An innovative method for controlled synthesis of bicomponent monolayer films obtained by reduction of diazonium.

This study presents a novel method based on the electrochemical co-reduction of two aryldiazonium salts, enabling the synthesis of controlled two-component monolayer thin films on carbon in a single step. By introducing a 12-carbon alkyl chain as a spacer between the aryldiazonium function and the functional group, precise control over film thickness and composition was achieved. The alkyl chain effectively standardizes the reduction potential, enabling the equalization of reactivity and precise stoichiometric control. Experimental results from spectroscopic, electrochemical, and X-ray photoelectron spectroscopy analyses validate the effectiveness of the method in controlling the composition of the mixed layers.

Highly Reactive Diazenyl Radical Species Evidenced during Aryldiazonium Electroreduction.

We report the experimental reassessment of the widely admitted concerted reduction mechanism for diazonium electroreduction. Ultrafast cyclic voltammetry was exploited to demonstrate the existence of a stepwise pathway, and real-time spectroelectrochemistry experiments allowed visualization of the spectral signature of an evolution product of the phenyldiazenyl radical intermediate. Unambiguous identification of the diazenyl species was achieved by radical trapping followed by X-ray structure resolution. The electrochemical generation of this transient under intermediate energetic conditions calls into question our comprehension of the layer structuration when surface modification is achieved via the diazonium electrografting technique as this azo-containing intermediate could be responsible for the systematic presence of azo bridges in nanometric films.

No more compromise: a facile route towards functionalized surfaces with stable monolayers.

The results reported in this study clearly show that it is possible to easily control the formation of a functional monolayer by spontaneous reduction of an aryldiazonium salt on gold in a single step, mimicking the SAM technique.

From Monolayer to Multilayer: Perylenediimide Diazonium Derivative Acting Either as a Growth Inhibitor or a Growth Enhancer.

Fine control of electrografting kinetics of diazonium salts is of paramount importance, particularly when considering the application of diazoniums for the fabrication of 2D nanomaterials. In this work, we develop controlled grafting of a perylenediimide (PDI) moiety separated with a 12-carbon aliphatic chain from aryldiazonium. The particular design of the diazonium cation synthesized for this study allows for fine tuning of the surface coverage by simple adjustment of the applied potential. Indeed, according to the potential imposed at the working electrode, the PDI moiety can either enhance the charge propagation within the growing layer or consume the diazonium salt in the bulk solution via redox cross-reaction. With this approach, the surface functionalization can be restricted to a monolayer or a multilayer in a robust and elegant manner, obeying Langmuir or first-order kinetics of electrografting, respectively. The experimental observations are supported with in situ spectroelectrochemical investigations aimed to differentiate the reduction of PDI moieties in the deposited layer and the bulk solution. A tentative mechanistic scheme is proposed, and numerical simulations are undertaken to rationalize the data.

Capacitive Impedance for Following In-Situ Grafting Kinetics of Diazonium Salts.

A new method to follow in-situ grafting kinetics of diazonium compounds based on imposing small amplitude high frequency AC oscillations at grafting potential, is outlined. This enables the time-resolved measurements of capacitive impedance concomitantly with the growth of the organic layer at the working electrode. The impedance values were quantitatively correlated with the ex-situ (from voltammograms) and in-situ (from quartz crystal microbalance) measured surface coverages, providing a validation of the new methodology. The versatility of the developed approach was demonstrated on the grafting via reduction of 4-nitrobenzenediazonium on Au and glassy carbon (GC) substrates and via deposition of in-situ generated diazonium salts from 1-aminoanthraquinone and 4-ferrocenylaniline on GC. The capacitive impedance measurements are simple, fast, and non-destructive, making it an appealing methodology for an exploration of grafting kinetics of a wide range of diazonium salts.

Supramolecular chemistry of helical foldamers at the solid-liquid interface: self-assembled monolayers and anion recognition.

The synthesis of a redox-active helical foldamer and its immobilization onto a gold electrode are described. These large molecular architectures are grafted in a reproducible manner and provide foldamer-based self-assembled monolayers displaying recognition properties.

Redox-controlled hybridization of helical foldamers.

Tetrathiafulvalene redox units were grafted at both extremities of an oligopyridine-dicarboxamide foldamer through a straightforward copper-catalyzed azide-alkyne cycloaddition. The present work demonstrates that the hybridization equilibrium of foldamers can be tuned through redox stimulations.

Controlled diazonium electrografting driven by overpotential reduction: a general strategy to prepare ultrathin layers.

A global and extremely simple strategy to prepare a covalently attached monolayered organic film on a carbon surface is presented. The approach is centered on the strict control of the radical polymerization traditionally observed when aryldiazonium salts are reduced. By exploiting the reductive properties of superoxide ions generated from atmospheric dioxygen at the grafting potential, the diazonium concentration is drastically lowered at the substrate/solution interface, resulting in the formation of ultrathin films. As the presented approach does not require any specific synthesis or any redox mediator addition, and is only diffusion controlled by the dissolved dioxygen, it is suitable for the preparation of a large range of functional surfaces on the nanometric scale.

Click Chemistry: A Versatile Method for Tuning the Composition of Mixed Organic Layers Obtained by Reduction of Diazonium Cations.

Postfunctionalization of glassy carbon electrodes previously modified by reduction of 4-azidobenzenediazonium was exploited to conveniently synthesize controlled mixed organic layers. Huisgen 1,3-dipolar cycloaddition was used to anchor functional entities to azide platform. By this way, ((4-ethynylphenyl)carbamoyl)ferrocene (ϕ-Fc) was coimmobilized with a set of acetylene derivatives: 1-ethynyl-4-nitrobenzene (ϕ-NO2), 4-ethynylaniline (ϕ-NH2) or ethylnylbenzene (ϕ). The composition of the resulting organic layers was tuned by adjusting the acetylene derivatives ratio in the postfunctionalization binary solution. Electronic properties of the substituents beared by the aromatic rings were found to have a strong impact on the cycloaddition kinetics toward the confined azide moieties. From this study, rules to prepare finely tuned bifunctional organic layers can be anticipated.

Thienylene vinylene dimerization: from solution to self-assembled monolayer on gold.

The electrochemical and spectroelectrochemical studies of thienylene vinylene (TV) derivatives in the immobilized state are compared with the ones obtained in solution. The results highlight the exaltation of the dimerization process onto TV-based self-assembled monolayers, in which the π interaction is maintained even after 75% dilution.

Host-guest complexation of [60]fullerenes and porphyrins enabled by "click chemistry".

Herein the synthesis, characterization, and organization of a first-generation dendritic fulleropyrrolidine bearing two pending porphyrins are reported. Both the dendron and the fullerene derivatives were synthesized by Cu(I) -catalyzed alkyne-azide cycloaddition (CuAAC). The electron-donor-acceptor conjugate possesses a shape that allows the formation of supramolecular complexes by encapsulation of C60 within the jaws of the two porphyrins of another molecule. The interactions between the two photoactive units (i.e., C60 and Zn-porphyrin) were confirmed by cyclic voltammetry as well as by steady-state and time-resolved spectroscopy. For example, a shift of about 85 mV was found for the first reduction of C60 in the electron-donor-acceptor conjugate compared with the parent molecules, which indicates that C60 is included in the jaws of the porphyrin. The fulleropyrrolidine compound exhibits a rich polymorphism, which was corroborated by AFM and SEM. In particular, it was found to form supramolecular fibrils when deposited on substrates. The morphology of the fibrils suggests that they are formed by several rows of fullerene-porphyrin complexes.

Electrochemical transduction on self-assembled monolayers: are covalent links essential?

Electrochemical transduction without covalent links between redox and complexant units in a complexing self-assembled monolayer has been established. The results demonstrate that transduction depends on the crown ether/ferrocene ratio and appears to be tunable.

Amino acid derivatives of perylenediimide and their N-H···O peptide bond dipoles-templated solid state assembly into stacks.

A methodology is proposed to provide direct access in good yields to peptide residues-appended perylenediimides PDI-(Cl(4))-[Gly-Ala(OEt)](2), 2a, PDI-(Cl(4))-[Gly-Val(OEt)](2), 2b and PDI-(Cl(4))-[Gly-Gly(OEt)](2), 2c from a generic perylenediimide (PDI) platform symmetrically functionalized with carboxylic acids at the imide sites, PDI-(Cl(4))-[Gly(OH)](2), 1. The latter is obtained in good purity by a non classical two-steps route avoiding the many, notoriously cumbersome successive chromatography steps typical of PDI chemistry, and including a single final purification allowing to crystallize the water soluble pure diacid 1, of great interest in its own right for further developments in a variety of fields. Then, the synthesis, crystallization and analysis of the crystal structures of 2a and 2b reveal a common pattern of self-assembly of the outer peptide residues based on collections of parallel N-H···O peptidic hydrogen bonds running alongside stacks where the constraints imposed upon on the inner PDI skeletons by long range interaction of these parallel electric dipoles reduce the dihedral angles around the bay regions by as much as 11% down to 32°.

Intermolecular interactions in self-assembled monolayers of tetrathiafulvalene derivatives.

The elaboration of mixed self-assembled monolayers (SAMs) of tetrathiafulvalene derivatives allows the modulation of intermolecular interactions and provides evidence of segregated distribution of redox centers.

Versatile functionalization of nanoelectrodes by oligonucleotides via pyrrole electrochemistry.

Surface modification at the nanometer scale is a challenge for the future of molecular electronics. In particular, the precise anchoring and electrical addressing of biological scaffolds such as complex DNA nanonetworks is of importance for generating bio-directed assemblies of nano-objects for nanocircuit purposes. Herein, we consider the individual modification of nanoelectrodes with different oligonucleotide sequences by an electrochemically driven co-polymerization process of pyrrole and modified oligonucleotide sequences bearing pyrrole monomers. We demonstrate that this one-step technique presents the advantages of simplicity, localization of surface modification, mechanical, biological and chemical stability of the coatings, and high lateral resolution.

Phase segregation on electroactive self-assembled monolayers: a numerical approach for describing lateral interactions between redox centers.

A numerical method is proposed in order to differentiate a random distribution from a phase segregation of redox centers on (mixed) SAMs. This approach is compared to Laviron's interactions model and voltammetric data of nitroxylalkanethiolate SAMs.

Hierarchical functionalisation of single-wall carbon nanotubes with DNA through positively charged pyrene.

A simple and efficient method to link reversibly DNA to SWNTs via electrostatic interaction is reported. The DNA/nanotube hybrids are characterised by a combination of gel electrophoresis and AFM.

Redox and ion-exchange properties in surface-tethered DNA-conducting polymers.

A poly(cyclopentadithiophene) matrix modified by DNA covalently fixed to the surface has been designed to study the redox and ion-exchange properties in surface-tethered DNA-conducting polymers. Voltammetric investigations show an improvement in conductivity, originating from DNA modification, probably due to changes in charged-density and size of dopant species. Cyclic voltammetry with concomitant QCM measurements indicate that the mass changes are consistent with an ejection of Na(+) cations associated to the anionic phosphate groups, attesting a DNA contribution to the p-doping process. So, in contrast to the classic doping patterns, the p-doping process of surface-tethered DNA-copolymer exhibits a cation-controlled transport mechanism. Impedimetric investigations indicate that for long enough DNA target sequence, nucleic acid preserves certain flexibility and is involved in the p-doping process through a diffusion-like motion. These results give new opportunities for genesensors development and for a better understanding of bioactive conducting surfaces.