Electrochemical activation of halogen bonding

International audienceIn the past, noncovalent interactions have been extensively studied by electrochemical methods. In this context, halogen bonding (XB) has been a long-time overlooked item in the toolbox of supramolecular chemistry. The article is treating electrochemical activation of XB in solution and at the solid–liquid interface. Key principles and recent work on the use of electrochemistry as a tool for detecting and controlling XB are reported. Different types of redox-switching XB are identified in the context of molecular recognition and detection. First evidence for XB promoted electron transfer reactions involving the activation of covalent bonds represents a completely new and emerging domain, ripe for exploration

Asymmetric and Anharmonic Electrode Kinetics: Evaluation of a Model for Electron Transfer with Concerted Rupture of Weak, Inner Shell Interactions

A surface-integrated form of the widely used (anharmonic) Lennard-Jones 12–6 interaction potential, the Lennard-Jones 9–3 potential, is used to develop a quadratic activation/driving force relationship that gives rise to asymmetric Tafel plots for electron transfer occurring with simultaneous interaction rupture. The Tafel plots are shown to exhibit linearity over a wide potential range, depending on the ratio of the Gibbs interaction well to the solvent reorganisation free energy. The fit of the model to experimental data for a ferrocene-based self-assembled monolayer (SAM) bathed by aqueous perchloric acid suggests ion pairing between ferricenium and perchlorate ions. This crude and primitive model readily enables experimentalists to obtain a parametric understanding of the physicochemical dynamics underpinning interaction rupture in concert with electron transfer, which may empower routes to improve the efficiency of a plethora of topical electrochemical technologies

Single step synthesis of an ethynylferrocenyl-[4]-ferrocenophane

International audienceA single step preparation of a novel [4]-ferrocenophane containing an ethynyl-ferrocene directly connectedto the unsaturated heteroannular bridge starting from 1,10-diformyl-ferrocene is reported. Thesuggested mechanism involves the reaction of water with the unstable diethynyl-ferrocene intermediate.The crystallographic structure of this multi-functional molecule has been resolved

Halogen bonding effect on electrochemical anion oxidation in ionic liquids †

International audienceThree Ionic liquids (ILs) based on an imidazolium core have been compared and used as solvents for the oxidation of various anions. Electrochemical experiments as well as NMR titrations and X-ray diffraction analyses unambiguously confirm the crucial role of non-covalent halogen bonding on the oxidation potentials and consequently the electrochemical window of the respective ILs

Synthesis and electrochemical behaviour of new electroreducible amphiphilic saccharide derivatives

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Electrochemical behaviour of new electroreducible amphiphilic saccharide derivatives II: Electroreduction in protic media

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Adsorption of Glycosidic Surfactants at the Mercury Electrode

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Switching On/Off the Chemisorption of Thiocticbased Self-Assembled Monolayers on Gold by Applying a Moderate Cathodic/Anodic Potential

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Synthesis and characterization of oligonucleotide conjugates bearing electroactive labels

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