+ than for Ru(bpy)3 2+, and it increases for both complexes in the order PhOH < 4-ClPhOH < 3-ClPhOH < 2-ClPhOH.

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