Effects of long-range electron transfer on charge transport in static assemblies of redox centers

Blauch, David N.; Savéant, Jean Michel

doi:10.1021/j100126a019

Cited by 85 publications

(75 citation statements)

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“…However, because of the low apparent electron diffusion coefficient, D app , of the hydrogel formed from the cross-linked polymer, 1.2 · 10 À9 cm 2 s À1 , the maximal current density was low, only 150 lA cm À2 [29] To increase D app and decrease the overpotential for glucose electro-oxidation, Heller and coworkers [29] tethered redox centers to a PVP backbone through 13 atom long flexible spacer arms. Consistently with the prediction of the model of Blauch and Savéant, [30,31] the long tethers increased D app to an unprecedented value of 5 · 8.10 À6 cm 2 s À1 . To downshift the redox potential, the Os 2+/3+ inner sphere ligands were three N,N 0 -dialkylated-2,2 0 -biimidazoles.…”

Section: Introductionsupporting

confidence: 83%

On the parameters affecting the characteristics of the “wired” glucose oxidase anode

Mano

Mao

Heller

2005

Journal of Electroanalytical Chemistry

116

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Section: Introductionsupporting

confidence: 83%

On the parameters affecting the characteristics of the “wired” glucose oxidase anode

Mano

Mao

Heller

2005

Journal of Electroanalytical Chemistry

116

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“…Specifically a shift of the percolation threshold to lower densities of the electroactive species and higher values of the apparent diffusion coefficient have been predicted as a result of finite rates of electron transfer at distances larger than contact. 41 Since one of our motivations has been to study long-range electron transfer kinetics, we attempted to form such two-component monolayers. Thus far, the results have been disappointing.…”

Section: Resultsmentioning

confidence: 99%

“…A small shift of the percolation threshold to lower X values could be the result of long-range electron transfer contributions in the electron hopping as described by Blauch and Savéant. 41 However, limited precision of the experimental data does not allow us to make …”

Section: Resultsmentioning

confidence: 99%

Structure and Lateral Electron Hopping in Osmium-tris-4,7-diphenylphenanthroline Perchlorate Monolayers at the Air/Water Interface

et al. 1999

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Osmium tris-diphenylphenanthroline perchlorate (Os(DPP) 3 ) can be spread at the air/water interface where it forms solid monolayer films. Brewster angle microscopy revealed that these films consist of irregular ca. 100 to 1000 µm diameter 2D aggregates which coalesce upon compression to form continuous films. Grazing incidence X-ray diffraction data showed that the structure of the aggregates is independent of the degree of monolayer compression and features a 2D lattice of hexagonally close-packed Os(DPP) 3 centers with Os-Os distances of 12.57 Å. The latter is 4 to 24% shorter than the Ru-Ru distances found in the 3D monoclinic crystal of an isostructural Ru (DPP) 3 . Two dimensional electrochemical measurements carried out with line microelectrodes at the air/water interface were used to study kinetics of the lateral electron transport in these Langmuir monolayers. Electron transport involves electron hopping on the 2D lattice of the osmium sites where the individual electron transfer steps between Os II (DPP) 3 and Os III (DPP) 3 take place with the rate constant k 1 ) 4.7 × 10 8 s -1 . Percolation theory was used to account for the observed increase of the electron hopping rates during monolayer compression on the water surface resulting in an increase of the extent of connectivity and thus electroactivity of the initially formed 2D Os(DPP) 3 aggregates. Percolation theory also accounts well for the dependence of the electron hopping rates on the composition of fully compressed Os-(DPP) 3 /Ru(DPP) 3 monolayers in which the ruthenium species were used to homogeneously dilute the Os-(DPP) 3 sites. In contrast, in Os(DPP) 3 /octadecanol monolayers, macroscopic self-segregation of the two components was inferred from a larger positive shift of the apparent percolation threshold in the lateral electron hopping.

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“…It has also been employed for studying the electron transfer mechanism of the redox moieties involved in supramolecular systems [10][11][12][13] relevant to biological electron transport as well as electric and photoelectric functional devices [14]. The electron propagation by redox species in a polymer film has been studied extensively in recent years, and many papers have been published on its kinetics [15][16][17][18][19][20][21].…”

Section: Introductionmentioning

confidence: 99%

Electron transfer in the redox reaction of cobalt tetraphenylporphyrin incorporated in a Nafion film

Zhao

Zhang

Kaneko

2000

J. Porphyrins Phthalocyanines

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Potential step chronoamperospectrometry (PSCAS) was carried out to analyze electron transfer in the redox reaction processes of 5,10,15,20-tetraphenylporphyrinatocobalt(II) ( Co II TPP (-2)) incorporated in a Nafion film. The reactions of Co II TPP (-2) to [ Co III TPP (-2)]+ and of [ Co III TPP (-2)]+ to Co II TPP (-2) took place through a diffusion mechanism, as confirmed by the first-order initial reaction rate with respect to the complex concentration in the matrix. However, the reaction of [ Co III TPP (-2)]+ to [ Co III TPP (-1)]2+ occurred by an electron-hopping mechanism, as confirmed by the second-order initial reaction rate with respect to the complex concentration. The fraction of electroactive complex (Rct) increased with the sample time after the potential step until it reached saturation. In the reactions of Co II TPP (-2) to [ Co III TPP (-2)]+ and of [ Co III TPP (-2)]+ to Co II TPP (-2), Rct approached 1.0, while in the reaction of [ Co III TPP (-2)]+ to [ Co III TPP (-1)]2+, only about 0.3 was reached. The apparent diffusion coefficient (Dapp) decreased in the order of [ Co III TPP (-2)]+ to Co II TPP (-2) > Co II TPP (-2) to [ Co III TPP (-2)]+>[ Co III TPP (-2)]+ to [ Co III TPP (-1)]2+. The different behavior of these redox reactions was ascribed to the microenvironment of the redox species in the matrix, interaction of the redox centers, especially the product with the framework, and counter ion migration.

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Effects of long-range electron transfer on charge transport in static assemblies of redox centers

Cited by 85 publications

References 0 publications

On the parameters affecting the characteristics of the “wired” glucose oxidase anode

On the parameters affecting the characteristics of the “wired” glucose oxidase anode

Structure and Lateral Electron Hopping in Osmium-tris-4,7-diphenylphenanthroline Perchlorate Monolayers at the Air/Water Interface

Electron transfer in the redox reaction of cobalt tetraphenylporphyrin incorporated in a Nafion film

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