Pierre Audebert

s-Tetrazines as Building Blocks for New Functional Molecules and Molecular Materials

4. Physical Chemistry of Tetrazines 3303 4.1. Electrochemistry of Tetrazines 3303 4.2. Photophysical Properties of Simple Tetrazines 3305 4.3. Computational Chemistry on Tetrazines 3307 5. Applications of Tetrazines 3309 5.1. Energetic Materials from Tetrazines 3309 5.2. NLO-phores with Tetrazine 3309 5.3. Active Polymers Including Tetrazines 3309 5.4. Supermolecular Tetrazines and Supramolecular Applications 3310

Synthesis of new substituted tetrazines: electrochemical and spectroscopic properties

Original tetrazines substituted by heterocyclic rings have been prepared. Their syntheses, as well as their electrochemical and spectroscopic features, are described. Calculations have also been made on the cation radicals, anion radicals and neutral compounds and are in correct agreement with the experimental results. All compounds are electroactive, both in oxidation and reduction, and display two absorption bands in the UV and visible regions of the spectrum. Reduction potentials and maximum wavelengths are correlated with the electron-rich character of the heterocyclic substituent on the tetrazine ring. None of these compounds gives good quality polymers upon electro-oxidation, which was unexpected, especially for the bis(2-pyrrolyl) tetrazine. This latter result can be explained by the occurrence of a self-deprotonation equilibrium in the cation radical.

Synthesis and electrochemical polymerization of bis-dithienyl cyclophane

Functionalized compressed ring cyclophanes are interesting oligomers because such compounds may provide as interchain connections or recombining fluorescent center when they are polymerized into a conducting polymer. The synthesis and the electro-oxidation of bis-dithienyl cyclophane are reported along with the main electrochemical characteristics of the resulting polymer.

Stable Solution‐Processed Molecular n‐Channel Organic Field‐Effect Transistors

A new solution-processable small-molecule containing electron-poor naphthalene diimide and tetrazine moieties has been synthesized. The optimized spin-coated n-channel OFETs on glass substrate shows electron mobility value up to 0.15 cm(2) V(-1) s(-1) . Inkjet-printed OFETs are fabricated in ambient atmosphere on flexible plastic substrates, which exhibits an electron mobility value up to 0.17 cm(2) V(-1) s(-1) and also shows excellent environmental and operational stability.

Behaviour of some poly(pyrrole-anthraquinone) films in DMSO electrolytes

Abstract Several films of poly(pyrrole-anthraquinone) have been prepared by the electropolymerization in organic media of anthraquinones adequately substituted by some N-alkylpyrroles. These films have been studied mainly by electrochemical methods in DMSO with either TEAFB or LiClO4 as the supporting salt. Bonded anthraquinones can be reversibly reduced to their radical anions or dianions with a fair yield, except on slow or prolonged cycling where the protonation effect modifies this behaviour. Spectroelectrochemical studies confirm these facts and additionally allow the probable complex formations in fully reduced films to be detected.

White Fluorescence from Core–Shell Silica Nanoparticles†

Into the white: Encapsulation of a naphthalimide moiety in the core of silica nanoparticles afforded nanospheres with a strong green excimeric emission. Together with the blue emission of the monomeric naphthalimide and the yellow fluorescence of the tetrazine acceptor on the outer shell, the added contributions provide intense white fluorescence upon 330 nm UV excitation.

Synthesis and electrochemical polymerization of new oligothiophene functionalized fluorocyclophanes

New oligothiophene functionalized fluorocyclophanes have been prepared and electropolymerized. The resulting polymers display the classical electroactivity of polythiophenes, showing that the cyclophane ring allows the charge to flow in the polymer. The charge transfer has been shown to be rather similar to that in a functionalized polythiophene, than that in a pendent group polymer.

Preparations and Characterizations of Luminescent Two Dimensional Organic-inorganic Perovskite Semiconductors

This article reviews the synthesis, structural and optical characterizations of some novel luminescent two dimensional organic-inorganic perovskite (2DOIP) semiconductors. These 2DOIP semiconductors show a self-assembled nano-layered structure, having the electronic structure of multi-quantum wells. 2DOIP thin layers and nanoparticles have been prepared through different methods. The structures of the 2DOIP semiconductors are characterized by atomic force microscopy and X-ray diffraction. The optical properties of the 2DOIP semiconductors are characterized from absorption and photoluminescence spectra measured at room and low temperatures. Influences of different components, in particular the organic parts, on the structural and optical properties of the 2DOIP semiconductors are discussed.

Electrochemical Monitoring of the Fluorescence Emission of Tetrazine and Bodipy Dyes Using Total Internal Reflection Fluorescence Microscopy Coupled to Electrochemistry

A very sensitive technique where an electrochemical cell is coupled to a total internal reflection fluorescence microscopy setup is described and applied for the first time to the electrochemical monitoring of the fluorescence of organic dyes in solution. It is shown that this setup basically allows both spatial and time resolution for the recorded fluorescence signal as a function of the electrode potential: indeed the variations of the emission intensity are recorded within the diffusion layer for a classical cyclic voltammetry or chronoamperometry experiment inducing the redox conversion of an emissive form into a non emissive one (and conversely). Simultaneously, the variations of the emissive state lifetime are measured to discriminate between a mechanism involving only the conversion into a non emissive form from one involving a quenching between the emitter and the electrogenerated species. The results concerning the investigation of the electrochemical monitoring of the fluorescence properties for two types of original dyes are presented, demonstrating the possibility to switch on and off the emission in a fully reversible way and to investigate in depth the mechanisms associated to this switch.

Fast scan rate cyclic voltammetry for conducting polymers electropolymerized on ultramicroelectrodes

With the aim of showing the possibility of obtaining fast kinetic information about the redox behaviour of conducting polymer films we have examined three classical polymers in the most widely studied families: polyaniline, poly(3,4-dimethylpyrrole) and poly(3-methylthiophene) under conditions in which they are usually studied. The dependence on the scan rate of peak potentials and currents was analysed and compared