Ferrocenyl Oligo(phenylene‐vinylene) Thiols for the Construction of Self‐Assembled Monolayers

Amatore, Christian; Gazard, Stephen; Maisonhaute, Emmanuel; Pebay, Cécile; Schöllhorn, Bernd; Syssa-Magalé, Jean-Laurent; Wadhawan, Jay D.

doi:10.1002/ejic.200700266

Cited by 16 publications

(19 citation statements)

References 30 publications

(20 reference statements)

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“…[50,69] The synthesis of the novel bisferrocene thiol 1 will be published elsewhere. [50] SAM formation (see below) was performed with chloroform (HPLC grade, Acros) for 1-3 or ethanol (HPLC grade, Fischer Scientific) for 4 and 5. These solvents were used without further purification.…”

Section: Methodsmentioning

confidence: 99%

“…[45,48,49] These deviations from ideality are consistent with the literature [20,33] and diminish if larger electrodes are used. [50] Nevertheless, the above thermodynamic effects and deviations from nonideal behavior may be considered irrelevant in the scope of our present work if they are not concerted with the molecular reorganization of the individual ferrocene centers upon electron transfer. We now turn to quantification of the electron-transfer kinetics.…”

Section: Redmentioning

confidence: 98%

“…This unusual behavior has been confirmed in solution for synthetic precursors of 1, and is similar to what was reported previously for polyvinylferrocenes and carotenoids. [50][51][52][53][54][55][56][57] For such long conjugated two-center systems, the charge is delocalized over the whole molecule in the monocation obtained after a first electron transfer. Hence, the solvent stabilization is very weak.…”

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confidence: 99%

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Ultrafast Voltammetry for Probing Interfacial Electron Transfer in Molecular Wires

et al. 2007

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Electron transfer inside self-assembled monolayers made from complex redox-active oligophenylenevinylene molecular wires is examined by ultrafast cyclic voltammetry. Rate constants above 10(6) s(-1) are measured when the electroactive moieties are easily accessible to counterions from the electrolyte. These counterion movements are necessary to compensate the local charge created upon electron transfer. Conversely, if the redox center is buried within long hydrophobic diluents, the counterion movement towards the redox entity becomes rate limiting, thus drastically altering the rate magnitude and its physical meaning. This change in the mechanism is examined both for superexchange or when one electron-hopping step is involved.

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Section: Methodsmentioning

confidence: 99%

Section: Redmentioning

confidence: 98%

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confidence: 99%

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Ultrafast Voltammetry for Probing Interfacial Electron Transfer in Molecular Wires

et al. 2007

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“…Ultrafast voltammetry has been used to measure very large (10 6 s −1 ) rate constants across oligophenylenevinylene and other bridges to coordinated ferrocene moieties. (33,34) As shown in Figure 5, these systems show well-defined voltammograms even at megavolt per second scan rates. A key finding of this work is that the movement of the charge-compensating counterions required for electroneutrality can significantly influence the switching rate.…”

Section: Adsorbates and Interfacial Processesmentioning

confidence: 99%

Ultrafast Electrochemical TechniquesUpdate based on the original article by Robert J. Forster, Encyclopedia of Analytical Chemistry , © 2000, John Wiley & Sons, Ltd.

Mallon

Keyes

Forster

2013

Encyclopedia of Analytical Chemistry

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Ultrafast electrochemical techniques provide information about the kinetics and thermodynamics of redox processes that occur at microsecond to nanosecond timescales. This short timescale is achieved either by making very rapid transient measurements or by using ultrasmall probes to achieve very high rates of diffusion under steady‐state conditions. Micro‐ and nanoelectrodes, i.e., electrodes with critical dimensions in the micrometer to nanometer range, play pivotal roles in both approaches. Electrochemistry has several advantages over spectroscopy in that it provides direct information about electron transfer and coupled chemical reactions. Here, we discuss the key factors that influence the ability to make short timescale measurements using dynamic and steady‐state approaches, as well as applications ranging from heterogeneous and homogeneous electron transfer dynamics to analytical applications.

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“…Among the different strategies for immobilisation (polymeric, [4] layer-by-layer [5] ), the self-assembly of monolayers (SAMs) by thiolate chemisorption on metallic surfaces is undoubtedly the most popular because it offers the advantage of yielding well-organised and controlled modified surfaces relatively easily. [6] Beyond the fundamental aspects of electron-transfer kinetics and surface self-organisation, [7][8][9][10] this approach has led to the direct immobilisation of a vast number of terminal active groups with specific properties. [6,11] However, the main drawback remains the lack of versatility.…”

Section: Introductionmentioning

confidence: 99%

A Generic Platform for the Addressable Functionalisation of Electrode Surfaces through Self‐Induced “Electroclick”

Orain

Poul

Gomila

et al. 2011

Chemistry A European J

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A novel and general strategy for the immobilisation of functional objects onto electrodes is described. The concept is based on the addition of two pendant ethynyl groups onto a bis(pyridyl)amine derivative, which acts as a molecular platform. This platform is pre-functionalised with an N(3)-tagged object of interest by Huisgen cycloaddition to one of the ethynyl groups in biphasic conditions. Hence, when complexed by Cu(II) , this molecular-object holder can be immobilised, by a "self-induced electroclick", through the second ethynyl group onto N(3)-alkanethiol self-assembled monolayers on a gold electrode. Two different functional groups, a redox innocent ((CH(2))(3)-Ph) and an electrochemical probe (ferrocene), were immobilised by following this strategy. The in situ electrochemical grafting showed, for both systems, that the kinetics of immobilisation is fast. The voltammetric characterisation of the surface-tagged functionalised copper complexes indicated that a good surface coverage was achieved and that a moderately fast electron-transfer reaction occurs. Remarkably, in the case of the redox-active ferrocenyl-immobilised system, the electrochemical response highlighted the involvement of the copper ion of the platform in the kinetics of the electron transfer to the ferrocene moiety. This platform is a promising candidate for applications in surface addressing in areas as diverse as biology and materials.

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Ferrocenyl Oligo(phenylene‐vinylene) Thiols for the Construction of Self‐Assembled Monolayers

Cited by 16 publications

References 30 publications

Ultrafast Voltammetry for Probing Interfacial Electron Transfer in Molecular Wires

Ultrafast Voltammetry for Probing Interfacial Electron Transfer in Molecular Wires

Ultrafast Electrochemical TechniquesUpdate based on the original article by Robert J. Forster, Encyclopedia of Analytical Chemistry , © 2000, John Wiley & Sons, Ltd.

A Generic Platform for the Addressable Functionalisation of Electrode Surfaces through Self‐Induced “Electroclick”

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