1991
DOI: 10.1016/s0020-1693(00)84943-9
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Properties of ruthenium bipyridyl dimers bridged by disubstituted anthraquinones

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Cited by 21 publications
(12 citation statements)
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“…[36] The appreciable effect of the electronic structure of BL 2-on the first oxidation potential of [1][2][3][4][5][6][7][8] 2+ (Table 5) indeed justifies its preferential involvement. The above assignments are in good agreement with the computed HOMO energies of [1a] 2+ at the B3LYP level ( Figure 10 and Table 7 [10] [{(bpy) 2 Ru} 2 (µ-BL 4 2-)] 3+ , [11] and [{(bpy) 2 Ru} 2 (µ-BL 8 2-)] 3+ [11] were, however, ascribed to a mixed-valence Ru II Ru III situation based on the EPR spectrum of the isolated polycrystalline [{(bpy) 2 Ru} 2 (µ-BL 1 2-)] 3+ at 77 K (g 1 = 2.33, g 2 = 2.01, and g 3 = 1.88; ∆g = 0. 45 and ϽgϾ = 2.08) and the near-IR transition at 2083 nm in CH 3 CN (ε = 9120  -1 cm -1 , ∆ν 1/2 = 3000 cm -1 ).…”
Section: Electrochemistry Epr Spectroscopy Spectrolectrochemistry supporting
confidence: 84%
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“…[36] The appreciable effect of the electronic structure of BL 2-on the first oxidation potential of [1][2][3][4][5][6][7][8] 2+ (Table 5) indeed justifies its preferential involvement. The above assignments are in good agreement with the computed HOMO energies of [1a] 2+ at the B3LYP level ( Figure 10 and Table 7 [10] [{(bpy) 2 Ru} 2 (µ-BL 4 2-)] 3+ , [11] and [{(bpy) 2 Ru} 2 (µ-BL 8 2-)] 3+ [11] were, however, ascribed to a mixed-valence Ru II Ru III situation based on the EPR spectrum of the isolated polycrystalline [{(bpy) 2 Ru} 2 (µ-BL 1 2-)] 3+ at 77 K (g 1 = 2.33, g 2 = 2.01, and g 3 = 1.88; ∆g = 0. 45 and ϽgϾ = 2.08) and the near-IR transition at 2083 nm in CH 3 CN (ε = 9120  -1 cm -1 , ∆ν 1/2 = 3000 cm -1 ).…”
Section: Electrochemistry Epr Spectroscopy Spectrolectrochemistry supporting
confidence: 84%
“…It is interesting to note that the occupied frontier orbitals (HOMO to HOMO-2) exhibit a fairly good mixing with the π orbitals of pap in [1a] 2+ ( Figure 10 and Table 7). The formulations of analogous two-electron-oxidized bpy complexes [{(bpy) 2 Both the ancillary (aap) [37] and bridging ligand (BL 2-) [10,11] are known to successively accept two electrons each in their LUMOs (Scheme 3), therefore ideally a total of ten one-electron reduction processes (eight from four aap ligands and two from BL 2-) are expected for [1][2][3][4][5][6][7][8] 2+ . The complexes indeed display multiple reductions in CH 3 CN or CH 2 Cl 2 ( Figure 8 and Table 5) within the accessible potential limit of -2.0 V. However, instead of ten successive oneelectron reduction processes, simultaneous two-electron processes are also detected along with the clear one-electron responses, as confirmed by comparing the current heights of their respective DPVs (differential pulse voltammograms) with that of the coulometrically established one-electron oxidation processes.…”
Section: Electrochemistry Epr Spectroscopy Spectrolectrochemistry mentioning
confidence: 99%
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“…Unlike 2 3+ , the corresponding system 4 n was reported to be isolated with the dianionic 1,4-dioxido-9,10-anthraquinone bridging ligand in [(bpy) 2 Ru II (μ-QL 2− )-Ru II (bpy) 2 ] 2+ , exhibiting two reversible oxidation and three reversible reduction processes at 0.59 V, 0.86 V and −0.95 V, −1.38 V, −1.73 V, respectively. 18 Relative to oxido substituents the imino groups in the H 2 L n bridge of 2 3+ thus decrease the oxidation potential and shift the reduction potential to more negative values (Table 4).…”
Section: ■ Introductionmentioning
confidence: 99%