Self-induced “electroclick” immobilization of a copper complex onto self-assembled monolayers on a gold electrode

Gomila, Antoine; Poul, Nicolas Le; Cosquer, Nathalie; Kerbaol, Jean-Michel; Noël, Jean‐Marc; Reddy, M. Thirupalu; Jabin, Ivan; Reinaud, Olivia; Conan, Françoise; Mest, Yves Le

doi:10.1039/c0dt01093f

Cited by 17 publications

(20 citation statements)

References 35 publications

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“…We have recently described a novel strategy for the immobilization of diverse functional objects on SAMs of azidoundecanethiol grafted on gold electrodes [26]. The procedure consists in two steps (Scheme 1): (i) a prefunctionalization of a 6TIPSeBMPPA generic platform (TIPS = triisopropylsilyl, eBMPPA = ethynyl-bis(methylpyridyl)propargylamine) by a molecular object of interest (R) through a Copper catalysed Azide-Alkyne Cycloaddition (CuAAC click reaction); (ii) an immobilization in aqueous media onto an azido-alkane modified gold electrode by using the self-induced electroclick approach [27] (Scheme 1). As preliminary trials, two different molecular objects were attached: one bearing a phenylpropyl (R=PhPr) group as a refering non-redox system, and the other a ferrocenylmethyl (R=FcMe) unit as an electrochemical probe [26].…”

Section: Introductionmentioning

confidence: 99%

Electron transfer properties of mono- and diferrocenyl based Cu complexes attached as self-assembled monolayers on gold electrodes by “self-induced” electroclick

Orain

Poul

Mest

et al. 2013

Journal of Electroanalytical Chemistry

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Two new Cu complexes bearing a 6-ethynyl bis-(methyl-pyridyl)amine (6eBMPA) moiety, as an electroclickable function linked to a ferrocenylbased triazolyl arm (ligands 3 and 4) have been synthetized and characterized by UV-Visible, EPR spectroscopies and cyclic voltammetry in acetonitrile. Two different spacer groups between the terminal ferrocene and the triazolyl group were inserted: an hexyl chain in the case of the complex Cu-3, an ethenyl-bridged diferrocenyl system for the complex Cu-4. The monoelectronic oxidation of the diferrocenyl species yields a stable mixed-valence complex. NIR-Visible spectroscopic studies show a moderate interaction between ferrocenyl units (class II according to the Robin-Day classification). The immobilization of these systems as SAMs on an azidoundecanethiol modified gold electrode has been successfully operated by using the "self-induced electroclick" procedure. The voltammetric characterization of the surface-tagged Cu complexes indicates that good surface coverage was achieved, with moderately fast electron-transfer reaction between the electrode and the redox active immobilized systems (k 0 (Cu) = 2-4 s −1 , k 0 (Fc) = 20-90 s −1). Remarkably, the rate of charge transport is significantly controlled by the nature of the spacer on the ferrocenyl triazole arm.

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Section: Introductionmentioning

confidence: 99%

Electron transfer properties of mono- and diferrocenyl based Cu complexes attached as self-assembled monolayers on gold electrodes by “self-induced” electroclick

Orain

Poul

Mest

et al. 2013

Journal of Electroanalytical Chemistry

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“…[22] The complexes were grafted by cycling between 0.60 and À0.20 V with a 3 min hold at À0.20 V between each cycle in a 50 mm solution of [Cu(6)] or [Cu(7)] in H 2 O with KNO 3 as the supporting electrolyte under an atmosphere of N 2 . As shown in Figure 2A for the [Cu(7)] complex, the increase in the cathodic current intensity at + 0.45 V (Fc) and À0.10 V (Cu) with cycling indicates that effective immobilisation of the complex has occurred on the electrode surface.…”

Section: Resultsmentioning

confidence: 99%

“…[22] In our report on that work we emphasised the concept of a self-induced electroclick reaction, which allows the direct grafting of the Cu-TMPA complex in a simple electrochemical step. In this work we show that this concept can be extended to the surface immobilisation of diverse objects (R in Schemes 1 and 2).…”

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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“…A variant of the SAM electroclick functionalization has been extensively developed by the group of Le Mest where Cu(II) ions were directly complexed to clickable molecules, allowing their ''self-induced'' electroclick reticulation on SAMs (Fig. 14) [346,347]. This surface immobilization of copper complexes lead to tunable electron transfer and electrocatalytic activity [348,349].…”

Section: Electroclick On Monolayersmentioning

confidence: 99%

“…In this system, electroclick was used to lock the polyrotaxane geometry, allowing their spontaneous Figure 14 Self-induced electroclick chemistry. Rather than using potentially bio-disturbing free Cu(II) ions in solution, copper ions are trapped on the functional molecules to be clicked [346,347]. self-assembly by non-covalent interactions.…”

Section: Electroclick As a Buildup Stimulus For Polymer Platformsmentioning

confidence: 99%

Electrochemical nanoarchitectonics and layer-by-layer assembly: From basics to future

et al. 2015

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No. of Pages 30 2 G. Rydzek et al. SummaryDuring the last few decades, electrochemistry and electrode modification have seen a tremendous fall off in creativity with the emergence of the nanoarchitectonic-based layerby-layer (LbL) film deposition technique. An unprecedented variety of building blocks can be immobilized on surfaces, leading to progress in several fields including sensing, electrochromic, electro-responsive and energy devices. This review describes the state of the art of electrochemical devices based on LbL assemblies, with a focus on supercapacitors, biosensors, and electroresponsive LbL such as electrodissolution/electroswelling of coatings. Recently, electrochemistry has also been used as an ''active trigger'' to induce the formation of films by covalent coupling, leading to new nanoarchitectonic approaches beyond the LbL strategy. These emerging electro-coupling reactions, including electroclick and carbazole chemistry, open new perspectives toward architecture and patterning of functional films and are extensively reviewed.

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Self-induced “electroclick” immobilization of a copper complex onto self-assembled monolayers on a gold electrode

Cited by 17 publications

References 35 publications

Electron transfer properties of mono- and diferrocenyl based Cu complexes attached as self-assembled monolayers on gold electrodes by “self-induced” electroclick

Electron transfer properties of mono- and diferrocenyl based Cu complexes attached as self-assembled monolayers on gold electrodes by “self-induced” electroclick

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

Electrochemical nanoarchitectonics and layer-by-layer assembly: From basics to future

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