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  • P. Galiyeva, H. Alem, H. Rinnert, L. Balan, S. Blanchard, G. Medjahdi, B. Uralbekov, and R. Schneider, “Highly fluorescent, color tunable and magnetic quaternary Ag–In–Mn–Zn–S quantum dots”, Inorganic Chemistry Frontiers, vol. 6, no. 6, p. 1422-1431, Jun. 2019.
    Abstract: Mn-Doped quantum dots (QDs) are of high interest for numerous applications like solar cells, optoelectronics, optosensing, or bioimaging. Here, we report the preparation of quaternary (AgInS2)x(MnS)y(ZnS)1−x−y QDs, thereafter noted Mn : AIZS via a thermally induced decomposition of Ag, In, Zn and Mn precursors in the presence of oleylamine and dodecanethiol. The Mn : AIZS QDs have an average diameter of 3.5 nm and their XRD patterns can be indexed with the orthorhombic phase of AgInS2. The incorporation of Mn2+ ions in the AIZS crystal lattice results in a red-shift of the photoluminescence (PL) emission maximum depending on the Mn2+ content. The PL quantum yields decrease upon loading with Mn2+ but remained high (53–31%) until 50% theoretical loading in Mn2+. Steady state, PL excitation and time-resolved PL measurements suggest that Mn2+-dependent trap states are involved in the PL emission. Mn : AIZS QDs exhibit also magnetic properties. In addition, Mn : AIZS QDs can easily be transferred to the aqueous phase using the PMAO amphiphilic polymer without alteration of their optical properties (PL quantum yield up to 51%), revealing their high potential for biological applications.
    Tags: E-POM, POLE 2.

  • Y. Gao, Z. Cao, Z. Han, Q. Zhang, J. Hu, R. Guo, X. He, F. Ding, Q. You, and Y. Zhang, “Synthesis of Azidosphingosine from D-Galactose or L-Arabinose”, Chinese Journal of Organic Chemistry, vol. 39, no. 2, p. 390, 2019.

  • Y. Gao, Z. Cao, Q. Zhang, R. Guo, F. Ding, Q. You, J. Bi, and Y. Zhang, “Total Synthesis of the Proposed Structure of Penasulfate A:l-Arabinose as a Source of Chirality”, Journal of Natural Products, vol. 82, no. 7, p. 1908-1916, Jul. 2019.

  • D. Garnier, A. Mondal, Y. Li, P. Herson, L. - M. Chamoreau, L. Toupet, M. Buron Le Cointe, E. M. B. Moos, F. Breher, and R. Lescouëzec, “Tetranuclear [FeII2FeIII2]2+ molecular switches: [FeII(bik)2(N–)2] spin-crossover complexes containing [FeIII(Tp)(CN)3]– metalloligands as N-donor”, Comptes Rendus Chimie, May 2019.
    Abstract: Three novel mixed valence cyanide-bridged {FeIII2FeII2} square complexes were obtained through the self-assembling of [FeIII(Tp)(CN)3]- or [FeIII(Tp*)(CN)3]− cyanido building blocks with the in situ formed [FeII(bik)2(S)2] complex (Tp = hydrotris (pyrazol-1-yl)borate, Tp* = hydrotris (3,5-dimethyl-pyrazol-1-yl)borate, bik = bis(1-methylimidazol-2-yl)ketone, S = solvent). The structures of these three complexes (2, 3 and 4) are reminiscent of that of our previously published square complex {[FeIII(Tp)(CN)3]2 [FeII(bik)2]2}·[FeIII(Tp)(CN)3]2·18H2O·4CH3OH (1). They consist of cyanide-bridged square dicationic complexes, ClO4− (2 and 3) or BF4− (4) counterions and solvate molecules. The FT-IR cyanide stretching vibrations observed at νCN ≈ 2145–60 cm−1 are typical of {FeIII–CN–FeII} moieties. The investigation of the magnetic properties of 2 reveals the occurrence of spin-crossover centered at T1/2 = 227 K. The χMT variation, ca. 7 cm3 mol−1 K, reflects the complete spin-state change occurring on both {FeII(bik)(–NC)2} moieties (–NC represents the cyanido building blocks). The Slichter–Drickamer model leads to a weak cooperativity factor, Γ = 1.6 kJ mol−1 (with Γ < 2RT1/2), which reflects the gradual spin-state change. This is in agreement with the molecular structure of 2, which does not present significant intermolecular interactions. The calculated enthalpy and entropy variations associated with the spin-state equilibrium are ΔH = 24 kJ mol−1 and ΔS = 105 J K−1 mol−1. In contrast, 3 and 4 show only partial spin-crossover in the accessible temperature range (2–400 K) as the T1/2 are shifted toward higher temperatures (ca. T1/2 > 400 K). Although no photomagnetic effect is observed for 3, compound 4 shows a moderate increase in the magnetization upon irradiation at low temperature. This phenomenon is ascribed to the light-induced excited spin-state trapping (LIESST) effect. Interestingly, the complex 2 also shows a remarkable LIESST effect, which is observed with different laser lights covering the visible and near-infrared range. The resulting χMT value obtained in the photoinduced state suggests the occurrence of a ferromagnetic interaction inside the {FeIII–CN–FeII} units. Résumé Trois nouveaux complexes carrés {FeIII2FeII2} à pont cyanure et à valence mixte ont été obtenus par auto-assemblage des précurseurs cyanurés [FeIII(Tp)(CN)3]− ou [FeIII(Tp*)(CN)3]− et du complexe cationique [FeII(bik)2(S)2] formé in situ (Tp = hydrotris (pyrazol-1-yl)borate, Tp* = hydrotris (3,5-dimethyl-pyrazol-1-yl)borate, bik = bis(1-methylimidazol-2-yl)cétone, S = solvant). Les structures de ces trois complexes (2, 3 et 4) sont similaires à celle du complexe {[FeIII(Tp)(CN)3]2[FeII(bik)2]2}[FeIII(Tp)(CN)3]2·18H2O·4CH3OH (1) préalablement publié. Elles sont constituées de complexes carrés dicationiques à pont cyanure, de contre-ions ClO4− (2 and 3) ou BF4− (4) et de molécules de solvant. Les vibrations d’élongation des cyanures, observée en spectroscopie IR à νCN ≈ 2145–60 cm−1, sont caractéristiques d'unités {FeIII–CN–FeII}. L’étude des propriétés magnétiques de 2 révèle un équilibre de spin centré à T1/2 = 227 K. La variation du produit χMT, ca. 7 cm3 mol−1 K, traduit une conversion de spin complète sur chacune des unités {FeII(bik)(–NC)2} du carré (–NC représente le complexe précurseur cyanuré). L'analyse des données par le modèle de Slichter–Drickamer conduit à un faible facteur de coopérativité, Γ = 1.6 kJ mol−1 K (with Γ < 2RT1/2), en accord avec un changement d’état de spin graduel. Ces données sont en accord avec la structure de 2 qui ne montre pas d'interactions intermoléculaires notables. Les valeurs des variations d'enthalpie et d'entropie associées à la conversion de spin sont ΔH = 24 kJ mol−1 et ΔS = 105 J K−1 mol−1. Au contraire de 2, les composés 3 and 4 présentent seulement une conversion de spin partielle dans le domaine de température exploré (2–400 K), avec des valeurs T1/2 déplacées vers les hautes températures (ca. T1/2 > 400 K). Tandis qu'on n'observe pas d'effet photomagnétique pour 3 et seulement un faible effet dans 4, le composé 2 présente une forte augmentation de son aimantation sous irradiation à basse température. Cet effet est dû au piégeage photo-induit d'un état excité de spin (effet « LIESST », Light-Induced Excited Spin-State Trapping). Il est observé avec différentes sources laser couvrant le spectre visible et le proche infrarouge. Les valeurs de χMT obtenues dans l’état photo-induit suggèrent la présence d'une interaction ferromagnétique au sein de la paire {FeIII–CN–FeII}.
    Tags: ERMMES, POLE 2.

  • M. Girardi, D. Platzer, S. Griveau, F. Bedioui, S. Alves, A. Proust, and S. Blanchard, “Assessing the Electrocatalytic Properties of the Cp*RhIII2+-Polyoxometalate Derivative [H2PW11O39RhIIICp*(OH2)]3– towards CO2 Reduction”, European Journal of Inorganic Chemistry, vol. 2019, no. 3-4, p. 387-393, 2019.
    Abstract: Storage of electricity produced intermittently by renewable energy sources is a societal issue. Besides the use of batteries and supercapacitors, conversion of excess electricity into chemical energy is also actively investigated. The conversion of CO2 to fuel or fuel precursors is an option that requires the use of a catalyst to overcome the high activation energy barrier. Of molecular catalysts, metal complexes with polypyridyl ligands are well represented, among which the [Cp*Rh(bpy)Cl]+ and [M(bpy)(CO)3X] (M = Re, Mn) complexes. As redox non-innocent ligand, the bipyridine ligand is generally involved in the reduction mechanisms. It is thus tempting to replace it by other redox non-innocent ligands such as vacant polyoxometalates (POMs). We have thus prepared [α-H2PW11O39RhIIICp*(OH2)]3– which is closely related to [Cp*RhIII(bpy)Cl]+ by substitution of the monovacant [PW11O39]7– Keggin-type POM for the bipyridine ligand. Its activity towards CO2 reduction has been assessed in acetonitrile in the presence of water. Compared to [Cp*Rh(bpy)Cl]+ that produces formate selectively over CO and H2, the POM derived catalyst favors proton reduction over CO2 reduction.
    Tags: Carbon dioxide fixation, CSOB, E-POM, Non-innocent ligands, POLE 2, POLE 3, Polyoxometalates, Redox chemistry.
    Attachment Full Text PDF 974.1 kb (source)

  • C. Grazon, Y. Si, J. - P. Placial, J. Rieger, R. Méallet-Renault, and G. Clavier, “Core–shell polymeric nanoparticles comprising BODIPY and fluorescein as ultra-bright ratiometric fluorescent pH sensors”, Photochemical & Photobiological Sciences, vol. 18, no. 5, p. 1156-1165, 2019.

  • A. Groué, J. - P. Tranchier, M. - N. Rager, G. Gontard, M. Jean, N. Vanthuyne, H. R. Pearce, A. L. Cooksy, and H. Amouri, “Unique Class of Enantiopure N-Heterocyclic Carbene Half-Sandwich Iridium(III) Complexes with Stable Configurations: Probing Five-Membered versus Six-Membered Iridacycles”, Inorganic Chemistry, vol. 58, no. 5, p. 2930-2933, Mar. 2019.
    Abstract: A unique class of enantiopure N-heterocyclic carbene half-sandwich iridium complexes is reported. These compounds display stable configurations at the metal center, as demonstrated by their chiroptical properties. Remarkably, because of the nature of the naphthalimide molecule, two regioisomers containing five-membered [(R)-2a and (S)-2a] and six-membered [(R)-2b and (S)-2b] iridacycles were obtained. Density functional theory calculations are advanced to rationalize their relative stability.
    Tags: ARC, POLE 1.
    Attachment Full Text PDF 819.3 kb (source)

  • L. Guyon, E. Lepeltier, J. - C. Gimel, B. Calvignac, F. Franconi, N. Lautram, A. Dupont, C. Bourgaux, P. Pigeon, P. Saulnier, G. Jaouen, and C. Passirani, “Importance of Combining Advanced Particle Size Analysis Techniques To Characterize Cell-Penetrating Peptide–Ferrocifen Self-Assemblies”, The Journal of Physical Chemistry Letters, vol. 10, no. 21, p. 6613-6620, Oct. 2019.
    Tags: CHEMBIO, POLE 3.
    Note Note
    <p>doi: 10.1021/acs.jpclett.9b01493</p>

  • A. Harbi, H. Moutaabbid, Y. Li, C. Renero-Lecuna, M. Fialin, Y. Le Godec, S. Benmokhtar, and M. Moutaabbid, “The effect of cation disorder on magnetic properties of new double perovskites La2NixCo1-xMnO6 (x = 0.2–0.8)”, Journal of Alloys and Compounds, vol. 778, p. 105-114, Mar. 2019.
    Abstract: Solid solutions of new double perovskite oxides La2NixCo1-xMnO6 (x = 0.2, 0.25, 0.5, 0.75, 0.8) were synthesized by solid-state reaction method. The X-ray powder diffraction data show that all the compounds crystallize in the monoclinic structure with space group P21/n at room temperature. The elementary composition of the powders was determined by the electron Probe Microanalysis. Raman and IR spectra show strong bands at (520, 650 cm−1) and (426, 600 cm−1) respectively, attributed to the stretching vibration of Ni/Co-O and Mn-O bonds in the structure. The magnetic studies for all the compounds have been performed in both DC and AC magnetic fields in the temperature range from 2 to 300 K. All samples exhibit a main paramagnetic to ferromagnetic (PM-FM) transition between 232 K and 260 K, and their Curie temperature increases rapidly with increasing x values. Three samples with x = 0.2, 0.25 and 0.5 respectively display also a secondary PM-FM transition between 200 K and 208 K. The thermal variation of out of phase component of AC susceptibility presents also frequency-dependent transitions between 65 K and 110 K unfolding the existence of super-paramagnetic mono-domains in all samples. The band gap energy has been calculated and revealing semiconductor behavior for all samples.
    Tags: ERMMES, POLE 2.

  • T. Hautbergue, E. L. Jamin, R. Costantino, S. Tadrist, L. Meneghetti, J. - C. Tabet, L. Debrauwer, I. P. Oswald, and O. Puel, “Combination of Isotope Labeling and Molecular Networking of Tandem Mass Spectrometry Data To Reveal 69 Unknown Metabolites Produced by <i>Penicillium nordicum</i>”, Analytical Chemistry, vol. 91, no. 19, p. 12191-12202, 2019.

  • J. Hendricks, A. Louhichi, V. Metri, R. Fournier, N. Reddy, L. Bouteiller, M. Cloitre, C. Clasen, D. Vlassopoulos, and W.  J. Briels, “Nonmonotonic Stress Relaxation after Cessation of Steady Shear Flow in Supramolecular Assemblies”, Physical Review Letters, vol. 123, no. 21, p. 218003, Nov. 2019.
    Abstract: Stress relaxation upon cessation of shear flow is known to be described by single-mode or multimode monotonic exponential decays. This is considered to be ubiquitous in nature. However, we found that, in some cases, the relaxation becomes anomalous in that an increase in the relaxing stress is observed. Those observations were made for physicochemically very different systems, having in common, however, the presence of self-associating units generating structures at large length scales. The nonmonotonic stress relaxation can be described phenomenologically by a generic model based on a redistribution of energy after the flow has stopped. When broken bonds are reestablished after flow cessation, the released energy is partly used to locally increase the elastic energy by the formation of deformed domains. If shear has induced order such that these elastic domains are partly aligned, the reestablishing of bonds gives rise to an increase of the overall stress.
    Tags: POLYMERES.
    Attachment Full Text PDF 597.7 kb (source)

  • N. Illy, V. Corcé, J. Zimbron, V. Molinié, M. Labourel, G. Tresset, J. Degrouard, M. Salmain, and P. Guégan, “pH-Sensitive Poly(ethylene glycol)/Poly(ethoxyethyl glycidyl ether) Block Copolymers: Synthesis, Characterization, Encapsulation, and Delivery of a Hydrophobic Drug”, Macromolecular Chemistry and Physics, vol. 220, no. 16, p. 1900210, 2019.
    Abstract: Abstract Curcumin is a natural polyphenolic compound known for its numerous pharmacological properties. However, its low water solubility and instability at neutral pH are serious drawbacks preventing its use as an oral drug. Well-defined amphiphilic poly(ethylene glycol)-block-poly(ethoxyethyl glycidyl ether) (PEG-b-PEEGE) block copolymers carrying acid-labile acetal groups are synthesized by anionic ring-opening polymerization and investigated as potential pH-sensitive nano-carriers for delivery of curcumin to cancer cells. The nanoparticles, resulting from copolymer self-assembly in aqueous media, are characterized by dynamic light scattering and cryo-transmission electron microscopy. The nanoparticles? stabilities are evaluated in three different phosphate buffers (pH = 7.2, 6.4, and 5.3). The stability decreases at lower pH and a complete disappearance of the nanoparticles is noticed after 4 days at pH 5.3. Curcumin is encapsulated in hydrophobic core of mPEG40-b-PEEGE25 nanoparticles allowing significant enhancements of curcumin solubility in water and lifetime at neutral pH. In vitro curcumin release is studied at different pH by UV-spectroscopy and high-performance liquid chromatography (HPLC). The cytotoxicity of curcumin and curcumin encapsulated in micelles is evaluated by cell viability 3-(4,5-Dimethyl-2-thiazolyl)-2,5-diphenyl-2H-tetrazolium bromide (MTT) assay on MDA-MB-231 human breast cancer cells.
    Tags: amphiphilic polyethers, anionic-ring opening polymerization, CHEMBIO, curcumin encapsulation, pH-sensitive copolymers, POLE 3, POLE 4, POLYMERES, self-assembly.
    Attachment Full Text PDF 1.8 Mb (source)
    Note Note
    <p>doi: 10.1002/macp.201900210</p>

  • N. Illy, D. Urayeneza, A. V. Maryasevskaya, L. Michely, S. Boileau, B. Brissault, E. A. Bersenev, D. V. Anokhin, D. A. Ivanov, and J. Penelle, “Synthesis and Solid-State Properties of PolyC3 (Co)polymers Containing (CH2–CH2–C(COOR)2) Repeat Units with Densely Packed Fluorocarbon Lateral Chains”, Macromolecules, vol. 52, no. 23, p. 9199-9207, Dec. 2019.
    Abstract: The synthesis and structural characterization of linear PolyC3 polymers containing trimethylene-1,1-dicarboxylate structural repeat units with C6F13 and C8F17 fluorinated side chains is described for the first time, and their properties were compared with the traditional polyvinyl structures that display the fluorinated chain on every second rather than on every third carbon alongside the backbone. Homopolymers as well as statistical and block copolymers with n-propyl and/or allyl trimethylene-1,1-dicarboxylate blocks have been obtained from PolyC3 precursors containing diallyl trimethylene-1,1-dicarboxylate units, by reacting C6F13–C2H4–SH and C8F17–C2H4–SH thiols with the allyl groups using a thiol–ene post-polymerization modification reaction. Solid-state properties have been investigated by differential scanning calorimetry for all of the (co)polymers and by small-angle X-ray scattering/wide-angle X-ray scattering for the C8F17 homopolymer at several temperatures. The structure of the homopolymer consistently shows a coexistence of two smectic phases at room temperature, which can be identified as SmB and SmC. This coexistence is assumed to arise from the fact that the distances between carboxylic oxygens bonded to the same carbon are very close to the ones between the neighboring carboxylic oxygens alongside the backbone, resulting in two possible ways of packing the pendent fluoroalkyl chains arranged in a hexatic order.
    Tags: POLE 4, POLYMERES.
    Attachment Full Text PDF 2.5 Mb (source)

  • E. L. Jamin, C. Jacques, L. Jourdes, J. - C. Tabet, N. Borotra, S. Bessou-Touya, L. Debrauwer, and H. Duplan, “Identification of lipids of the stratum corneum by high performance thin layer chromatography and mass spectrometry”, European Journal of Mass Spectrometry, vol. 25, no. 3, p. 278-290, 2019.

  • P. Jiao, S. Wang, S. Liang, M. Li, Q. Gao, D. Ji, Y. Chen, H. Li, F. Ran, Y. Zhang, L. Zhang, D. Zhou, and S. Xiao, “Facile preparation and characterization of novel oleanane-type triterpene functionalized β-cyclodextrin conjugates”, Chinese

    Chemical Letters
    , vol. 30, no. 3, p. 690-693, 2019.

  • C. M. Kronfel, C. V. Hernandez, J. P. Frick, L. S. Hernandez, A. Gutu, J. A. Karty, M. N. Boutaghou, D. M. Kehoe, R. B. Cole, and W. M. Schluchter, “CpeF is the bilin lyase that ligates the doubly linked phycoerythrobilin on β-phycoerythrin in the cyanobacterium <i>Fremyella diplosiphon</i>”, Journal of Biological Chemistry, p. jbc.RA118.007221, Jan. 2019.

  • J. Lalande and G. Poli, “Dialogue entre thermodynamique et chimie organique : manipuler avec soin concepts et vocabulaire”, L'Actualité Chimique, no. 437, p. 9-11, 2019.

  • M. Lansalot and J. Rieger, “Polymerization-Induced Self-Assembly”, Macromolecular Rapid Communications, vol. 40, no. 2, p. 1800885, 2019.

  • K. J. Lee, Y. Xiao, E. S. Kim, F. Mathevet, L. Mager, O. Cregut, Frédéric Fages, J. - C. Ribierre, J. W. Wu, and A. D’Aléo, “Donor–Acceptor Distance-Dependent Charge Transfer Dynamics Controlled by Metamaterial Structures”, ACS Photonics, vol. 6, no. 11, p. 2649-2654, Nov. 2019.
    Abstract: The capability to control charge transfer dynamics in a donor–acceptor molecule is important for efficient optoelectronic devices. Charge transfer dynamics is governed by thermodynamics of donor–acceptor charges in a given dielectric environment. Metamaterial structure has been shown to be able to control charge separation and charge recombination processes via nonlocal effect on dielectric permittivity for a fixed donor–acceptor distance organic film. Here, we report the influence of the metamaterial structure on the donor–acceptor distance dependence of the electron transfer process occurring in liquid crystalline organic semiconductor thin films. By examining the charge recombination rate in three different donor–acceptor distances, it is found that the barrier height β increases from 0.084 to 0.137 Å–1 by 63% in the presence of metal-dielectric multilayered metamaterial structures. Based on the Marcus theory on the charge transfer process, we show that a further increase in the driving force for a larger donor–acceptor distance is mainly responsible for the barrier height increase in the presence of a multilayered metamaterial substrate when compared with a glass substrate. This study will provide a significant step forward in enabling more efficient hybrid organic-optoelectronic devices associated with the charge transfer process.
    Tags: POLYMERES.
    Attachment Full Text PDF 1.7 Mb (source)

  • S. H. Z. Lee, F. Chau, S. Top, G. Jaouen, A. Vessières, E. Labbé, and O. Buriez, “New mechanistic insights into osmium-based tamoxifen derivatives”, Electrochimica Acta, vol. 302, p. 130-136, 2019.
    Abstract: The electrochemical behavior of osmociphenol (3, Oc-OH), an organometallic osmium-based anticancer drug candidate, has been investigated by cyclic voltammetry in the absence and presence of lutidine used as a base model. Osmociphenol exhibited spontaneous deprotonation of the phenol function upon oxidation of the osmocene moiety due to its high acidity. In the presence of lutidine, a base-dependent and different electrochemical behavior was observed at low scan rates indicating a second oxidation step leading to the corresponding cationic quinone methide precursor (3b+). However, compared to ruthenocene derivatives, the stability of 3b+ prevented its conversion into quinone methide as the final and stable complex. Despite differences in their oxidative processes, osmociphenol and ruthenociphenol derivatives exhibit similar biological activities.
    Tags: Anti-cancer, Bioorganometallic, CHEMBIO, Cyclic voltammetry, Osmium, POLE 3, Tamoxifen.

  • Y. U. Lee, O. P. M. Gaudin, K. J. Lee, E. Choi, V. Placide, K. Takaishi, T. Muto, P. André, A. Muranaka, M. Uchiyama, F. Mathevet, T. Aoyama, J. W. Wu, A. D’Aléo, and J. - C. Ribierre, “Organic Monolithic Natural Hyperbolic Material”, ACS Photonics, vol. 6, no. 7, p. 1681-1689, Jul. 2019.
    Abstract: Materials with hyperbolic dispersion are the key to a variety of photonic applications involving nanoimaging, hyper-lensing, and spontaneous emission engineering, due to the availability of high k modes. Here we demonstrate that spin-coated polycrystalline organic semiconducting films with a layered molecular packing structure can exhibit a hyperbolic dispersion over a wide spectral range and support the presence of surface excitonic polaritons. This was evidenced from 670 to 920 nm and is related to the negative real part of the dielectric permittivity of the selected quinoidal organic semiconductor. In addition, the accessible high k modes lead to changes in the spontaneous emission decay rate and photoluminescence quantum yield of emitters placed nearby the organic monolithic (composed of only one molecule and not necessitating an alternating multilayer structure) natural hyperbolic material. This study opens a new route toward single-step solution manufacturing of large-area, low-cost, and flexible organic photonic metadevices with hyperbolic dispersion.
    Tags: POLYMERES.
    Attachment Full Text PDF 3.3 Mb (source)

  • L. Lempenauer, G. Lemière, and E. Duñach, “Cyclisation Reactions Involving Alkyl Enol Ethers”, Advanced Synthesis & Catalysis, vol. 361, no. 23, p. 5284-5304, 2019.
    Abstract: Enol ethers are a fascinating product class and valuable building blocks with versatile reactivities and synthetic applications. With the emergence of silyl enol ethers, the chemistry of simple alkyl enol ethers has received less attention and targeted reviews of their chemistry are scarce. Especially intramolecular reactions under participation of an enol ether function have never been specifically surveyed. The construction of cyclic scaffolds is arguably one of the most important and challenging tasks of the organic chemist and intramolecular cyclisations represent the most straight-forward tool to achieve this goal. The potential of enol ether-containing substrates to form oxygenated carbo- and heterocycles is obvious. The purpose of this review is to discuss their particular reactivity and to direct the reader's attention to how their unique properties have been harnessed by organic chemists for the construction of rings.
    Tags: catalysis, cyclisations, enol ethers, intramolecular reactions, Lewis acids, MACO, POLE 1.
    Attachment Full Text PDF 1.1 Mb (source)

  • D. Lesage, S. Mezzache, Y. Gimbert, H. Dossmann, and J. - C. Tabet, “Extended kinetic method and RRKM modeling to reinvestigate proline’s proton affinity and approach the meaning of effective temperature”, European Journal of Mass Spectrometry, p. 146906671882205, Jan. 2019.

  • C. Lévêque, E. Levernier, V. Corcé, L. Fensterbank, M. Malacria, and C. Ollivier, “Photoredox Catalysis, an Opportunity for Sustainable Radical Chemistry”, in Advanced Green Chemistry, vol. Volume 6, World Scientific, 2019, p. 49-121.
    Abstract: The following sections are included: List of Abbreviations Introduction The Photoredox Catalysis as an Alternative Nature as a Source of Inspiration Artificial Redox Photocatalysts Photophysical Properties Principle of Photoredox Catalysis Formation of Carbon Centered Radicals Merging Photoredox and Organometallic Catalysis for Cross-Coupling Reactions Context Radical Trapping by Transition Metals Cobalt Nickel Copper Genesis of the Photoredox/Transition Metal Dual Catalysis: Ruthenium and Palladium Towards Photoredox/Transition Metal Dual Catalysis Processes Processes without Radical Formation: Catalysis of Redox Steps Processes with Radical Formation: Catalysis of Downstream Steps Conclusion Acknowledgments References
    Tags: CHEMBIO, MACO, POLE 1, POLE 3.
    Note Note

  • E. Levernier, V. Corcé, L. - M. Rakotoarison, A. Smith, M. Zhang, S. Ognier, M. Tatoulian, C. Ollivier, and L. Fensterbank, “Cross coupling of alkylsilicates with acyl chlorides via photoredox/nickel dual catalysis: a new synthesis method for ketones”, Organic Chemistry Frontiers, vol. 6, no. 9, p. 1378-1382, Apr. 2019.
    Abstract: Photoredox/nickel dual catalysis using easily oxidized bis-catecholato hypercoordinated silicon derivatives as radical sources and acyl chlorides as electrophiles allows a new method of formation of dialkyl and alkyl-aryl ketones as well as dibenzyl ketones which are less easily accessed. Flow chemistry can be used.
    Tags: CHEMBIO, MACO, POLE 1, POLE 3.
    Attachment Version soumise 654.1 kb (source)

  • H. Li, M. Li, R. Xu, S. Wang, Y. Zhang, L. Zhang, D. Zhou, and S. Xiao, “Synthesis, structure activity relationship and in vitro anti-influenza virus activity of novel polyphenol-pentacyclic triterpene conjugates”, European Journal of Medicinal Chemistry, vol. 163, p. 560-568, 2019.

  • Y. Li, L. Bouteiller, and M. Raynal, “Catalysts Supported by Homochiral Molecular Helices: A New Concept to Implement Asymmetric Amplification in Catalytic Science”, ChemCatChem, vol. 11, no. 21, p. 5212-5226, 2019.
    Abstract: Connecting intrinsically achiral catalytic centers to helical polymers provides a new class of asymmetric catalysts whose selectivity exclusively stems from the chiral environment provided by the helical polymer. Chirality amplification phenomena allow to control the handedness and the helical sense excess of these polymers which in turn dictate the stereochemical direction and the extent of enantioinduction, respectively, obtained in the course of the asymmetric reaction. This minireview is focused on such helical catalysts built either on a covalent or a non-covalent scaffold and for which the handedness is controlled by an asymmetric polymerization reaction, by enantiopure monomers or by chiral additives. The selectivity of catalysts based on a dynamic helical backbone can be tuned by changing the solvent or with additives. The fact that the enantiomeric state of such asymmetric catalysts can be switched in a predictable way is particularly emphasized.
    Tags: asymmetric catalysis, chirality amplification, macromolecular helices, POLYMERES, supramolecular helices, switchable catalysis.
    Attachment Full Text PDF 3.2 Mb (source)

  • Y. Li, X. Caumes, M. Raynal, and L. Bouteiller, “Modulation of catalyst enantioselectivity through reversible assembly of supramolecular helices”, Chemical Communications, vol. 55, no. 15, p. 2162-2165, Feb. 2019.
    Abstract: A multi-configurable catalyst, for which the degree of enantioinduction in successive reactions is varied between 6% ee and 52% ee, is achieved by supporting copper centres at the periphery of supramolecular helices. Precise characterization of the co-assemblies corroborates the relation between helix length and catalyst selectivity.
    Tags: POLYMERES.
    Attachment Full Text PDF 2.6 Mb (source)

  • Y. Li, L. Dubreucq, B. G. Alvarenga, M. Raynal, and L. Bouteiller, “N-Substituted Benzene-1-Urea-3,5-Biscarboxamide (BUBA): Easily Accessible C2-Symmetric Monomers for the Construction of Reversible and Chirally Amplified Helical Assemblies”, Chemistry – A European Journal, vol. 25, no. 45, p. 10650-10661, 2019.
    Abstract: Non-C3-symmetric supramolecular helices are gaining interest for the design of hierarchical assemblies, for the compartmentalisation or the self-assembly of polymer chains and for application in asymmetric catalysis. Herein, N-substituted benzene-1-urea-3,5-biscarboxamide (BUBA) monomers, which consist of one urea and two carbon-connected amide functions linked to an aromatic ring, are introduced as an easily accessible class of C2-symmetric supramolecular synthons. In apolar solvents, BUBA monomers assemble into long helical assemblies by means of hydrogen-bonding and aromatic interactions, as assessed by several analytical techniques. To probe the influence of the urea function, BUBA and related benzene-1,3,5-tricarboxamide (BTA) helical polymers have been compared, in terms of their thermodynamics of formation, stability, reversibility and chiral amplification properties. Similar to BTA, BUBA monomers form long helices reversibly through a highly cooperative mechanism and the helicity of their assemblies is governed by chiral amplification effects. However, precise quantification of their properties reveals that BUBA monomers assemble in a more cooperative manner. Also, chiral amplification operates to a higher extent in BUBA helices, as probed by both sergeants-and-soldiers and majority-rules experiments. Compatibility between urea and amide functions also allows the formation of co-assemblies that incorporate both BUBA and BTA monomers. Importantly, a small amount of chiral BUBA monomers in these co-assemblies is sufficient to obtain single-handed helices; thus paving the way towards the development of functional supramolecular helices.
    Tags: chirality, cooperative effects, helical structures, noncovalent interactions, POLYMERES, self-assembly.
    Attachment Full Text PDF 1.9 Mb (source)

  • S. Liang, M. Li, X. Yu, H. Jin, Y. Zhang, L. Zhang, D. Zhou, and S. Xiao, “Synthesis and structure-activity relationship studies of water-soluble β-cyclodextrin-glycyrrhetinic acid conjugates as potential anti-influenza virus agents”, European Journal of Medicinal Chemistry, vol. 166, p. 328-338, 2019.

  • Y. Liu, J. Oble, and G. Poli, “Switchable selectivity in Pd-catalyzed [3 + 2] annulations of γ-oxy-2-cycloalkenones with 3-oxoglutarates: C–C/C–C vs C–C/O–C bond formation”, Beilstein Journal of Organic Chemistry, vol. 15, no. 1, p. 1107-1115, May 2019.
    Abstract: Beilstein Journal of Organic Chemistry
    Tags: POLE 1, ROCS.
    Attachment Full Text PDF 559.7 kb (source)

  • J. Liu, P. Yu, M. Sollogoub, and Y. Zhang, “Functionalized Cyclodextrins and Their Applications in Biodelivery”, in Handbook of Macrocyclic Supramolecular Assembly, Y. Liu, Y. Chen, and H. - Y. Zhang, Eds. Singapore: Springer Singapore, 2019, p. 1-39.

  • A. Loiseau, V. Asila, G. Boitel-Aullen, M. Lam, M. Salmain, and S. Boujday, “Silver-Based Plasmonic Nanoparticles for and Their Use in Biosensing”, Biosensors, vol. 9, no. 2, p. 78, 2019.
    Abstract: The localized surface plasmon resonance (LSPR) property of metallic nanoparticles is widely exploited for chemical and biological sensing. Selective biosensing of molecules using functionalized nanoparticles has become a major research interdisciplinary area between chemistry, biology and material science. Noble metals, especially gold (Au) and silver (Ag) nanoparticles, exhibit unique and tunable plasmonic properties; the control over these metal nanostructures size and shape allows manipulating their LSPR and their response to the local environment. In this review, we will focus on Ag-based nanoparticles, a metal that has probably played the most important role in the development of the latest plasmonic applications, owing to its unique properties. We will first browse the methods for AgNPs synthesis allowing for controlled size, uniformity and shape. Ag-based biosensing is often performed with coated particles; therefore, in a second part, we will explore various coating strategies (organics, polymers, and inorganics) and their influence on coated-AgNPs properties. The third part will be devoted to the combination of gold and silver for plasmonic biosensing, in particular the use of mixed Ag and AuNPs, i.e., AgAu alloys or Ag-Au core@shell nanoparticles will be outlined. In the last part, selected examples of Ag and AgAu-based plasmonic biosensors will be presented.
    Tags: alloy, biosensors, CHEMBIO, coating, core@shell, LSPR, POLE 3, silver nanoparticles, synthesis.

  • A. Loiseau, L. Zhang, D. Hu, M. Salmain, Y. Mazouzi, R. Flack, B. Liedberg, and S. Boujday, “Core–Shell Gold/Silver Nanoparticles for Localized Surface Plasmon Resonance-Based Naked-Eye Toxin Biosensing”, ACS Applied Materials & Interfaces, vol. 11, no. 50, p. 46462-46471, Dec. 2019.
    Abstract: The localized surface plasmon resonance (LSPR) phenomenon provides a versatile property for biodetection. Herein, this unique feature was employed to build a homogeneous optical biosensor to detect staphylococcal enterotoxin A (SEA) in solution down to very low levels by naked-eye readout. If the initial position of the LSPR band is located in the cyan region, even a small red shift (∼2–3 nm) induced by a refractive index change close to the surface of nanoparticles (NPs) could make the light absorption transit from cyan to green and become visually detectable via a concomitant change in the complementary colors. In this work, we aimed at synthesizing two types of NPs based on compositionally complex core–shell NPs—Ag shells on AuNPs (Au@AgNPs) and Ag inside gold nanoshells (Ag@AuNPs). By controlling the thickness of the shells and their surface chemistry with anti-SEA antibody (Ab), the LSPR band was tuned to near 495 and 520 nm for Ag@AuNPs and Au@AgNPs, respectively. The two particle systems were subsequently applied to spectroscopically and visually detect anti-SEA Ab–SEA interactions. Upon the addition of SEA, large red shifts of the LSPR band were observed spectroscopically and the limits of detection (LODs) were estimated to be 0.2 and 0.4 nM for Au@AgNPs and Ag@AuNPs, respectively. Although the two sets of NPs gave almost identical LODs, the Ag@AuNPs whose initial position of the LSPR band was tuned in the cyan to green region (∼500 nm) displayed a substantially more distinct color change from orange to red, as revealed by the naked eye. We foresee significant potential to this strategy in medical diagnostics and environmental monitoring, especially when basic laboratory infrastructure is sparse or nonexistent.
    Tags: CHEMBIO, POLE 3.
    Note Note
    <p>doi: 10.1021/acsami.9b14980</p>

  • K. Lu, M. Li, Y. Huang, Y. Sun, Z. Gong, Q. Wei, X. Zhao, Y. Zhang, and P. Yu, “Total synthesis of wikstrol A and wikstrol B”, Organic & Biomolecular Chemistry, vol. 17, no. 35, p. 8206-8213, 2019.
    Abstract: The first total synthesis of wikstrol A and wikstrol B was achieved via Sharpless asymmetric dihydroxylation, Sonogashira and rhodium-catalyzed oxidative coupling as key steps. , The first total synthesis of wikstrol A and wikstrol B was achieved by employing aldol reaction, Sharpless asymmetric dihydroxylation, regioselective iodination, Sonogashira coupling, and rhodium-catalyzed oxidative coupling as key steps. The structure of the key intermediate for wikstrol A was confirmed via its derivative by single-crystal X-ray analysis.
    Tags: GOBS, POLE 3.

  • L. Luconi, G. Tuci, D. Yakhvarov, G. Poli, A. Rossin, A. Khusnuriyalova, and G. Giambastiani, “Imidazole-Bridged Tetrameric Group(IV) Heteroleptic Complexes from the Spontaneous Metal-Ligand Assembly of a Potentially N4-Tetradentate Ligand”, European Journal of Inorganic Chemistry, vol. 2019, no. 39-40, p. 4384-4393, Oct. 2019.
    Abstract: The imidazole-containing N4-tetradentate ligand N-(2-(1H-imidazol-2-yl)-3-(pyridin-2-yl)propyl)-2,6-diisopropylaniline (L2H) and its N-benzyl-protected variant (L2Bn) at the imidazole fragment have been synthesized and fully characterized. Both molecules contain an unresolved Csp3 stereogenic center. The coordination behavior of the newly prepared ligands towards group IV metal ions (MIV = Zr, Hf) has been examined through multinuclear 1H and 13C{1H} NMR spectroscopy and selected single-crystal X-ray structural analyses. The ability of the imidazole fragment to enter the metal coordination sphere as a neutral or a monoanionic system has also been investigated, unveiling quite original coordination modes as well as unexpected molecular architectures. When one N imidazole atom is blocked by a benzyl protecting group (L2Bn), the ligand reaction with MIV(NMe2)4 (MIV = Zr, Hf) as metal precursor gives rise to discrete monometallic tris(dimethylamido) 5-coordinated compounds of general formula L2BnM(NMe2)3. The ligand chelates the metal ion as a bidentate monoanionic ?2{N?,N} system through the imidazole moiety and the anilido N donor while an uncoordinated picolyl arm dangles away from the metal center. Upon coordination to the metal ion, the unprotected L2H undergoes a unique self-assembly of the chiral racemic ligand to generate an achiral tetrameric network featuring a regularly alternating (R*,S*,R*,S*) configuration around the 6-coordinated metal centers. The resulting bis(dimethylamido) tetrameric architectures of formula [L2HM(NMe2)2]4 named ?poker complexes? contain the imidazole fragment of each ligand bridging two adjacent MIV ions in a µ-?{N}:?{N?} coordination hapticity. At the same time, the picolyl fragments of each chelating L2H ligand ?sting? a neighboring metal center as unconventional scorpion's tails that impose further rigidity to the tetrameric structure.
    Tags: Hafnium, Imidazole, N ligands, POLE 1, ROCS, S4 symmetry, Supramolecular assembly, Zirconium.
    Note Note
    <p>doi: 10.1002/ejic.201900763</p>

  • G. Maestri and E. Derat, “Alkenyl boost for Catellani”, Nature Chemistry, vol. 11, no. 12, p. 1082-1084, Dec. 2019.
    Abstract: The Catellani reaction is a multi-component cascade sequence, catalysed by palladium and norbornene, which typically uses aromatic starting materials. Now, through the use of a modified norbornene co-catalyst, the scope of this reaction has been extended to alkenyl reagents, enabling the preparation of all-carbon tetrasubstituted olefins.
    Tags: MACO, POLE 1.
    Attachment Full Text PDF 736.2 kb (source)

  • O. Makrygenni, F. L. Bentaleb, D. Brouri, A. Proust, F. Launay, and R. Villanneau, “Selective uptake of La3+ ions with polyoxometalates-functionalized mesoporous SBA-15: An EXAFS study”, Microporous and Mesoporous Materials, vol. 287, p. 264-270, Oct. 2019.
    Abstract: In this work, mesoporous materials based on inorganic/organic polyoxometalate (POMs) hybrids with the ability of further incorporating heterometallic lanthanum cations were designed. On the basis of the La3+ coordination to vacant organophosphonyle derivatives of POMs previously studied, herein POMs-grafted onto an amino-functionalized mesoporous SBA-15 ({NH2}-SBA-15) with incorporated La3+ ions were synthesized by varying the amounts of the latter. LIII-edge La EXAFS spectroscopy of the resulting materials provided local structural information around LaIII ions (i.e. number, nature and distances of neighboring atoms), which are comparable to that of the LaIII complexes of POMs hybrids. This technique, in addition with 31P CP-MAS NMR spectroscopy, gave definitive clues for a selective uptake of the incorporated La3+ ions by the POMs grafted onto the {NH2}-SBA-15 supports. This study is a clear demonstration that, due to their chelate effect, POMs hybrids act as efficient ligands for La3+ even in the presence of competitive adsorption sites. Consequently, a regular distribution of the La3+ ions along the channels of the SBA-15 is thus observed in these materials due to the nanostructuration of the POMs onto the support.
    Tags: E-POM, EXAFS, Lanthanum, Mesoporous silica, POLE 2, Polyoxometalates.

  • O. Makrygenni, D. Brouri, A. Proust, F. Launay, a

    nd R. Villanneau, “Immobilization of polyoxometalate hybrid catalysts onto mesoporous silica supports using phenylene diisothiocyanate as a cross-linking agent”, Microporous and Mesoporous Materials, vol. 278, p. 314-321, Apr. 2019.
    Abstract: The hybrid derivative of heteropolytungstate bearing two aniline groups, namely (nBu4N)3[NaHPW9O34{As(O)C6H4NH2}2], was post-functionalized in the presence of 1,4-phenylene diisothiocyanate (PDITC). The resulting molecular moiety was characterized by IR, 1H and 31P NMR spectroscopy. In a second step, this post-functionalized hybrid of polyoxometalate was covalently grafted onto the surface of an amino-functionalized SBA-15 silica by means of the formation of thiourea bonds. This simple and efficient strategy of immobilization did not require the use of a coupling agent and was performed in mild reaction conditions. Various physicochemical techniques (13C and 31P CPMAS NMR spectroscopies, XPS, XRF, HR-TEM microscopy and N2 sorption) contributed to the full characterization of the supported catalyst. In addition HR-TEM was found to be an essential technique for the identification of the polyoxometalate units inside the pores of SBA-15. Finally, the catalytic performances of the supported polyoxometalates were evaluated in the epoxidation of cyclooctene with aqueous H2O2 in acetonitrile at 50 °C.
    Tags: Anchored homogeneous catalysts, E-POM, Epoxidation catalysis, Functionalized mesoporous silica materials, POLE 2, Polyoxometalate hybrids.

  • C. Medena, F. Calogero, Q. Lemoine, C. Aubert, E. Derat, L. Fensterbank, G. Gontard, O. Khaled, N. Vanthuyne, J. Moussa, C. Ollivier, M. Petit, and M. Barbazanges, “A HELIXOL-Derived Bisphosphinite Ligand: Synthesis and Application in Gold-Catalyzed Enynes Cycloisomerization”, European Journal of Organic Chemistry, vol. 2019, no. 11, p. 2129-2137, 2019.
    Abstract: The synthesis, optical resolution through derivatization, characterization, and utilization of a new helical bis(phosphinite gold) complex derived from HELIXOL are described. By using an efficient cobalt catalyst, neither irradiation nor high catalytic loading was required to access the helicene of interest. The latter was phosphorylated to afford a new chiral ligand that was studied. Especially, treatment with AuCl(SMe2) gives a dinuclear gold complex that was used in cycloisomerization reactions.
    Tags: ARC, Chirality, Enyne Cycloisomerization, Helicene, Homogeneous catalysis, MACO, Phosphinite, POLE 1.
    Attachment Full Text PDF 1.5 Mb (source)

  • F. Medici, J. Maury, G. Lemière, and L. Fensterbank, “Interaction between Spirosilanes and Lewis Bases: from Coordination to Frustration”, Chemistry – A European Journal, vol. 25, no. 40, p. 9438-9442, 2019.
    Abstract: In this work, the interaction between Lewis bases, especially N-heterocyclic carbenes (NHCs), and hindered neutral silicon derivatives featuring high Lewis acidity is described. The formation of normal and abnormal Lewis adducts could be controlled by varying the acidity of the corresponding tetravalent spiro organosilane. Some DFT calculations permitted to gain insight into the thermodynamics of the NHC–spirosilane interaction featuring various NHCs differing in size and σ-donor capacity. Spirosilanes are introduced as new Lewis partners in frustrated Lewis pair (FLP) chemistry and some FLP-type reactivities are presented, in particular the activation of formaldehyde that could occur with both hindered NHCs and phosphines.
    Tags: frustrated Lewis pairs, Lewis acid, MACO, pentavalent silicon, POLE 1, spirosilanes.
    Attachment Full Text PDF 969.8 kb (source)

  • T. Neva, T. Carmona, J. M. Benito, C. Przybylski, C. Ortiz Mellet, F. Mendicuti, and J. M. García Fernández, “Dynamic Control of the Self-Assembling Properties of Cyclodextrins by the Interplay of Aromatic and Host-Guest Interactions”, Frontiers in Chemistry, vol. 7, p. 72, 2019.
    Abstract: The presence of a doubly-linked naphthylene clip at the O-2I and O-3II positions in the secondary ring of -cyclodextrin (CD) derivatives promoted their self-assembly into head-to-head supramolecular dimers in which the aromatic modules act either as cavity extension walls (if the naphthalene moiety is 1,8-disubstituted) or as folding screens that separate the individual CD units (if 2,3-disubstituted). Dimer architecture is governed by the conformational properties of the monomer constituents, as determined by NMR, fluorescence, circular dichroism and computational techniques. In a second supramolecular organization level, the topology of the assembly directs host-guest interactions and, reciprocally, guest inclusion impacts the stability of the supramolecular edifice. Thus, inclusion of adamantane carboxylate, a well-known CD cavity-fitting guest, was found to either preserve the dimeric arrangement, leading to multicomponent species, or elicit dimer disruption. The ensemble of results highlights the potential of the approach to program self-organization and external stimuli responsiveness of CD devices in a controlled manner while keeping full diastereomeric purity.
    Tags: CSOB, POLE 3.

  • T. H. N. Nguyen, F. Balligand, A. Bormann, V. Bennevault, and P. Guégan, “Synthesis of new biobased linear poly(ester amide)s”, European Polymer Journal, vol. 121, p. 109314, Dec. 2019.
    Abstract: In the present work, we investigated the synthesis of new biobased linear aliphatic PEAs with a controlled regicity, in a two steps procedure. First, dioldiamide derivatives were successfully synthesized, then polycondensation reaction using the usual alcohol plus acid reaction was performed. NMR analyses demonstrate that dioldiamide can be synthesized in one step from diacid and ethanolamine condensation with high conversion. A new library of polymers was then synthesized, and characterized. Overall, the reactivity of amine or alcohol or acid functions is investigated by in-depth 1H and 13C NMR versus HSQC NMR analysis. These results can be used to follow the complex evolution of monoesterification or diesterification reactions, monoamidation or diamidation reactions when dicarboxylic acids versus alcohol or amine are reacted. Thermal degradation was examined, and a good stability of all the polymers was evidenced. The thermal properties of the polymers were also analyzed, and high melting temperatures were measured, thanks to the control of the regicity. Comparing the melting and crystallization temperature revealed a fast rate of crystallization, an important feature for polymer melt processing. The solubility behavior of these polymers was found to be close to the one of polyamides, suggesting the use of this new polymers library to replace polyamides in applications where biodegradability of the materials is required.
    Tags: Biomass, Dicarboxylic acid, Dioldiamide monomer, Poly(ester amide)s, POLYMERES, Thermal behaviors.

  • M. Okubo, J. Long, D. R. Talham, and R. Lescouëzec, “Solid-state electrochemistry of metal cyanides”, Comptes Rendus Chimie, vol. 22, no. 6, p. 483 - 489, 2019.
    Abstract: Efficient energy storage in the form of batteries contributes to building sustainable society. As advanced batteries need positive electrode materials capable of larger capacity, higher voltage, and lower cost, it is important to search for novel electrode materials. Among various inorganic/organic materials, cyanido-bridged coordination compounds are promising candidates for battery electrodes due to their ability to undergo solid-state redox reaction associated with ion (de)intercalation. In this review, recent results about the thermodynamic and kinetic aspects of the solid-state electrochemistry of cyanido-bridged coordination compounds are summarized, providing a fundamental basis toward developing cyanide electrodes for advanced batteries. Résumé Le stockage de l’énergie dans des batteries performantes est un élément clé pour le développement des énergies renouvelables et d'un modèle de société durable. Un des défis pour construire de nouvelles batteries plus performantes est le développement de matériaux d'intercalation pour cathode présentant de plus grandes capacités, de plus grands voltages et des coûts réduits. Parmi les divers matériaux organiques et inorganiques explorés, les polymères de coordination à pont cyanure sont des candidats prometteurs. Ceux ci peuvent s'oxyder et se réduire à l’état solide en (dés)intercalant des ions. Dans cette revue, quelques résultats récents sur les aspects thermodynamiques et cinétiques des propriétés électrochimiques des polymères de coordination à pont cyanure sont résumés, démontrant leur potentiel intérêt comme életcrodes dans de nouvelles batteries.
    Tags: ERMMES, POLE 2.
    Note Note
    <p>Forty years of exchange interactions on the occasion of the 75th birthday of Michel Verdaguer</p>

  • W. X. C. Oliveira, W. D. do Pim, C. B. Pinheiro, Y. Journaux, M. Julve, and C. L. M. Pereira, “Monitoring the

    hydrogen bond net configuration and the dimensionality of aniline and phenyloxamate by adding 1H-pyrazole and isoxazole as substituents for molecular self-recognition”, CrystEngComm, vol. 21, no. 17, p. 2818-2833, Apr. 2019.
    Abstract: This work describes the synthesis and characterization of a new class of oxamic acid derivatives containing pyrazole and isoxazole as substituents to investigate their ability to form hydrogen bonds aiming at applying them in crystal engineering and molecular self-recognition. In this respect, we report a new synthesis of 2-(4-nitrophenyl)-1,3-propanedial (1) in high yield using SOCl2 as a chlorinating agent. The new oxamic esters 4-(1H-pyrazol-4-yl)phenylene-N-(ethyloxamate) (2d) and 4-(1,2-oxazol-4-yl)phenylene-N-(ethyloxamate) (3d) were prepared from 1. The synthetic route consists of the cyclisation of 1 either with hydrazine to afford 4-(-aminophenyl)-1H-pyrazole (2a) or with hydroxylamine to obtain the isoxazole-based molecule 4-(4-nitrophenyl)-1,2-oxazole (3a). The reduction of 2a and 3a was carried out in an acidic/tin solution to yield 4-(4-ammoniophenyl)-1H-pyrazol-2-ium trichlorostannate(II) chloride monohydrate (2b) and 4-(4-ammoniophenyl)-1,2-oxazole hexachlorostannate(IV) (3b). Basic extraction of 3b provided 4-(4-aminophenyl)-1,2-oxazole (3c). The reduction of 2a to 4-(4-aminophenyl)-1H-pyrazole (2c) was achieved by means of hydrazine associated with supported palladium on carbon. The condensation of 2c and 3c with ethyl chlorooxoacetate delivers oxamic esters 2d and 3d. In n-tetrabutylammonium hydroxide solution 2d is fully hydrolyzed, obtaining the n-tetrabutylammonium salt of 4-(1H-pyrazole-4-yl)phenylene-N-oxamate as a hemihydrate (2e). The low stability of isoxazole molecules in basic solutions was proved by crystallizing the n-tetrabutylammonium salt of 1-cyano-1-(4-nitrophenyl)-2-oxoethanide (3f) (obtained by cleavage of 3d with n-Bu4NOH) and preparing its conjugated acid 2-(4-nitrophenyl-3-oxopropanenitrile (3e). The structures of 2b, 3b, 3d and 2e were solved by single crystal X-ray diffraction techniques. The analysis of their crystal packing reveals hydrogen bond features compatible for all compounds as well as some differences depending on the pH of the crystallization solution and the presence or absence of the oxamate group due to the increase of hydrogen bond donors and acceptors.
    Tags: ERMMES, POLE 2.
    Attachment Full Text PDF 3.1 Mb (source)

  • C. Przybylski, V. Bonnet, and R. R. Vivès, “A microscale double labelling of GAG oligosaccharides compatible with enzymatic treatment and mass spectrometry”, Chemical Communications, vol. 55, no. 29, p. 4182-4185, 2019.

  • C. Przybylski, H. Ramoul, V. Bonnet, M. Abad, and N. Jarroux, “Harnessing Polyisobutylene by Rotaxanation with γ-Cyclodextrin: Opportunities for Making Smart Molecular Necklaces”, Macromolecular Chemistry and Physics, vol. 220, no. 5, p. 1800502, Mar. 2019.
    Abstract: Abstract A new type of polyrotaxane based on the threading of ?-cyclodextrins (?-CDs) along a highly hydrophobic polymer, polyisobutylene (PIB), is successfully prepared and finely characterized. The used radical coupling associated with tuned reaction time and temperature leads to a fast and controlled necklace synthesis with low reagent consumption. Synthesis exhibits appealing conversion and threading rates with almost 100% and 62?73%, respectively. A combination of well-established SEC and NMR techniques, with a more forefront MALDI-TOF MS approach, provides details on the original PIB and the resulting polyrotaxanes (M w, M n, PDI, and average number of ?-CD threaded). Interestingly, tetramethylguanidinium-2-(4-hydroxyphenylazo)benzoate in DMF for MALDI analysis is revealed as a suitable matrix to overcome solubility troubles widely observed with PIB. Moreover, rotaxanation appears as an alternative to the grafting of polar groups to modify/handle hydrophobic polymers. Such an approach offers new opportunities to achieve the synthesis, with unambiguous evidence, of new supramolecular necklaces based on highly hydrophobic polymers.
    Tags: CSOB, cyclodextrins, mass spectrometry, POLE 3, polyisobutylene, polyrotaxane, radical coupling.
    Note Note
    <p>doi: 10.1002/macp.201800502</p>

  • E. Puig, C. Desmarets, G. Gontard, M. N. Rager, A. L. Cooksy, and H. Amouri, “Capturing a Square Planar Gold(III) Complex Inside a Platinum Nanocage: A Combined Experimental and Theoretical Study”, Inorganic Chemistry, vol. 58, no. 5, p. 3189-3195, Mar. 2019.
    Abstract: A novel synthetic procedure was set up to gain access to platinum coordination cages Pt2L4, which are less investigated compared to their palladium counterparts. This Pt2L4 nanocage exhibits an adequate cavity for guest encapsulation. Indeed, the Au(III) metal complex [Au(bdt)2]− (bdt = benzene-1,2-dithiolate) was successfully captured inside the cavity, in contrast to the analogous palladium cage which failed to host the gold complex. This result represents a rare example where a metal complex with thio-ligands can be encapsulated in a coordination cage. Moreover, it highlights the role of the metal center and the robustness of the platinum cage for host–guest chemistry. This discovery will inspire researchers in this area to pay more attention to Pt-cages. The host–guest system was fully characterized by NMR techniques and X-ray crystallographic analysis. Moreover, the nature of the host–guest interaction in this unique example was investigated and rationalized by DFT computational studies.
    Tags: ARC, POLE 1.
    Attachment Full Text PDF 1.1 Mb (source)

  • J. Qu, C. Livache, B. Martinez, C. Gréboval, A. Chu, E. Meriggio, J. Ramade, H. Cruguel, X. Z. Xu, A. Proust, F. Volatron, G. Cabailh, N. Goubet, and E. Lhuillier, “Transport in ITO Nanocrystals with Short- to Long-Wave Infrared Absorption for Heavy-Metal-Free Infrared Photodetection”, ACS Applied Nano Materials, vol. 2, no. 3, p. 1621-1630, Mar. 2019.
    Abstract: Nanocrystals are often described as interesting materials for the design of low-cost optoelectronic devices, especially in the infrared range. However, the driving materials reaching infrared absorption generally contain heavy metals (Pb and Hg) with a high toxicity. An alternative strategy to achieve infrared transition is the use of doped semiconductors presenting intraband or plasmonic transition in the short-, mid-, and long-wave infrared. This strategy may offer more flexibility regarding the range of possible candidate materials. In particular, significant progress has been achieved for the synthesis of doped oxides and for the control of their doping magnitude. Among them, tin doped indium oxide (ITO) is the one providing the broadest spectral tunability. Here we test the potential of such ITO nanoparticles for photoconduction in the infrared. We demonstrate that In2O3 nanoparticles present an intraband absorption in the mid-infrared range which is transformed into a plasmonic feature as doping is introduced. We have determined the cross section associated with the plasmonic transition to be in the 1–3 × 10–13 cm2 range. We have observed that the nanocrystals can be made conductive and photoconductive thanks to a ligand exchange using a short carboxylic acid, leading to a dark conduction with n-type character. We present evidence that the observed photoresponse in the infrared is the result of a bolometric effect.
    Tags: E-POM, POLE 2.
    Attachment Full Text PDF 4.3 Mb (source)

  • J. M. J. M. Ravasco, C. M. Monteiro, F. Siopa, A. F. Trindade, J. Oble, G. Poli, S. P. Simeonov, and C. A. M. Afonso, “Creating Diversity from Biomass: A Tandem Bio/Metal-Catalysis towards Chemoselective Synthesis of Densely Substituted Furans”, ChemSusChem, vol. 12, no. 20, p. 4629-4635, 2019.
    Abstract: A new chemoselective (enzymatic desymmetrization/Ru-catalyzed C−H activation) sequence to obtain differently substituted furans from the largely available 2,5-furandicarboxylic acid (FDCA) was developed. Series of di- and trisubstituted furans were prepared in very good yields and excellent chemoselectivity. This study discloses a new approach towards valorization of the furanics platform through the use of FDCA as a stable intermediate, thus circumventing the chemical instability of the parent 5-hydroxymethylfurfural.
    Tags: POLE 1, ROCS.
    Attachment Full Text PDF 1.8 Mb (source)
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