The Kinetics of Electron Transfer Through Ferrocene-Terminated Alkanethiol Monolayers on Gold

Smalley, John F.; Feldberg, Stephen W.; Chidsey, Christopher E. D.; Linford, Matthew R.; Newton, Marshall D.; Liu, Yiping

doi:10.1021/j100035a016

Cited by 576 publications

(782 citation statements)

References 7 publications

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“…The driving force-optimized azurin tunneling timetable reveals a nearly perfect exponential distance dependence, with a decay constant (␤) of 1.1 Å Ϫ1 , and an intercept at close contact (r o ϭ 3 Å) of 10 13 s Ϫ1 . This decay constant is quite similar to that found for superexchange-mediated tunneling across saturated alkane bridges (␤ Ϸ1.0 Å Ϫ1 ) (12,35), strongly indicating that a similar coupling mechanism is operative in the polypeptide (Fig. 1).…”

Section: Ru-proteinssupporting

confidence: 77%

Long-range electron transfer

Gray

Winkler

2005

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

767

841

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Recent investigations have shed much light on the nuclear and electronic factors that control the rates of long-range electron tunneling through molecules in aqueous and organic glasses as well as through bonds in donor-bridge-acceptor complexes. Couplings through covalent and hydrogen bonds are much stronger than those across van der Waals gaps, and these differences in coupling between bonded and nonbonded atoms account for the dependence of tunneling rates on the structure of the media between redox sites in Ru-modified proteins and protein-protein complexes.electron tunneling ͉ hopping ͉ glass ͉ protein

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Section: Ru-proteinssupporting

confidence: 77%

Long-range electron transfer

Gray

Winkler

2005

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

767

841

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“…This rate constant seems much too small when related data are considered. For example, the rate constant 21,22 for oxidation of ferrocene linked to Au through a well-ordered hexanethiolate linker (the same number of intervening carbons as the TBBT linker) is 2.5 × 10 5 s -1 , or over 10 4 times larger. Such a large difference seems unlikely, even allowing for electronic uncoupling incurred by twisting of the phenyl rings in the 4,4′-thiobisbenzenethiol linker molecule.…”

Section: Resultsmentioning

confidence: 99%

Electrochemical Quantized Capacitance Charging of Surface Ensembles of Gold Nanoparticles

1999

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Quantized double layer capacitance charging is observed for monolayers of nanometer-sized monolayer protected gold clusters (Au MPCs) anchored to macroscopic gold electrodes. The clusters were anchored in two ways. One method involves ligand place-exchange binding of an MPC covered with a butanethiolate monolayer to a preformed, self-assembled monolayer of 4,4′-thiobisbenzenethiol (TBBT) on Au. In the second method, an MPC with a mixed TBBT/heptanethiolate monolayer is prepared; this surface-reactive cluster anchors itself onto a gold electrode surface. Differential pulse voltammetry (DPV) of these MPC monolayers displays a succession of current peaks whose regular spacing on the potential axis is similar to that in DPV of solutions of the same, nonanchored MPCs. AC impedance measurements of the MPC monolayers show capacitance undulations that mirror the DPV results.

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“…is the extrapolated value of the rate constant for r = 0. 62 This analysis predicts a 1.1-fold increase in the rate constant when the tilt angle is increased from 33° to 42°. The opposite trend was observed here: k s,opt for (terphenyl) 2 -PDI-IP-PA was 14-fold less than k s,opt for alkyl-PDI-PA (Table 2).…”

Section: Electron-transfer Kinetics At the Pdi Film/ito Interfacementioning

confidence: 96%

Influence of Molecular Aggregation on Electron Transfer at the Perylene Diimide/Indium-Tin Oxide Interface

Zheng

Jradi

Parker

et al. 2016

ACS Appl. Mater. Interfaces

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Chemisorption of an organic monolayer to tune the surface properties of a transparent conductive oxide (TCO) electrode can improve the performance of organic electronic devices that rely on efficient charge transfer between an organic active layer and a TCO contact. Here a series of perylene diimides (PDIs) was synthesized and used to study relationships between monolayer structure/properties and electron transfer kinetics at PDI-modified indium tin oxide (ITO) electrodes. In these PDI molecules, one of the imide substituents is a benzene ring bearing a phosphonic acid (PA) and the other is a bulky aryl group that is twisted out of the plane of the PDI core. The size of the bulky aryl group and the substitution of the benzene ring bearing the PA were both varied which altered the extent of aggregation when these molecules were absorbed as monolayer films (MLs) on ITO, as revealed by both attenuated total reflectance (ATR) and total internal reflection fluorescence (TIRF) spectra. Polarized ATR measurements indicate that in these MLs, the long axis of the PDI core is tilted at an angle of 33˚-42˚ relative to the surface normal; the tilt angle increased as the degree of bulky substitution increased. Rate constants for electron transfer (k s,opt ) between these redox-active modifiers and ITO were determined by potential-modulated ATR spectroscopy. As the degree of PDI aggregation was reduced, k s,opt declined which is attributed to a reduction in the lateral electron self-exchange rate between adsorbed PDI molecules, as well as the heterogeneous conductivity of the ITO electrode surface. Photoelectrochemical measurements using a dissolved aluminum phthalocyanine as an electron donor showed that ITO modified with any of these PDIs is a more effective electron-collecting electrode than bare ITO.

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The Kinetics of Electron Transfer Through Ferrocene-Terminated Alkanethiol Monolayers on Gold

Cited by 576 publications

References 7 publications

Long-range electron transfer

Long-range electron transfer

Electrochemical Quantized Capacitance Charging of Surface Ensembles of Gold Nanoparticles

Influence of Molecular Aggregation on Electron Transfer at the Perylene Diimide/Indium-Tin Oxide Interface

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