Resonance Raman spectra of the ground and excited states of specifically deuterated tris(2,2'-bipyridine)ruthenium(II)

Localized 3MLCT Transitions in [Ru(bpy)3-x(bpy-6,6‘-d2)x]2+ (x = 0−3, bpy = 2,2‘-Bipyridine). Probing Minimally Perturbed Chromophores

“…[2][3][4][5][6][7][8] This result provides an upper limit of ∼200 cm -1 for the excitation exchange interaction between metal-ligand subunits. The effects of any interaction are diminished by the nanoheterogeneity of the ligands.…”

Vibrational Sidelines in the Localized 3MLCT Emission of [Ru(bpy)2(bpz)]2+ in [Zn(bpy)3](ClO4)2 (bpy = 2,2‘-Bipyridine, bpz = 2,2‘-Bipyrazine)

“…In Figure 6 the spectrum of [Ru(bpy) 2 3 ]-(ClO 4 ) 2 . We note here that there is a substantial difference in the intensities of modes in the perprotonated ruthenium and osmium complexes.…”

“…For example, independent 3 MLCT transitions involving the bpy or the bpy-d 8 ligands are observed in the complexes [Ru(bpy) 3-x (bpy-d 8 ) x ] 2+ (x ) 1, 2) in [Zn(bpy) 3 ](ClO 4 ) 2 . 9,13 By using time-resolved luminescence line-narrowing experiments, we have shown that stochastic excitation energy transfer ()interligand "electron" transfer) between equivalent ligands occurs as slowly as ≈1 × 10 8 s -1 in level II at 1.8 K.…”

“…We have observed energy differences of ≈360 and ≈600 cm -1 for the 3,3′-bipyridazine (bprid) ligand in the [Ru(bpy) 2 (bprid)] 2+ and [Os(bpy-d 8 ) 2 -(bprid)] 2+ complexes, respectively. 11,18 It is accepted that the lowest-excited 3 MLCT states in the [Ru(bpy) 2 (bpz)] 2+ complex are localized on the Ru-bpz subunit as the π* orbital of the bpz ligand is ≈3000 cm -1 lower in energy than that of the bpy ligands. 4,19, 20 Braun et al 20 reported luminescence spectra of the complexes [Ru(bpy) 2 (L)] 2+ with L ) bpy-d 8 that vibrational sidelines associated with the Ru-bpy subunit occur in the 0-600 cm -1 range in the luminescence of the [Ru(bpy) 2 (bpz)] 2+ complex, but they were not able to identify high-frequency bpy ligand-centered modes.…”

“…In contrast, sidelines involving the bpy ligands will show variations in frequency and intensity. 3 ]-(ClO 4 ) 2 were grown from aqueous solutions. 9 A Spectra Physics 375 standing wave dye laser (DCM) pumped by a Spectra Physics 171 Ar + laser was used as the excitation source.…”