.omega.-Hydroxythiol Monolayers at Au Electrodes. 5. Insulated Electrode Voltammetric Studies of Cyano/Bipyridyl Iron Complexes

Terrettaz, Samuel; Becka, Anne M.; Traub, Michael J.; Fettinger, James C.; Miller, Cary J.

doi:10.1021/j100028a024

Cited by 81 publications

(115 citation statements)

References 2 publications

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“…No microelectrode-type behavior, typical of the presence of pinholes in the film, 46 was observed in the CV curve associated with the 11-MUA modified gold surface, indicating that electron transfer occurs preferentially by through-film tunneling. 46,[50][51][52] The very low level of defects in the film was also assessed by performing an EIS analysis under the conditions of Figure 6. [The presence of unbound or disulfide thiol species evidenced by XPS could introduce defect sites in the monolayer; however, the latter did not affect the electrochemical blocking behavior of the SAM, a The error on the experimental atomic percentages was estimated to be 2% for C, 5% for O, 10% for S, and 15% for N.…”

Section: Xps Analysismentioning

confidence: 99%

Structural, Electrochemical, and Photophysical Properties of a Molecular Shuttle Attached to an Acid-Terminated Self-Assembled Monolayer

Cecchet¹,

Rudolf²,

Rapino³

et al. 2004

J. Phys. Chem. B

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Structural, electrochemical, and photophysical properties of a molecular shuttle attached to an acid-terminated self-assembled monolayer Cecchet, F; Rudolf, Petra; Rapino, S; Margotti, M; Paolucci, F; Baggerman, J; Kay, ER; Wong, JKY; Leigh, DA; Kay, Euan R. Take-down policy If you believe that this document breaches copyright please contact us providing details, and we will remove access to the work immediately and investigate your claim.Downloaded from the University of Groningen/UMCG research database (Pure): http://www.rug.nl/research/portal. For technical reasons the number of authors shown on this cover page is limited to 10 maximum. March 30, 2004; In Final Form: July 6, 2004 A benzylic amide macrocycle containing a pyridine moiety (macrocycle 2) and a related benzylic amide macrocycle-based molecular shuttle (naphthalimide rotaxane) with two pyridine moieties on the macrocyclic unit were grafted onto a self-assembled monolayer (SAM) of 11-mercaptoundecanoic acid (11-MUA) on gold. X-ray photoelectron spectroscopy (XPS) indicates that the molecules are linked to the SAM by hydrogenbonding. Electrochemical investigations show that the self-assembled monolayer is densely packed and well ordered and allows the estimation of the average thickness of the SAM alone and of the SAM functionalized with either macrocycle 2 or with naphthalimide rotaxane. The estimated thickness values suggest that the 11-MUA chains in the SAM are tilted with respect to the surface normal, as expected for ordered and stable SAMs, whereas the rotaxane molecules are oriented with the thread parallel to the SAM surface and macrocycle plan preferentially perpendicular to the surface. The photophysical studies of the naphthalimide rotaxane grafted onto the SAM on gold demonstrated that fluorescence is partially quenched but still remains easily measurable because the presence of the SAM reduces the quenching effect of the metal substrate. Moreover, the photophysical analysis clearly indicates that the naphthalimide part of the rotaxane strongly interacts with the carboxylic groups of the SAM, in agreement with the orientation of the molecule obtained from the electrochemistry.

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Section: Xps Analysismentioning

confidence: 99%

Structural, Electrochemical, and Photophysical Properties of a Molecular Shuttle Attached to an Acid-Terminated Self-Assembled Monolayer

Cecchet¹,

Rudolf²,

Rapino³

et al. 2004

J. Phys. Chem. B

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“…The l values are also in surprisingly good agreement with a simple theoretical equation based on the energy of a charged sphere in a dielectric continuum. 162,228 Table 3 lists selected l values obtained in aqueous electrolytes.…”

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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“…Systematic studies of structural effects in electron transfer have often been carried out by covalently binding electroactive species to the end group [7,42,[44][45][46][47][85][86][87], in which precise control over the dielectric barrier thickness is achieved by varying the number of methylene units in the spacer chain. Freely diffusing (non-bonded) redox couples have also been used for this purpose, though care must be taken to eliminate [44][45][46][47] or account for [7,88,89] defects (pinholes and/or collapsed sites).…”

Section: Applicationsmentioning

confidence: 99%

Electron Transfer Reactivity Patterns at Chemically Modified Electrodes: Fundamentals and Application to the Optimization of Redox Recycling Amplification Systems

Bergren

2006

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.omega.-Hydroxythiol Monolayers at Au Electrodes. 5. Insulated Electrode Voltammetric Studies of Cyano/Bipyridyl Iron Complexes

Cited by 81 publications

References 2 publications

Structural, Electrochemical, and Photophysical Properties of a Molecular Shuttle Attached to an Acid-Terminated Self-Assembled Monolayer

Structural, Electrochemical, and Photophysical Properties of a Molecular Shuttle Attached to an Acid-Terminated Self-Assembled Monolayer

Self‐Assembled Monolayers on Electrodes

Electron Transfer Reactivity Patterns at Chemically Modified Electrodes: Fundamentals and Application to the Optimization of Redox Recycling Amplification Systems

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