Modulation of Electronic Coupling through Self-Assembled Monolayers via Internal Chemical Modification

Cheng, Jun; Sághi-Szabó, G.; Tossell, J. A.; Miller, Cary J.

doi:10.1021/ja953210y

Cited by 71 publications

(90 citation statements)

References 51 publications

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“…This result is attributed to a decrease in H AB [325]. H AB between the redox species and the electrode is dependent upon the overlap of the σ and σ* orbitals of the individual atoms in the hydrocarbon chain of the bridge with the orbitals of the nearest neighboring 2–3 atoms [40,326–329].…”

Section: Bridge and Diluentmentioning

confidence: 99%

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Electrochemistry of redox-active self-assembled monolayers

Eckermann

Feld

Shaw

et al. 2010

Coordination Chemistry Reviews

523

492

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Redox-active self-assembled monolayers (SAMs) provide an excellent platform for investigating electron transfer kinetics. Using a well-defined bridge, a redox center can be positioned at a fixed distance from the electrode and electron transfer kinetics probed using a variety of electrochemical techniques. Cyclic voltammetry, AC voltammetry, electrochemical impedance spectroscopy, and chronoamperometry are most commonly used to determine the rate of electron transfer of redoxactivated SAMs. A variety of redox species have been attached to SAMs, and include transition metal complexes (e.g., ferrocene, ruthenium pentaammine, osmium bisbipyridine, metal clusters) and organic molecules (e.g., galvinol, C 60 ). SAMs offer an ideal environment to study the outer-sphere interactions of redox species. The composition and integrity of the monolayer and the electrode material influence the electron transfer kinetics and can be investigated using electrochemical methods. Theoretical models have been developed for investigating SAM structure. This review discusses methods and monolayer compositions for electrochemical measurements of redox-active SAMs.

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Section: Bridge and Diluentmentioning

confidence: 99%

“…Interrupting this σ and σ* orbital overlap within the bridge by an alkene or alkyne results in two, long, through space interactions. The result is a less effective electronic coupling pathway as compared to unmodified alkane thiol bridges [325]. …”

Section: Bridge and Diluentmentioning

confidence: 99%

Electrochemistry of redox-active self-assembled monolayers

Eckermann

Feld

Shaw

et al. 2010

Coordination Chemistry Reviews

523

492

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“…29 Insertion of a heteroatom, a double bond or a triple bond into the repeating CH 2 spacer unit in an alkane chain reduces the electronic coupling. 227 Several experiments suggest that electronic coupling through alkane chains not attached to or in contact with the redox center can contribute significantly to the total electronic coupling. 75,221 In general, reorganization energies obtained from Tafel plots and Arrhenius plots are in agreement.…”

Section: Long-range Electron Transfermentioning

confidence: 99%

Self‐Assembled Monolayers on Electrodes

Finklea

2000

Encyclopedia of Analytical Chemistry

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Alkanethiols and related molecules spontaneously adsorb from solution or vapor phase onto oxide‐free metals, especially gold, to form close‐packed oriented monolayers. The ease and flexibility of the self‐assembly process provides a convenient method for altering the properties of the metal as an electrode. The close‐packed hydrocarbon layer blocks access of most solution species to the electrode surface. Consequently, interfacial capacitances are markedly reduced and most electron‐transfer reactions are strongly inhibited. The monolayers also provide a foundation for attachment of additional molecules or molecular layers to electrodes. Self‐assembled monolayers (SAMs) on electrodes have been used in voltammetric methods to improve the analytical sensitivity and to impart greater selectivity towards specific analytes. Redox molecules have been anchored at fixed and controllable distances from the electrode surface, thereby permitting the study of electron‐transfer kinetics over long distances and at large driving forces. The ability of SAMs to inhibit metal corrosion and to promote better adhesion of electroactive polymers has been demonstrated.

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“…In this last case, nonlinear decay plots, approaching a kinetic saturation regime, have been reported [21]. Insertion of single ether, alkyne or alkene linkages into alkanethiol chains has been shown to reduce the electronic coupling across the monolayer [22], whereas extensive amide-amide hydrogen bonding interactions between neighboring organic chains results in higher electron transfer rates [23].…”

Section: Introductionmentioning

confidence: 99%