Temperature, pressure, and electrolyte dependence of the ferrocene/ferrocenium electron self-exchange in acetonitrile-d3

Kirchner, Karl; Dang, Shu; Stebler, M.; Dodgen, Harold W.; Wherland, Scot; Hunt, John P.

doi:10.1021/ic00317a042

Cited by 26 publications

(21 citation statements)

References 6 publications

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“…17 The radius of ferrocene is r Fc = 4 Å. 18 Density functional theory calculations by Mori and co-workers on the dye MK3, a close structural analogue of MK1, suggested that the dyes can be described as an ellipse with r x,y = 4.5 Å and r z = 10 Å. 19 If dense packing of the dye on the TiO 2 surface is assumed, the ethylcarbazole-based dye molecule can be approximated as a hemisphere with a radius of r dye = 4.5 Å.…”

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confidence: 99%

Dye Regeneration Kinetics in Dye-Sensitized Solar Cells

et al. 2012

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The ideal driving force for dye regeneration is an important parameter for the design of efficient dye-sensitized solar cells. Here, nanosecond laser transient absorption spectroscopy was used to measure the rates of regeneration of six organic carbazole-based dyes by nine ferrocene derivatives whose redox potentials vary by 0.85 V, resulting in 54 different driving-force conditions. It was found that the reaction follows the behavior expected for the Marcus normal region for driving forces below 29 kJ mol(-1) (ΔE = 0.30 V). Driving forces of 29-101 kJ mol(-1) (ΔE = 0.30-1.05 V) resulted in similar reaction rates, indicating that dye regeneration is diffusion controlled. Quantitative dye regeneration (theoretical regeneration yield 99.9%) can be achieved with a driving force of 20-25 kJ mol(-1) (ΔE ≈ 0.20-0.25 V).

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confidence: 99%

Dye Regeneration Kinetics in Dye-Sensitized Solar Cells

et al. 2012

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“…Run a:[5] = 0.5343 M, [S'+PF,-] = 11.7,mM. T("C) (AAul12, HzJ 5.2 (3.1}, 10.5 13.71, 17.3 (4.6), 20.2 {5.1}, 22.4 (5.4).…”

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confidence: 99%

Ferrocene-sesquibicyclic hydrazine cross-electron-transfer rates

Nelsen¹,

Wang²,

Ramm³

et al. 1992

J. Phys. Chem.

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“…7,36 We have therefore determined the self-exchange rate for BuFc/BuFc + by NMR spectroscopy. This has been done previously for ferrocene [37][38][39][40] and various alkylated ferrocenes, 38,39 but never for n-butylferrocene.…”

Section: Electron Transfer Self-exchange Rates and Predicted Conducti...mentioning

confidence: 99%

Electrical conductivity in two mixed-valence liquids

Yao

Kelley

Rogers

et al. 2015

Phys. Chem. Chem. Phys.

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Two different room-temperature liquid systems were investigated, both of which conduct a DC electrical current without decomposition or net chemical transformation. DC electrical conductivity is possible in both cases because of the presence of two different oxidation states of a redox-active species. One system is a 1 : 1 molar mixture of n-butylferrocene (BuFc) and its cation bis(trifluoromethane)sulfonimide salt, [BuFc(+)][NTf2(-)], while the other is a 1 : 1 molar mixture of TEMPO and its cation bis(trifluoromethane)sulfonimide salt, [TEMPO(+)][NTf2(-)]. The TEMPO-[TEMPO(+)][NTf2(-)] system is notable in that it is an electrically conducting liquid in which the conductivity originates from an organic molecule in two different oxidation states, with no metals present. Single-crystal X-ray diffraction of [TEMPO(+)][NTf2(-)] revealed a complex structure with structurally different cation-anion interactions for cis- and trans [NTf2(-)] conformers. The electron transfer self-exchange rate constant for BuFc/BuFc(+) in CD3CN was determined by (1)H NMR spectroscopy to be 5.4 × 10(6) M(-1) s(-1). The rate constant allowed calculation of an estimated electrical conductivity of 7.6 × 10(-5)Ω(-1) cm(-1) for BuFc-[BuFc(+)][NTf2(-)], twice the measured value of 3.8 × 10(-5)Ω(-1) cm(-1). Similarly, a previously reported self-exchange rate constant for TEMPO/TEMPO(+) in CH3CN led to an estimated conductivity of 1.3 × 10(-4)Ω(-1) cm(-1) for TEMPO-[TEMPO(+)][NTf2(-)], a factor of about 3 higher than the measured value of 4.3 × 10(-5)Ω(-1) cm(-1).

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Temperature, pressure, and electrolyte dependence of the ferrocene/ferrocenium electron self-exchange in acetonitrile-d3

Cited by 26 publications

References 6 publications

Dye Regeneration Kinetics in Dye-Sensitized Solar Cells

Dye Regeneration Kinetics in Dye-Sensitized Solar Cells

Ferrocene-sesquibicyclic hydrazine cross-electron-transfer rates

Electrical conductivity in two mixed-valence liquids

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