Outer-sphere charge transfer in mixed-metal ion pairs

Curtis, James A.; Meyer, Thomas J.

doi:10.1021/ic00134a059

Cited by 137 publications

(73 citation statements)

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“…Moreover, for this often studied redox system Fe(CN) 6 4À/3À , it has been suggested that it is an outer-sphere charge-transfer route in aqueous solution. [17] To the contrary, McCreery and co-workers [2] have reported that this couple is very sensitive to surface structures, which greatly influences the observed electron transfer rates. By the use of adsorption effects of AQDS on the rate constant for A C H T U N G T R E N N U N G Fe(CN) 6 3À/4À , it was found that the decrease of the rate constant is much larger than the decease in the rate constant observed for other outer-sphere route couples.…”

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confidence: 98%

Oxygenated Edge Plane Sites Slow the Electron Transfer of the Ferro‐/Ferricyanide Redox Couple at Graphite Electrodes

et al. 2006

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The electron transfer kinetics of ferrocyanide, potassium hexachloroiridate(III), hexaammineruthenium(III) chloride, and N,N,N',N'-tetramethyl-p-phenylenediamine (TMPD) have been examined at basal plane and edge plane pyrolytic graphite electrodes which have been allowed to oxidise in air for various periods of time. It is demonstrated via voltammetric and X-ray photoelectron spectroscopy (XPS) analysis that oxygenated species formed at edge plane sites/defects decrease the electron transfer kinetics of ferrocyanide but that the rates for potassium hexachloroiridate(III), hexaammineruthenium(III) chloride and TMPD are insensitive to the oxygenated species. The behaviour of the ferro-/ferricyanide couple contrasts with that seen on single-walled carbon nanotubes where oxygenation of the tube ends is known to speed up the electron transfer kinetics (A. Chou, T. Bocking, N. K. Singh, J. J. Gooding, Chem. Commun. 2005, 842); the possible reasons for this contrasting behaviour are discussed.

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confidence: 98%

Oxygenated Edge Plane Sites Slow the Electron Transfer of the Ferro‐/Ferricyanide Redox Couple at Graphite Electrodes

et al. 2006

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“…1, essentially complete complex formation begins at ∼30 mM N-methyl-4,4′-bipyridinium with 30 mM added phenol. Spectrophotometric analyses of complex formation, with the evaluation of equilibrium constants for association, K A , were carried out under conditions with less than 100% complex formation by the method of Curtis and Meyer (34). Based on the K A values, free energies of formation for the series of H-bonded adducts were ∼2 kcal/mol (700 cm −1 ) ( Table 1), within the range expected for hydrogen bond interactions 1-5 kcal/mol (300-1,500 cm −1 ) (Supporting Information) (16,35).…”

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confidence: 99%

Direct observation of light-driven, concerted electron–proton transfer

Gagliardi

Wang

Dongare

et al. 2016

Proc. Natl. Acad. Sci. U.S.A.

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The phenols 4-methylphenol, 4-methoxyphenol, and N-acetyl-tyrosine form hydrogen-bonded adducts with N-methyl-4, 4′-bipyridinium cation (MQ+) in aqueous solution as evidenced by the appearance of low-energy, low-absorptivity features in UV-visible spectra. They are assigned to the known examples of optically induced, concerted electron–proton transfer, photoEPT. The results of ultrafast transient absorption measurements on the assembly MeOPhO-H---MQ+ are consistent with concerted EPT by the instantaneous appearance of spectral features for MeOPhO·---H-MQ+ in the transient spectra at the first observation time of 0.1 ps. The transient decays to MeOPhO-H---MQ+ in 2.5 ps, accompanied by the appearance of oscillations in the decay traces with a period of ∼1 ps, consistent with a vibrational coherence and relaxation from a higher υ(N-H) vibrational level or levels on the timescale for back EPT.

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“…Potassium hexacyanoruthenate(ii) was prepared according to a literature method. [35] Infrared spectra were recorded as KBr discs in the region of 400Ϫ4000 cm Ϫ1 with an Avatar 360 FTIR spectrophotometer. Elemental analyses were carried out with an Elementar Vario EL Analyser.…”

Section: Methodsmentioning

confidence: 99%