Rates of Interfacial Electron Transfer through π-Conjugated Spacers

Sachs, Sandra B.; Dudek, Stephen P.; Hsung, Richard P.; Sita, Lawrence R.; Smalley, John F.; Newton, Marshall D.; Feldberg, Stephen W.; Chidsey, Christopher E. D.

doi:10.1021/ja972244y

Cited by 360 publications

(363 citation statements)

References 27 publications

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“…These results are expected based on previous work on mixed monolayers formed by coadsorption of diluent thiols with thiols terminated by redox species. 3,4,6,9,12,15,18 One sees from Table 1 that the rate of electron transfer to the clickcoupled redox couples can readily be scaled by over 4 orders of magnitude by modifying the nature of the azide-terminated mixed monolayer.…”

Section: Resultsmentioning

confidence: 99%

Rate of Interfacial Electron Transfer through the 1,2,3-Triazole Linkage

et al. 2006

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The rate of electron transfer is measured to two ferrocene and one iron tetraphenylporphyrin redox species coupled through terminal acetylenes to azide-terminated thiol monolayers by the Cu(I)-catalyzed azide-alkyne cycloaddition (a Sharpless "click" reaction) to form the 1,2,3-triazole linkage. The high yield, chemoselectivity, convenience, and broad applicability of this triazole formation reaction make such a modular assembly strategy very attractive. Electron-transfer rate constants from greater than 60,000 to 1 s −1 are obtained by varying the length and conjugation of the electron-transfer bridge and by varying the surrounding diluent thiols in the monolayer. Triazole and the triazole carbonyl linkages provide similar electronic coupling for electron transfer as esters. The ability to vary the rate of electron transfer to many different redox species over many orders of magnitude by using modular coupling chemistry provides a convenient way to study and control the delivery of electrons to multielectron redox catalysts and similar interfacial systems that require controlled delivery of electrons.

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Section: Resultsmentioning

confidence: 99%

Rate of Interfacial Electron Transfer through the 1,2,3-Triazole Linkage

et al. 2006

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“…The situation is almost the same as that of injecting electrons through insulating films. 84) Thus, it would be practically impossible to use these molecules in current injection type single molecule electronic systems, such as logic, memory and wiring units, because most of the molecules that have been described in §2.1, have a band gap energy of 2-3 eV, and are "insulators".…”

Section: Prediction Of Carrier Transport Through Single Molecule (1) mentioning

confidence: 99%

Prospects and Problems of Single Molecule Information Devices

Wada

Tsukada

Fujihira

et al. 2000

Jpn. J. Appl. Phys.

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Current information technologies use semiconductor devices and magnetic/optical discs, however, it is foreseen that they will all face fundamental limitations within a decade. This paper reviews the prospects and problems of single molecule devices, including switching devices, wires, nanotubes, optical devices, storage devices and sensing devices for future information technologies and other advanced applications in the next paradigm. The operation principles of these devices are based on the phenomena occurring within a single molecule, such as single electron transfer, direct electron-hole recombination, magnetic/charge storage and regand-receptor reaction. Four possible milestones for realizing the Peta (10 15 )-floating operations per second (P-FLOPS) personal molecular supercomputer are described, and the necessary technologies are listed. These include, (1) two terminal conductance measurement on single molecule, (2) demonstration of two terminal molecular device characteristics, (3) verification of three terminal molecular device characteristics and (4) integration of the functions of "molecular super chip". Thus, 1000 times higher performance information technologies would be realized with molecular devices.

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“…[22,23] In particular, electrochemical studies of a ferrocene monolayer on Au have contributed much to the understanding of long-range electron transfer between an electrode and redox molecules. [24][25][26] These studies have mainly been conducted on ferrocene linked to the surface via a long tether. Regarding experiments conducted on Si, the previously studied tethers are rather short, and future development of related technologies could benefit from an improved understanding of electron transfer between the Si electrode and the redox-active molecule, based on an investigation of the effect of linker length.…”

Section: Introductionmentioning

confidence: 99%

Ferrocene and Porphyrin Monolayers on Si(100) Surfaces: Preparation and Effect of Linker Length on Electron Transfer

et al. 2009

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The missing link: Ferrocene and porphyrin monolayers are tethered on silicon surfaces with short (see picture, left) or long (right) linkers. Electron transfer to the silicon substrate is faster for monolayers with a short linker.Ferrocene and porphyrin derivatives are anchored on Si(100) surfaces through either a short two-carbon or a long 11-carbon linker. The two tether lengths are obtained by using two different grafting procedures: a single-step hydrosilylation is used for the short linker, whereas for the long linker a multistep process involving a 1,3-dipolar cycloaddition is conducted, which affords ferrocene-triazole-(CH(2))(11)-Si or Zn(porphyrin)-triazole-(CH(2))(11)-Si links to the surface. The modified surfaces are characterized by X-ray photoelectron spectroscopy and Fourier transform infrared spectroscopy. Cyclic voltammetry experiments show that the redox activity of the tethered ferrocene or porphyrin is maintained for both linker types. Microelectrode capacitor devices incorporating these modified Si(100) surfaces are designed, and their capacitance-voltage (C-V) and conductance-voltage (G-V) profiles are investigated. Capacitance and conductance peaks are observed, which indicates efficient charge transfer between the redox-active monolayers and the electrode surface. Slower electron transfer between the ferrocene or porphyrin monolayer and the electrode surface is observed for the longer linker, which suggests that by adjusting the linker length, the electrical properties of the device, such as charging and discharging kinetics and retention time, could be tuned.

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Rates of Interfacial Electron Transfer through π-Conjugated Spacers

Cited by 360 publications

References 27 publications

Rate of Interfacial Electron Transfer through the 1,2,3-Triazole Linkage

Rate of Interfacial Electron Transfer through the 1,2,3-Triazole Linkage

Prospects and Problems of Single Molecule Information Devices

Ferrocene and Porphyrin Monolayers on Si(100) Surfaces: Preparation and Effect of Linker Length on Electron Transfer

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