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257 results on '"Dominique Luneau"'

1. Synthesis, Crystal Structure and Magnetic Properties of a Trinuclear Copper(II) Complex Based on P-Cresol-Substituted Bis(α-Nitronyl Nitroxide) Biradical

Author

Sabrina Grenda, Maxime Beau, and Dominique Luneau

Subjects
nitronyl nitroxide biradical, molecular magnetism, copper complex, Organic chemistry, QD241-441
Abstract

Trinuclear copper(II) complex [CuII3(NIT2PhO)2Cl4] was synthesized with p-cresol-substituted bis(α-nitronyl nitroxide) biradical: 4-methyl-2,6-bis(1-oxyl-3-oxido-4,4,5,5-tetramethyl-2-imidazolin-2-yl)phenol (NIT2PhOH). The crystal structure of this heterospin complex was determined using single-crystal X-ray diffraction analysis and exhibits four unusual seven-membered metallocycles formed from the coordination of oxygen atoms of the N-O groups and of bridging phenoxo (µ-PhO−) moieties with copper(II) ions. The crystal structure analysis reveals an incipient agostic interaction between a square planar copper center and a hydrogen-carbon bond from one methyl group carried on the coordinated nitronyl-nitroxide radical. The intramolecular Cu∙∙∙H-C interaction involves a six-membered metallocycle and may stabilize the copper center in square planar coordination mode. From the magnetic susceptibility measurements, the complex, which totals seven S = 1/2 spin carriers, has almost a ground state spin S = 1/2 at room temperature ascribed to strong antiferromagnetic interaction between the nitronyl nitroxide moieties and the copper(II) centers and in between the copper(II) centers through the bridging phenoxo oxygen atom.

Published
2022
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2. Polarized Neutron Diffraction: An Excellent Tool to Evidence the Magnetic Anisotropy—Structural Relationships in Molecules

Author

Dominique Luneau and Béatrice Gillon

Subjects
magnetic anisotropy, spin cluster, polarized neutron diffraction, local susceptibility tensor, molecular magnetism, transition metal complexes, Chemistry, QD1-999
Abstract

This publication reviews recent advances in polarized neutron diffraction (PND) studies of magnetic anisotropy in coordination compounds comprising d or f elements and having different nuclearities. All these studies illustrate the extent to which PND can provide precise and direct information on the relationship between molecular structure and the shape and axes of magnetic anisotropy of the individual metal sites. It makes this experimental technique (PND) an excellent tool to help in the design of molecular-based magnets and especially single-molecule magnets for which strong uniaxial magnetic anisotropy is required.

Published
2021
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3. Synthesis and Structure of Fluorinated (Benzo[d]imidazol-2-yl)methanols: Bench Compounds for Diverse Applications

Author

Vasily Romanov, Evgeny Tretyakov, Galina Selivanova, Jiayao Li, Irina Bagryanskaya, Alexander Makarov, and Dominique Luneau

Subjects
polyfluorinated 1,2-diaminobenzenes, heterocyclization, fluorinated benzimidazoles, crystal structure, H-bonding, 1D, 2D, and 3D structures, Crystallography, QD901-999
Abstract

A simple and general approach to the synthesis (from commercial precursors) of eight out of nine possible (benzo[d]imidazol-2-yl)methanols fluorinated on the benzene ring is reported. Molecular and crystalline structures of most compounds were solved by X-ray diffraction analysis. This made it possible to reveal the influence of the number and arrangement of fluorine atoms in the benzene cycle on the formation of intermolecular hydrogen bonds. It was found that the more fluorine atoms are present in a compound, the higher the dimensionality of the H-bonded structure is. Moreover, the presence of fluorine atoms in the synthesized compounds leads to the emergence of C–F…π interactions affecting crystal packing. The synthesized fluorinated (benzo[d]imidazol-2-yl)methanols may serve as excellent bench compounds for the synthesis of a systematic series of fluorine-containing derivatives to study structure–property correlations in various fields of research from medicine to materials science.

Published
2020
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4. Assembly of Imidazolyl-Substituted Nitronyl Nitroxides into Ferromagnetically Coupled Chains

Author

Vasily Romanov, Irina Bagryanskaya, Nina Gritsan, Dmitry Gorbunov, Yulia Vlasenko, Mehman Yusubov, Elena Zaytseva, Dominique Luneau, and Evgeny Tretyakov

Subjects
nitronyl nitroxides, imidazole, crystal structure, hydrogen bonding, exchange interaction, density functional theory, Crystallography, QD901-999
Abstract

New nitronyl nitroxides, namely, 2-(4,5-dimethylimidazol-2-yl)- and 2-(4,5-dichloroimidazol-2-yl)-4,4,5,5-tetramethyl-4,5-dihydro-1H-imidazol-3-oxide-1-oxyl, were prepared in crystalline form. According to single-crystal X-ray data, intra- and intermolecular hydrogen bonds are formed between NH groups of the imidazole cycles and O atoms of the nitroxide moieties. The intermolecular H-bonds contribute to the alignment of molecules into chains along the a-axis; this alignment causes short intrachain contacts between O and C atoms carrying spin density of opposite signs. Such an arrangement of nitroxides induces ferromagnetic intrachain interactions (J ≈ 10 cm−1) between neighboring radicals.

Published
2019
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5. A Crystallographic Study of a Novel Tetrazolyl-Substituted Nitronyl Nitroxide Radical

Author

Vasily E. Romanov, Irina Yu. Bagryanskaya, Dmitry E. Gorbunov, Nina P. Gritsan, Elena V. Zaytseva, Dominique Luneau, and Evgeny V. Tretyakov

Subjects
stable radicals, nitronyl nitroxides, tetrazoles, hydrogen bonding, crystal structure, exchange interaction, density functional theory, Crystallography, QD901-999
Abstract

Spin-labelled compounds are widely used in chemistry, physics, biology, and material sciences, but the directed synthesis of some functionalized organic radicals is still a challenge. We succeeded in the preparation of a tetrazolyl-substituted nitronyl nitroxide radical in pure crystalline form. According to the single-crystal X-ray data, intra- (NH…O, 2.43 Å) and inter-molecular hydrogen bonds (NH…O, 1.91 Å) are formed between NH groups of the tetrazole cycles and O atoms of the paramagnetic moieties. The intermolecular H-bonds connect the molecules forming chains along the a-axis. Moreover, there are short intermolecular contacts between the O atoms (3.096 Å) and between the O and C atoms (3.096 Å) of the nitronyl nitroxide moieties within the chain. The spin-unrestricted broken-symmetry calculations performed at the BS-UB3LYP/def2-TZVP level of theory predicted a sufficient ferromagnetic interaction (J ≈ 20 cm–1) between the adjacent radicals inside the chain, but a weak antiferromagnetic interaction (−J ≤0.2 cm−1) between the nearest radicals belonging to the different chains. Thus, a rare case when stable radicals, the tetrazolyl-substituted nitronyl nitroxides, are ordered into ferromagnetic chains was revealed; an investigation of the magneto-structural correlations inherent in the nitroxide radical will demand a special experiment in the sub-Kelvin regime.

Published
2018
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6. Mapping the Magnetic Anisotropy inside a Ni4 Cubane Spin Cluster Using Polarized Neutron Diffraction

Author

Olga Iasco, Yuri Chumakov, Frédéric Guégan, Béatrice Gillon, Marc Lenertz, Alexandre Bataille, Jean-François Jacquot, and Dominique Luneau

Subjects
magnetic anisotropy, spin cluster, polarized neutron diffraction, local susceptibility tensor, molecular magnetism, transition metal complexes, Chemistry, QD1-999
Abstract

In this publication, we report on the study of the magnetic anisotropy of the cubane type tetranuclear cluster of Ni(II), [Ni4(L)4(MeOH)4] (H2L = salicylidene-2-ethanolamine; MeOH = methanol), by the means of angular-resolved magnetometry and polarized neutron diffraction (PND). We show that better than other usual characterization techniques—such as electron paramagnetic resonance spectroscopy (EPR) or SQUID magnetometry—only PND enables the full determination of the local magnetic susceptibility tensor of the tetranuclear cluster and those of the individual Ni(II) ions and the antiferromagnetic pairs they form. This allows highlighting that, among the two antiferromagnetic pairs in the cluster, one has a stronger easy-axis type anisotropy. This distinctive feature can only be revealed by PND measurements, stressing the remarkable insights that they can bring to the understanding of the magnetic properties of transition metals clusters.

Published
2017
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7. Hydrogen bonding in cytosinium dihydrogen phosphite

Author

Nourredine Benali-Cherif, Amel Messai, Erwann Jeanneau, and Dominique Luneau

Subjects
Crystallography, QD901-999
Abstract

In the title compound, C4H8N3O4P+·H2PO3−, the cytosine molecule is monoprotonated and the phosphoric acid is in the monoionized state. Strong hydrogen bonds, dominated by N—H...O interactions, are responsible for cohesion between the organic and inorganic layers and maintain the stability of this structure.

Published
2009
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8. Synthesis, structure and magnetic properties of two bis(oxalato)cuprate(<scp>ii</scp>) salts with pyridinium type counter ions

Author

Cyrielle L. F. Dazem, A. Ken Inge, Dominique Luneau, Lars Öhrström, and Justin Nenwa

Subjects
General Materials Science, General Chemistry, Condensed Matter Physics
Abstract

In the Cu(ii) oxalate salts of (C5H7N2O)2[Cu(C2O4)2] 1 and C13H16N2[Cu(C2O4)2] 2, the oxalate adopts different coordination modes: the common bidentate chelating oxalate in 1 and the relatively scarce μ-oxalato-κ3O1,O2:O1′ in 2.

Published
2023

9. Mono-, Di-, and Tetranuclear Manganese(II) Complexes with p-Phenylsulfonylcalix[4]arene Macrocycles as Ligand Antennas: Synthesis, Structures, and Emission Properties

Author

Constance Lecourt, Yan Suffren, Erwann Jeanneau, Dominique Luneau, Cédric Desroches, Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA), Institut des Sciences Chimiques de Rennes (ISCR), Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Laboratoire des Multimatériaux et Interfaces (LMI), Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), and Universit? Claude Bernard Lyon 1

Subjects
Manganese compounds, Luminescence, Optical properties, Chelation, Excited states, Dimethylformamide, General Chemistry, Emission spectroscopy, Ligands, Condensed Matter Physics, Dinuclear, Emission properties, Excitation wavelength, Pseudo-polymorphs, As-ligands, Organic solvents, Synthesis (chemical), Structure property, [CHIM]Chemical Sciences, Antennas, Antenna synthesis, Coordination compounds, General Materials Science, N-N-dimethylformamide, Macrocycles
Abstract

International audience; Three manganese(II) coordination compounds with a p-phenylsulfonylcalix[4]arene (ppThiaSO2) ligand were synthetized and are denoted as follows: [MnII(ppThiaSO2)(DMF)4] (1) (DMF = N,N-dimethylformamide), [Mn2II(ppThiaSO2)(DMF)6] (2), and K[Mn4II(ppThiaSO2)2F] in the form of two pseudo-polymorphs (3a and 3b). Their electronic emission spectra were studied in the solid state at different temperatures and at various excitation wavelengths. All compounds (2, 3a, and 3b) except 1 present luminescent properties at UV excitation wavelength, with emission maxima centered at 695, 602, and 675 nm, respectively. Their structural and optical properties were compared to those of previously reported analogous compounds bearing the p-tert-butylsulfonylcalix[4]arene (ThiaSO2) ligand. The luminescence of these complexes was attributed to the spin-forbidden 4T1→ 6A1d-d transition of manganese(II). The emission depends on the coordination of the metal center, the conformation of the macrocycle, and the structural packing. Hereafter, we present the synthesis, structure, and excitation and emission spectra of each compound, together with the dependence of the emission quenching on molecular dioxygen. © 2022 American Chemical Society. All rights reserved.

Published
2022

10. Characteristic vibrational frequencies of osmium(<scp>ii</scp>) nitrosyl complexes probed by Raman spectroscopy and DFT calculations

Author

Nicolas Bélanger-Desmarais, Anatolie Gavriluta, Jean Bernard Tommasino, Christian Reber, and Dominique Luneau

Subjects
Materials Chemistry, General Chemistry, Catalysis
Abstract

Raman spectroscopy at variable temperature provides experimental frequencies for osmium(ii) nitrosyl complexes. Vibrational transitions are assigned using DFT calculations.

Published
2022

11. Series of Fluorinated Benzimidazole-Substituted Nitronyl Nitroxides: Synthesis, Structure, Acidity, Redox Properties, and Magnetostructural Correlations

Author

Evgeny Tretyakov, Pavel Fedyushin, Nadejda Bakuleva, Alexander Korlyukov, Pavel Dorovatovskii, Nina Gritsan, Alexey Dmitriev, Anna Akyeva, Mikhail Syroeshkin, Dmitri Stass, Mikhail Zykin, Nikolay Efimov, and Dominique Luneau

Subjects
Organic Chemistry
Abstract

A special series of nitronyl nitroxides was synthesized: 2-(benzimidazol-2'-yl)-4,4,5,5-tetramethyl-4,5-dihydro-1

Published
2022

13. Hypersensitive pressure-dependence of the conversion temperature of hysteretic valence tautomeric manganese–nitronyl nitroxide radical 2D-frameworks

Author

Christian Reber, Constance Lecourt, Nicolas Bélanger-Desmarais, Dominique Luneau, Katsuya Inoue, Cédric Desroches, Kseniya Maryunina, and Yuuta Izumi

Subjects
Valence (chemistry), Materials science, 010405 organic chemistry, Metals and Alloys, chemistry.chemical_element, General Chemistry, Manganese, Pressure dependence, 010402 general chemistry, 01 natural sciences, Tautomer, Nitroxide radical, Catalysis, 0104 chemical sciences, Surfaces, Coatings and Films, Electronic, Optical and Magnetic Materials, External pressure, Hot Temperature, Crystallography, chemistry, Materials Chemistry, Ceramics and Composites, Lamellar structure
Abstract

Valence tautomeric manganese(II)-radical lamellar compounds {[Mn2(NITIm)3]X}n with NITIm a nitronyl nitroxide radical and X = ClO4− (1) or BF4− (2) show a pressure-induced increase of their conversion temperature by approximately 40 K at a mild external pressure of 0.1 GPa, shifting the transition from near room temperature to hot temperature regions.

Published
2021

14. Functionalization of graphene oxide sheets with magnetite nanoparticles for the adsorption of copper ions and investigation of its potential catalytic activity toward the homocoupling of alkynes under green conditions

Author

Laroussi Chaabane, Mohammed Hassen V. Baouab, Emmanuel Beyou, Dominique Luneau, Ingénierie des Matériaux Polymères (IMP), Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-Institut National des Sciences Appliquées de Lyon (INSA Lyon), Université de Lyon-Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Université Jean Monnet [Saint-Étienne] (UJM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Laboratoire des Multimatériaux et Interfaces (LMI), and Université de Lyon-Université de Lyon-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)

Subjects
Aqueous solution, 010405 organic chemistry, Chemistry, Graphene, Inorganic chemistry, Oxide, chemistry.chemical_element, 010402 general chemistry, 01 natural sciences, Copper, Catalysis, 0104 chemical sciences, law.invention, chemistry.chemical_compound, Adsorption, Phenylacetylene, law, [CHIM]Chemical Sciences, Surface modification, Physical and Theoretical Chemistry
Abstract

This paper deals with the preparation of graphene oxide sheets (GO) modified with magnetite nanoparticles (Fe3O4NPs) for removing Cu(II) ions from aqueous solutions. Moreover, the recovered Cu(II)-based material was recycled as a catalyst for the homocoupling of a series of alkynes. The adsorption behavior of magnetic GO-based materials towards Cu(II) ions from aqueous solutions was studied as a function of the pH value and the contact time and it was observed that the magnetic GO-based absorbent can be separated quickly from its aqueous solution by using an external magnetic field. Its equilibrium adsorption capacity value for Cu(II) ions was as high as 3.808 ± 0.125 mmol.g−1 under neutral conditions. In addition, the catalytic activity of the resulting [GO-EDA-CAC@Fe3O4NPs]-BPED-Cu(II) material toward the homocoupling of phenylacetylene into 1,4-diphenylbuta-1,3-diyne was demonstrated with a yield up to 99%. Importantly, the [GO-EDA-CAC@Fe3O4NPs]-BPED-Cu(II) supported catalyst was consecutively reused for fifteen runs without a significant loss of its activity.

Published
2020

15. Coordination Chemistry of Nitronyl Nitroxide Radicals Has Memory

Author

Dominique Luneau, Laboratoire des Multimatériaux et Interfaces (LMI), Université Claude Bernard Lyon 1 (UCBL), and Université de Lyon-Université de Lyon-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)

Subjects
chemistry.chemical_classification, Nitroxide mediated radical polymerization, bistability, 010405 organic chemistry, Radical, chemistry.chemical_element, [CHIM.MATE]Chemical Sciences/Material chemistry, Manganese, radicals, 010402 general chemistry, Photochemistry, 01 natural sciences, Copper, Tautomer, 0104 chemical sciences, Coordination complex, Inorganic Chemistry, tautomerism, chemistry, manganese, [CHIM]Chemical Sciences, magnetic properties
Abstract

International audience; Nitronyl nitroxide free radicals, and particularly their coordination compounds, have played a major role in the development of molecular‐based magnetic materials. Nevertheless, recent results show that the metal‐nitroxide bond remains a source of very diverse and singular bistable magnetic systems. Furthermore, metal‐nitroxide systems provide a rare opportunity for studying the role of the various interactions governing magnetic properties or electron transfer. From this point of view, they contribute to extending our fundamental knowledge, with prospects for switchable and multifunctional materials. Herein, we review three types of bistability in these systems from our own research which are illustrative of the wealth of these systems. These comprise molecular entities with Cu(II)‐nitroxide bonds giving rise to a molecular‐spin transition, and coordination polymers with Mn(II)‐nitroxide bonds which may behave as magnets in some cases or are bistable by valence tautomerism in others.

Published
2020

16. Thermally-induced hysteretic valence tautomeric conversions in the solid state via two-step labile electron transfers in manganese-nitronyl nitroxide 2D-frameworks

Author

Lhoussain Khrouz, François Toche, Yuuta Izumi, Katsuya Inoue, Rodica Chiriac, Nicolas Bélanger-Desmarais, Constance Lecourt, Cédric Desroches, Dominique Luneau, Christian Reber, and Oscar Fabelo

Subjects
Nitroxide mediated radical polymerization, Valence (chemistry), Materials science, 010405 organic chemistry, Radical, chemistry.chemical_element, Manganese, 010402 general chemistry, 01 natural sciences, Redox, Tautomer, 0104 chemical sciences, law.invention, Inorganic Chemistry, Crystallography, chemistry, law, Electron paramagnetic resonance, Single crystal
Abstract

Near room temperature hysteretic thermo-induced valence tautomerism was discovered in a layered 2D-coordination polymer of manganese(II) with nitronyl nitroxide radicals separated by ClO4− anions (1). This opens a novel approach towards switchable materials with hysteresis and under ambient conditions with prospects for applications and for investigating solid-state intramolecular electron transfers. Herein, two new compounds with similar layered structures where the anions (X) are BF4− (2) or PF6− (3) are presented. Their magnetic behaviors also reveal hysteretic thermo-induced valence tautomeric conversions but in two steps and evidencing a strong effect of the anion. This occurs near room temperature (278–220 K) for 2 and higher for 3 (380–330 K). Their single crystal structures at different temperatures show that this involves two successive thermally-triggered electron transfers with switching between three redox tautomers formulated as {[MnII2−yMnIIIy(NITIm)3−y(NITRed)y]X}n, where y is temperature dependent. Upon cooling from the high-temperature redox-tautomer (y = 0) to the intermediate one (y = 1), half of the manganese(II) centers are oxidized to manganese(III) and 1/3 of the nitronyl nitroxide radicals (NITIm−) are reduced to the aminoxyl form (NITRed2−). On further cooling, the second half of the manganese(II) centers are oxidized and another 1/3 of the radicals are reduced to reach the low-temperature redox-tautomer (y = 2). Upon reheating, reverse electron transfers occur. This is complementarily supported by X-ray powder measurements, differential scanning calorimetry, and electron paramagnetic resonance and Raman spectroscopies. These multi-stable compounds in which manganese ions exchange reversibly their electron with the nitronyl nitroxide radical are outstanding rare examples of two-step valence tautomerism in the solid state promoted by the polymeric structure.

Published
2020

18. Through the challenging synthesis of tetraphenylporphyrin derivatives bearing nitroxide moieties

Author

Catherine Hirel, Ismail Fidan, Emel Önal, Dominique Luneau, Department of chemistry - Gebze Technical University, Gebze Teknik Üniversitesi [Gebze], Acibadem University, Laboratoire des Multimatériaux et Interfaces (LMI), Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Sabancı University SUNUM Nanotechnology Research Centre, and 0-Belirlenecek

Subjects
MALDI-TOF, Nitroxide mediated radical polymerization, Bearing (mechanical), 010405 organic chemistry, Chemistry, UV-vis, [CHIM.MATE]Chemical Sciences/Material chemistry, General Chemistry, QD241-441 Organic chemistry, 010402 general chemistry, Photochemistry, 01 natural sciences, Porphyrin, 0104 chemical sciences, law.invention, chemistry.chemical_compound, Ultraviolet visible spectroscopy, law, nitronyl and imino nitroxide, Tetraphenylporphyrin, [CHIM.CRIS]Chemical Sciences/Cristallography, [CHIM]Chemical Sciences, epr, Electron paramagnetic resonance, porphyrin
Abstract

Hirel, Catherine/0000-0002-6297-5650; LUNEAU, Dominique/0000-0002-1831-7693 Tetraphenylporphyrin derivatives a synthetic heterocycles with convenient preparation and a richness of properties which make them attractive in broad fields such as energy, life and materials sciences. Thus, in the quest for new radical architectures, tetraphenylporphyrins are prime candidates. To this end, we designed free-base tetraphenylporphyrins bearing nitronyl and imino nitroxide moieties covalently bonded to the para-position of the meso-phenyl substituent. Their detailed synthesis and characterization arc reported here. Scientific and Technological Research Council of Turkey-TUBITAKTurkiye Bilimsel ve Teknolojik Arastirma Kurumu (TUBITAK) [113Z005] Financial support from the Scientific and Technological Research Council of Turkey-TUBITAK (project 113Z005) is gratefully acknowledged. The authors declare no competing financial interest.

Published
2021

19. Intercalation of a manganese(II)-thiacalixarene luminescent complex in layered double hydroxides: synthesis and photophysical characterization

Author

Nicole Gilon, Arnaud Brioude, Yan Suffren, François Bessueille, Constance Lecourt, Dominique Luneau, Niall O'Toole, François Toche, Rodica Chiriac, Cédric Desroches, Erwann Jeanneau, Laboratoire des Multimatériaux et Interfaces (LMI), Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA), Institut des Sciences Chimiques de Rennes (ISCR), Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Plasma spectroscopies, hyphenated methods & speciation, Institut des Sciences Analytiques (ISA), Université de Lyon-Université de Lyon-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université Claude Bernard Lyon 1 (UCBL), Surfaces, Université Claude Bernard Lyon 1, Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES), Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA), Institut de Chimie du CNRS (INC)-Université Claude Bernard Lyon 1 (UCBL), and Université de Lyon-Université de Lyon-Centre National de la Recherche Scientifique (CNRS)

Subjects
Hexagonal prism, Singlet oxygen, Intercalation (chemistry), Layered double hydroxides, chemistry.chemical_element, 02 engineering and technology, General Chemistry, Manganese, engineering.material, 010402 general chemistry, 021001 nanoscience & nanotechnology, 01 natural sciences, Oxygen, Catalysis, 0104 chemical sciences, chemistry.chemical_compound, Crystallography, chemistry, Materials Chemistry, engineering, [CHIM]Chemical Sciences, Thiacalixarene, 0210 nano-technology, Luminescence
Abstract

International audience; Utilizing the osmotic swelling of Layered Double Hydroxides (LDHs, [Mg1-xAlx(OH)(2)](x+)(NO3-)(x)) in formamide, the anionic luminescent complex [(ThiaSO(2))(2)(Mn-II)(4)F](-) (ThiaSO(2) = p-tert-butylsulfonylcalixarene) is introduced between the positive layers, leading to doping of LDH. In the recovered LDH layers, the hexagonal prism morphology of the precursor is well retained. The formula of the resulting compound (Mg0.71Al0.29(OH)(2)(NO3)(0.288)((ThiaSO(2))(2)(Mn)(4)F)(0.002)(H2O)(0.5)) (1) was determined by elemental and thermogravimetric analysis. The low doping rate is attributed to the low negative charge density (e angstrom(-2)) of the complex. The basal spacing of 12.02 angstrom indicates that [(ThiaSO(2))(2)(Mn-II)(4)F](-) is sandwiched across the width by positive LDH layers. The photophysical properties of compound 1 were studied in the solid state. 1 presents luminescence properties upon UV excitation, with the emission maximum centered at 630 nm and 650 nm in the presence and the absence of atmospheric O-2, respectively. Photophysical studies have been carried out under different atmospheres and using various excitation wavelengths. The relationship of the extinction of emission with the presence of molecular oxygen is reported, and demonstrates the very high sensitivity of this compound to oxygen. Finally, incorporation of the luminescent complex within the LDH host allows the O-2-sensitivity to remain similar to that observed in solution whilst avoiding photo-degradation, thereby opening perspectives for use in oxygen sensing or singlet oxygen generation.

Published
2021

20. Thermally-induced hysteretic valence tautomeric conversions in the solid state

Author

Constance, Lecourt, Yuuta, Izumi, Lhoussain, Khrouz, François, Toche, Rodica, Chiriac, Nicolas, Bélanger-Desmarais, Christian, Reber, Oscar, Fabelo, Katsuya, Inoue, Cédric, Desroches, and Dominique, Luneau

Abstract

Near room temperature hysteretic thermo-induced valence tautomerism was discovered in a layered 2D-coordination polymer of manganese(ii) with nitronyl nitroxide radicals separated by ClO4- anions (1). This opens a novel approach towards switchable materials with hysteresis and under ambient conditions with prospects for applications and for investigating solid-state intramolecular electron transfers. Herein, two new compounds with similar layered structures where the anions (X) are BF4- (2) or PF6- (3) are presented. Their magnetic behaviors also reveal hysteretic thermo-induced valence tautomeric conversions but in two steps and evidencing a strong effect of the anion. This occurs near room temperature (278-220 K) for 2 and higher for 3 (380-330 K). Their single crystal structures at different temperatures show that this involves two successive thermally-triggered electron transfers with switching between three redox tautomers formulated as {[MnII2-yMnIIIy(NITIm)3-y(NITRed)y]X}n, where y is temperature dependent. Upon cooling from the high-temperature redox-tautomer (y = 0) to the intermediate one (y = 1), half of the manganese(ii) centers are oxidized to manganese(iii) and 1/3 of the nitronyl nitroxide radicals (NITIm-) are reduced to the aminoxyl form (NITRed2-). On further cooling, the second half of the manganese(ii) centers are oxidized and another 1/3 of the radicals are reduced to reach the low-temperature redox-tautomer (y = 2). Upon reheating, reverse electron transfers occur. This is complementarily supported by X-ray powder measurements, differential scanning calorimetry, and electron paramagnetic resonance and Raman spectroscopies. These multi-stable compounds in which manganese ions exchange reversibly their electron with the nitronyl nitroxide radical are outstanding rare examples of two-step valence tautomerism in the solid state promoted by the polymeric structure.

Published
2020

21. Synthesis and Structure of Fluorinated (Benzo[d]imidazol-2-yl)methanols: Bench Compounds for Diverse Applications

Author

Galina A. Selivanova, Irina Yu. Bagryanskaya, Dominique Luneau, Alexander Makarov, Vasily Romanov, Evgeny V. Tretyakov, and Jiayao Li

Subjects
H-bonding, Benzimidazole, crystal structure, General Chemical Engineering, chemistry.chemical_element, Crystal structure, 010402 general chemistry, Ring (chemistry), 01 natural sciences, Medicinal chemistry, polyfluorinated 1,2-diaminobenzenes, Inorganic Chemistry, chemistry.chemical_compound, fluorinated benzimidazoles, lcsh:QD901-999, Imidazole, General Materials Science, Benzene, 1D, 2D, and 3D structures, heterocyclization, 010405 organic chemistry, Hydrogen bond, Chemistry, Intermolecular force, Condensed Matter Physics, 0104 chemical sciences, Fluorine, lcsh:Crystallography
Abstract

A simple and general approach to the synthesis (from commercial precursors) of eight out of nine possible (benzo[d]imidazol-2-yl)methanols fluorinated on the benzene ring is reported. Molecular and crystalline structures of most compounds were solved by X-ray diffraction analysis. This made it possible to reveal the influence of the number and arrangement of fluorine atoms in the benzene cycle on the formation of intermolecular hydrogen bonds. It was found that the more fluorine atoms are present in a compound, the higher the dimensionality of the H-bonded structure is. Moreover, the presence of fluorine atoms in the synthesized compounds leads to the emergence of C&ndash, F&hellip, &pi, interactions affecting crystal packing. The synthesized fluorinated (benzo[d]imidazol-2-yl)methanols may serve as excellent bench compounds for the synthesis of a systematic series of fluorine-containing derivatives to study structure&ndash, property correlations in various fields of research from medicine to materials science.

Published
2020

22. Structural and spectroscopic investigations of nine-coordinate redox active lanthanide complexes with a pincer O,N,O ligand

Author

R. Barré, Christian Philouze, M Bryden, Daniel Imbert, Fabrice Thomas, D. Mouchel Dit Leguerrier, Olivier Jarjayes, Jennifer K. Molloy, Dominique Luneau, Département de Chimie Moléculaire - Chimie Inorganique Redox Biomimétique (DCM - CIRE ), Département de Chimie Moléculaire (DCM), Université Grenoble Alpes (UGA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université Grenoble Alpes (UGA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Catalyse Bioinorganique et Environnement (BioCE ), Laboratoire de Chimie et Biologie des Métaux (LCBM - UMR 5249), Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche Interdisciplinaire de Grenoble (IRIG), Direction de Recherche Fondamentale (CEA) (DRF (CEA)), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Direction de Recherche Fondamentale (CEA) (DRF (CEA)), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Grenoble Alpes (UGA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche Interdisciplinaire de Grenoble (IRIG), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Grenoble Alpes (UGA), Université Grenoble Alpes (UGA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Laboratoire des Multimatériaux et Interfaces (LMI), Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Département de Chimie Moléculaire - Chimie Inorganique Redox (DCM - CIRE ), Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université Grenoble Alpes (UGA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université Grenoble Alpes (UGA), Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université Grenoble Alpes (UGA), ANR-17-EURE-0003,CBH-EUR-GS,CBH-EUR-GS(2017), and ANR-17-CE07-0034,Co-lantha,Complexes de lanthanides comme sondes redox radicalaires(2017)

Subjects
Lanthanide, 010405 organic chemistry, Ligand, Chemistry, Diradical, Crystal structure, Zero field splitting, 010402 general chemistry, 01 natural sciences, 3. Good health, 0104 chemical sciences, law.invention, Inorganic Chemistry, Crystallography, Absorption band, law, [CHIM.CRIS]Chemical Sciences/Cristallography, Molecule, [CHIM.COOR]Chemical Sciences/Coordination chemistry, Electron paramagnetic resonance
Abstract

International audience; The lanthanide complexesEuL(3),GdL3,YbL(3)andLuL(3)of theN,N '-bis(2-hydroxy-di-3,5-tert-butylphenyl)amine were prepared. The X-Ray crystal structures ofGdL(3)andLuL(3)demonstrated a nine-coordinate sphere with three ligand molecules under their anionic diamagnetic form (Cat-N-BQ)(-). The complexes showed three oxidation events (Eox11/2 = 0.15-0.16 V,E-1/2(2)= 0.51-55 V, andE(1/2)(3)= 0.75-0.78 Vvs.Fc(+)/Fc)viacyclic voltammetry, corresponding to the successive oxidation of the aminophenolate moeities to iminosemiquinone species. The complexesGdL(3)andYbL(3)were characterized by EPR spectroscopy, allowing for the determination of the zero field splitting (ZFS) parameters in the first case. The monocations(LnL(3))(+)and monoanions(LnL(3))(-)were electrochemically generated (Ln = Eu, Gd, Yb, Lu), as well as the dicationsYbL(3)(2+)andLuL(3)(2+). The spins are antiferromagnetically exchange coupled in the diradical speciesLuL(3)(2+)(|D| = 260 MHz,E= 0). All the complexes (incl. neutral) possess a strong absorption band in the NIR region (730-840 nm,epsilon> 19 mM(-1)cm(-1)) corresponding to ligand-based transitions.

Published
2020

23. Understanding Chemical Selectivity through Well Selected Excited States

Author

Frédéric Guégan, Paul W. Ayers, F. De Proft, Christophe Morell, Vincent Tognetti, Henry Chermette, Dominique Luneau, Laurent Joubert, T. Pigeon, Institut de Chimie des Milieux et Matériaux de Poitiers (IC2MP), Université de Poitiers-Institut national des sciences de l'Univers (INSU - CNRS)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Chemometrics and Theoretical Chemistry - Chimiométrie et chimie théorique, Institut des Sciences Analytiques (ISA), Institut de Chimie du CNRS (INC)-Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-Centre National de la Recherche Scientifique (CNRS), Algemene Chemie, Vrije Universiteit Brussel (VUB), Chimie Organique et Bioorganique : Réactivité et Analyse (COBRA), Institut Normand de Chimie Moléculaire Médicinale et Macromoléculaire (INC3M), Institut de Chimie du CNRS (INC)-École Nationale Supérieure d'Ingénieurs de Caen (ENSICAEN), Normandie Université (NU)-Normandie Université (NU)-Institut national des sciences appliquées Rouen Normandie (INSA Rouen Normandie), Institut National des Sciences Appliquées (INSA)-Normandie Université (NU)-Institut National des Sciences Appliquées (INSA)-Université Le Havre Normandie (ULH), Normandie Université (NU)-Université de Rouen Normandie (UNIROUEN), Normandie Université (NU)-Centre National de la Recherche Scientifique (CNRS)-Université de Caen Normandie (UNICAEN), Normandie Université (NU)-Institut de Chimie du CNRS (INC)-École Nationale Supérieure d'Ingénieurs de Caen (ENSICAEN), Normandie Université (NU)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie Organique Fine (IRCOF), Université de Rouen Normandie (UNIROUEN), Institut National des Sciences Appliquées (INSA)-Normandie Université (NU)-Institut National des Sciences Appliquées (INSA)-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS), McMaster University Hamilton - Department of Chemistry & Chemical Biology, Laboratoire des Multimatériaux et Interfaces (LMI), Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), and Chemistry

Subjects
010304 chemical physics, Chemistry, 010402 general chemistry, 01 natural sciences, 0104 chemical sciences, [CHIM.THEO]Chemical Sciences/Theoretical and/or physical chemistry, Chemical physics, Excited state, 0103 physical sciences, [CHIM]Chemical Sciences, Reactivity (chemistry), Physical and Theoretical Chemistry, Perturbation theory, Selectivity
Abstract

International audience; In this publication, we propose a new set of reactivity/selectivity descriptors, derived within a Rayleigh–Schrödinger perturbation theory framework, for chemical systems undergoing an electrostatic (point-charge) perturbation. From the electron density polarization at first order, qualitative insight on reactivity is retrieved, while more quantitative information (noteworthy selectivity) can be obtained from either the second-order energy response or the number of shifted electrons under perturbation. Noteworthily, only a small number of excitations contribute significantly to the overall responses to perturbation, suggesting chemical reactivity could be foreseen by a careful scrutiny of the electron density reorganization upon excitation.

Published
2020

24. Photogeneration of Manganese(III) from Luminescent Manganese(II) Complexes with Thiacalixarene Ligands: Synthesis, Structures and Photophysical Properties

Author

Niall O'Toole, Lhoussain Khrouz, Arnaud Brioude, Dominique Luneau, Yan Suffren, Constance Lecourt, Andreas Hauser, Erwann Jeanneau, Cédric Desroches, Laboratoire des Multimatériaux et Interfaces (LMI), Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Institut des Sciences Chimiques de Rennes (ISCR), Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA), Université de Genève (UNIGE), Laboratoire de Chimie - UMR5182 (LC), Centre National de la Recherche Scientifique (CNRS)-Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-École normale supérieure - Lyon (ENS Lyon)-Institut de Chimie du CNRS (INC), Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Université de Genève = University of Geneva (UNIGE), and École normale supérieure de Lyon (ENS de Lyon)-Université Claude Bernard Lyon 1 (UCBL)

Subjects
Anganese, Luminescence, 010405 organic chemistry, Thiacalixarene, chemistry.chemical_element, Manganese, [CHIM.INOR]Chemical Sciences/Inorganic chemistry, 010402 general chemistry, 01 natural sciences, 0104 chemical sciences, Inorganic Chemistry, chemistry, Polymer chemistry, [CHIM.COOR]Chemical Sciences/Coordination chemistry, Photooxidation, ComputingMilieux_MISCELLANEOUS
Abstract

International audience

Published
2018

25. NO Releasing and Anticancer Properties of Octahedral Ruthenium–Nitrosyl Complexes with Equatorial 1H-Indazole Ligands

Author

Vladimir B. Arion, Wee Han Ang, Ewelina Orlowska, Tara E. McDonnell, Maria V. Babak, Peter Rapta, Chinju Govind, Dominik Schaniel, Orsolya Dömötör, Venugopal Karunakaran, Michal Malček, Dominique Luneau, Éva A. Enyedy, Lukáš Bučinský, Yusuf Chouthury Shaik Farid, Michal Zalibera, Universität Wien, National University of Singapore (NUS), University of Szeged [Szeged], Slovak University of Technology in Bratislava, REQUIMTE/LAQV, Faculdade de Ciências, Universidade do Porto, National Institute for Interdisciplinary Science and Technology (CSIR), National Institute for Interdisciplinary Science and Technology [India], Nanyang Polytechnic - NYP (REPUBLIC OF SINGAPORE), School of Biotechnology and Biomolecular Sciences, University of New South Wales [Sydney] (UNSW), Laboratoire des Multimatériaux et Interfaces (LMI), Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Cristallographie, Résonance Magnétique et Modélisations (CRM2), and Université de Lorraine (UL)-Centre National de la Recherche Scientifique (CNRS)

Subjects
Models, Molecular, Indazoles, Cell Survival, Blotting, Western, chemistry.chemical_element, Antineoplastic Agents, [CHIM.THER]Chemical Sciences/Medicinal Chemistry, [CHIM.INOR]Chemical Sciences/Inorganic chemistry, Ligands, Nitric Oxide, 010402 general chemistry, 01 natural sciences, Medicinal chemistry, Ruthenium, Inorganic Chemistry, Inhibitory Concentration 50, chemistry.chemical_compound, Deprotonation, Drug Stability, X-Ray Diffraction, [CHIM.ANAL]Chemical Sciences/Analytical chemistry, Electrochemistry, Organometallic Compounds, Acetone, Humans, Physical and Theoretical Chemistry, Dichloromethane, Indazole, 010405 organic chemistry, Water, HCT116 Cells, 0104 chemical sciences, [CHIM.THEO]Chemical Sciences/Theoretical and/or physical chemistry, chemistry, Octahedron, Proton NMR, Quantum Theory, Nitrogen Oxides, Cisplatin, Cyclic voltammetry
Abstract

International audience; With the aim of enhancing the biological activity of ruthenium−nitrosyl complexes, new compounds with four equatorially bound indazole ligands, namely, trans-[RuCl(Hind) 4 (NO)]Cl 2 •H 2 O ([3]Cl 2 •H 2 O) and trans-[RuOH(Hind) 4 (NO)]Cl 2 •H 2 O ([4]Cl 2 •H 2 O), have been prepared from trans-[Ru(NO 2) 2 (Hind) 4 ] ([2]). When the pH-dependent solution behavior of [3]Cl 2 •H 2 O and [4]Cl 2 • H 2 O was studied, two new complexes with two deprotonated indazole ligands were isolated, namely [RuCl(ind) 2 (Hind) 2 (NO)] ([5]) and [RuOH(ind) 2 (Hind) 2 (NO)] ([6]). All prepared compounds were comprehensively characterized by spectroscopic (IR, UV−vis, 1 H NMR) techniques. Compound [2], as well as [3]Cl 2 •2(CH 3) 2 CO, [4]Cl 2 •2(CH 3) 2 CO, and [5]•0.8CH 2 Cl 2 , the latter three obtained by recrystallization of the first isolated compounds (hydrates or anhydrous species) from acetone and dichloromethane, respectively, were studied by X-ray diffraction methods. The photoinduced release of NO in [3]Cl 2 and [4]Cl 2 was investigated by cyclic voltammetry and resulting paramagnetic NO species were detected by EPR spectroscopy. The quantum yields of NO release were calculated and found to be low (3−6%), which could be explained by NO dissociation and recombination dynamics, assessed by femtosecond pump−probe spectroscopy. The geometry and electronic parameters of Ru species formed upon NO release were identified by DFT calculations. The complexes [3]Cl 2 and [4]Cl 2 showed considerable antiproliferative activity in human cancer cell lines with IC 50 values in low micromolar or submicromolar concentration range and are suitable for further development as potential anticancer drugs. p53-dependence of Ru−NO complexes [3]Cl 2 and [4]Cl 2 was studied and p53-independent mode of action was confirmed. The effects of NO release on the cytotoxicity of the complexes with or without light irradiation were investigated using NO scavenger carboxy-PTIO.

Published
2018

26. Revisiting the Ullman's Radical Chemistry for Phthalocyanine Derivatives

Author

Ismail Fidan, Catherine Hirel, Dominique Luneau, Vefa Ahsen, Department of chemistry - Gebze Technical University, Gebze Teknik Üniversitesi [Gebze], Laboratoire des Multimatériaux et Interfaces (LMI), Université Claude Bernard Lyon 1 (UCBL), and Université de Lyon-Université de Lyon-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)

Subjects
Nitroxide mediated radical polymerization, Radical, Context (language use), 010402 general chemistry, Electrochemistry, 01 natural sciences, Catalysis, law.invention, chemistry.chemical_compound, law, Polymer chemistry, [CHIM]Chemical Sciences, Solubility, Electron paramagnetic resonance, Ullman's synthesis, radical, 010405 organic chemistry, Organic Chemistry, dehydration, [CHIM.MATE]Chemical Sciences/Material chemistry, General Chemistry, 0104 chemical sciences, chemistry, formys-substituted phthalocyanine, Phthalocyanine, Derivative (chemistry), imino nitroxide
Abstract

International audience; Phthalocyanine derivatives do not cease to gain attention due to their numerous properties and applications (e.g., sensor, PDT). This makes them a unique scaffold for the design of new material. In this context, we were interested to develop the synthesis of an imino nitroxide‐substituted phthalocyanine by Ullman's procedure; a challenge due to the intrinsic low solubility of most phthalocyanine derivative in much solvents. To overcome this solubility problem, we designed a phthalocyanine with bulky neopentyl substituents in peripheral positions as counterpart to the imino nitroxide moieties. The imino nitroxide‐substituted phthalocyanine was obtained by condensation of a monoformyl‐substituted phthalocyanine with 2,3‐bis(hydroxylamino)‐2,3‐dimethylbutane in refluxing THF–MeOH (2:1) mixture in the presence of p ‐toluenesulfonic acid monohydrate, follow by oxidation with PbO2. Characterization was performed by electrochemistry, UV/Vis and EPR spectroscopy in solution as well as SQUID in solid state.

Published
2018

27. Polarized Neutron Diffraction: An Excellent Tool to Evidence the Magnetic Anisotropy—Structural Relationships in Molecules

Author

Beatrice GILLON and Dominique LUNEAU

Subjects
spin cluster, polarized neutron diffraction, magnetic anisotropy, Chemistry, Chemistry (miscellaneous), molecular magnetism, Materials Chemistry, QD1-999, local susceptibility tensor, transition metal complexes, Electronic, Optical and Magnetic Materials
Abstract

This publication reviews recent advances in polarized neutron diffraction (PND) studies of magnetic anisotropy in coordination compounds comprising d or f elements and having different nuclearities. All these studies illustrate the extent to which PND can provide precise and direct information on the relationship between molecular structure and the shape and axes of magnetic anisotropy of the individual metal sites. It makes this experimental technique (PND) an excellent tool to help in the design of molecular-based magnets and especially single-molecule magnets for which strong uniaxial magnetic anisotropy is required.

Published
2021

28. Synthetic Access to a Pure Polyradical Architecture: Nucleophilic Insertion of Nitronyl Nitroxide on a Cyclotriphosphazene Scaffold

Author

Vefa Ahsen, Yusuf Yerli, Emel Önal, Dominique Luneau, Ismail Fidan, Catherine Hirel, Department of chemistry - Gebze Technical University, Gebze Teknik Üniversitesi [Gebze], Yildiz Technical University (YTU), Laboratoire des Multimatériaux et Interfaces (LMI), Université Claude Bernard Lyon 1 (UCBL), and Université de Lyon-Université de Lyon-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)

Subjects
Nitroxide mediated radical polymerization, Materials science, 010405 organic chemistry, Stereochemistry, Radical, cyclotriphosphazene, [CHIM.MATE]Chemical Sciences/Material chemistry, General Chemistry, polyradicals, 010402 general chemistry, Electrochemistry, 01 natural sciences, Combinatorial chemistry, 0104 chemical sciences, chemistry.chemical_compound, nitronyl nitroxide, Monomer, electrochemistry, chemistry, Nucleophile, Nucleophilic substitution, [CHIM]Chemical Sciences, Polyphosphazene, nucleophilic substitution, Voltammetry
Abstract

International audience; An optimized nucleophilic synthetic approach featuring mild conditions and microwave energy was utilized to circumvent the classical Ullman procedure and access a polynitronyl nitroxide radical easily and in pure form. The simultaneous controlled introduction of preformed nitronyl nitroxide radicals on a cyclotriphosphazene core leads to a novel polyphosphazene monomer which is suitable for both n‐ and a p‐type redox‐active material in organic rechargeable batteries as demonstrated by electrochemistry. Additionally, absorption spectra and square‐wave voltammetry were utilized to quantify the number of nitronyl nitroxide radical units on the cyclotriphosphazene scaffold.

Published
2017

29. Synchronous Temperature and Magnetic Field Dual‐Sensing by Luminescence in a Dysprosium Single‐Molecule Magnet

Author

Victor Moshchalkov, Luís D. Carlos, Liviu F. Chibotaru, Alexandre M. P. Botas, Jérôme Long, Mikhail V. Shestakov, Rute A. S. Ferreira, Yannick Guari, Ekaterina Mamontova, Dominique Luneau, Johan Vanacken, Joulia Larionova, Paulo André, Universidade de Aveiro, Institut Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier (ICGM ICMMM), Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Centre National de la Recherche Scientifique (CNRS)-Université de Montpellier (UM)-Université Montpellier 1 (UM1)-Université Montpellier 2 - Sciences et Techniques (UM2)-Institut de Chimie du CNRS (INC), Catholic University of Leuven - Katholieke Universiteit Leuven (KU Leuven), Université Claude Bernard Lyon 1 (UCBL), and Université de Lyon

Subjects
Materials science, business.industry, chemistry.chemical_element, 02 engineering and technology, 010402 general chemistry, 021001 nanoscience & nanotechnology, 01 natural sciences, Atomic and Molecular Physics, and Optics, 0104 chemical sciences, Electronic, Optical and Magnetic Materials, Dual (category theory), Magnetic field, chemistry, Dysprosium, Optoelectronics, [CHIM.COOR]Chemical Sciences/Coordination chemistry, Single-molecule magnet, 0210 nano-technology, Luminescence, business, ComputingMilieux_MISCELLANEOUS
Abstract

International audience

Published
2021

30. Magnetic properties of cellulose-grafted reduced graphite oxide decorated with Ni nanoparticles

Author

Mohammed Hassen V. Baouab, Emmanuel Beyou, Hend Jaoua-Bahloul, Abdelwaheb Dhahri, and Dominique Luneau

Subjects
Materials science, Polymers and Plastics, Hydrazine, Doping, Metallurgy, Nanoparticle, chemistry.chemical_element, Graphite oxide, 02 engineering and technology, General Chemistry, 010402 general chemistry, 021001 nanoscience & nanotechnology, 01 natural sciences, 0104 chemical sciences, chemistry.chemical_compound, Nickel, chemistry, Chemical engineering, Materials Chemistry, Chemical reduction, Cellulose, 0210 nano-technology
Abstract

We report the immobilization of nickel nanoparticles on the surface of cellulose-grated reduced graphite oxide sheets (rGO). The decoration of GO with magnetic nickel nanoparticles was conducted in three steps. First, pure graphite oxide (GO) was functionnalized by cellulose. Then, the corresponding material was doped with Ni nanoparticles (NiNPs) using NiCl2.6H2O followed by a chemical reduction in presence of hydrazine. The resulting NiNPs/cellulose-grafted rGO material with a 20 wt% NiNPs content was found to be nearly ferroramagnetic. POLYM. ENG. SCI., 2017. © 2017 Society of Plastics Engineers

Published
2017

31. Evidencing under-barrier phenomena in a Yb( iii ) SMM: a joint luminescence/neutron diffraction/SQUID study

Author

Christophe Morell, Frédéric Guégan, Julie Jung, Béatrice Gillon, François Riobé, Olivier Maury, Jean-François Jacquot, Dominique Luneau, Boris Le Guennic, Yannick Guyot, Laboratoire des Multimatériaux et Interfaces (LMI), Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Institut des Sciences Analytiques (ISA), Institut de Chimie du CNRS (INC)-Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-Centre National de la Recherche Scientifique (CNRS), Institut des Sciences Chimiques de Rennes (ISCR), Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA), Laboratoire de Chimie - UMR5182 (LC), Centre National de la Recherche Scientifique (CNRS)-Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-École normale supérieure - Lyon (ENS Lyon)-Institut de Chimie du CNRS (INC), Laboratoire Léon Brillouin (LLB - UMR 12), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Centre National de la Recherche Scientifique (CNRS)-Université Paris-Saclay, LLB - Nouvelles frontières dans les matériaux quantiques (NFMQ), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Centre National de la Recherche Scientifique (CNRS)-Université Paris-Saclay-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Centre National de la Recherche Scientifique (CNRS)-Université Paris-Saclay, Conception d’Architectures Moléculaires et Processus Electroniques (CAMPE), SYstèmes Moléculaires et nanoMatériaux pour l’Energie et la Santé (SYMMES), Institut de Chimie du CNRS (INC)-Université Grenoble Alpes [2016-2019] (UGA [2016-2019])-Institut de Recherche Interdisciplinaire de Grenoble (IRIG), Direction de Recherche Fondamentale (CEA) (DRF (CEA)), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Direction de Recherche Fondamentale (CEA) (DRF (CEA)), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université Grenoble Alpes [2016-2019] (UGA [2016-2019])-Institut de Recherche Interdisciplinaire de Grenoble (IRIG), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Centre National de la Recherche Scientifique (CNRS), Institut Lumière Matière [Villeurbanne] (ILM), Université de Lyon-Université de Lyon, Chemometrics and Theoretical Chemistry - Chimiométrie et chimie théorique, Université de Lyon-Université de Lyon-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université Claude Bernard Lyon 1 (UCBL), ANR-15-CE29-0019-02, Agence Nationale de la Recherche, Centre National de la Recherche Scientifique (CNRS)-Université de Lyon-Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-École normale supérieure - Lyon (ENS Lyon), Université de Lyon-École normale supérieure - Lyon (ENS Lyon)-Centre National de la Recherche Scientifique (CNRS)-Université de Lyon-Université Claude Bernard Lyon 1 (UCBL), Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Centre National de la Recherche Scientifique (CNRS)-Ecole Nationale Supérieure de Chimie de Rennes-Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES), École normale supérieure - Lyon (ENS Lyon)-Université Claude Bernard Lyon 1 (UCBL), Centre National de la Recherche Scientifique (CNRS)-Université Grenoble Alpes (UGA)-Institut de Recherche Interdisciplinaire de Grenoble (IRIG), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Centre National de la Recherche Scientifique (CNRS)-Université Grenoble Alpes (UGA)-Institut de Recherche Interdisciplinaire de Grenoble (IRIG), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA), OM and FR are grateful to ANR (REDIVALAN ANR-15-CE29-0019-02 and SCOSIMLIGHT ANR-13-BS07-0022-01) for financial support., ANR-15-CE29-0019,ReDivaLan,Transfert électronique dans les organolanthanides : une approche spectroscopique et théorique(2015), ANR-13-BS07-0022,SCOSIMLIGHT,Effet d'une irradiation lumineuse sur des ions aimants à transition de spin incorporant des ligands redox(2013), Université de Lyon-Université de Lyon-Centre National de la Recherche Scientifique (CNRS)-Université Claude Bernard Lyon 1 (UCBL), Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes-Centre National de la Recherche Scientifique (CNRS), Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), École normale supérieure de Lyon (ENS de Lyon)-Université Claude Bernard Lyon 1 (UCBL), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Centre National de la Recherche Scientifique (CNRS), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Centre National de la Recherche Scientifique (CNRS)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Centre National de la Recherche Scientifique (CNRS), Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université Grenoble Alpes [2016-2019] (UGA [2016-2019])-Institut de Recherche Interdisciplinaire de Grenoble (IRIG), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université Grenoble Alpes [2016-2019] (UGA [2016-2019])-Institut de Recherche Interdisciplinaire de Grenoble (IRIG), Chemometrics and theoretical chemistry. - Chimiométrie et chimie théorique, and Université de Lyon-Université de Lyon-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université Claude Bernard Lyon 1 (UCBL)

Subjects
Ytterbium, Materials science, [CHIM.ORGA]Chemical Sciences/Organic chemistry, Relaxation (NMR), Neutron diffraction, Ab initio, chemistry.chemical_element, 02 engineering and technology, 010402 general chemistry, 021001 nanoscience & nanotechnology, 01 natural sciences, Molecular physics, 0104 chemical sciences, law.invention, Inorganic Chemistry, SQUID, Magnetization, chemistry, law, [CHIM.ANAL]Chemical Sciences/Analytical chemistry, [CHIM.COOR]Chemical Sciences/Coordination chemistry, Physics::Atomic Physics, 0210 nano-technology, Luminescence, Joint (geology)
Abstract

International audience; We report the synthesis, spectroscopic and magnetic characterisation and ab initio investigation of a new mononuclear ytterbium based complex, [YbTp2NO3], and discuss the physical mechanisms underlying the slow relaxation of its magnetisation in a moderate static field and at low temperature.

Published
2019

32. Mononuclear manganese( iii ) complexes with reduced imino nitroxide radicals by single-electron transfer and intermolecular hydrogen bonds as an intramolecular structural driving force

Author

Constance Lecourt, Cédric Desroches, Vivian Ferreol, Lhoussain Khrouz, Christian Reber, Jean-Bernard Tommasino, Nicolas Bélanger-Desmarais, Warren Madanamoothoo, Dominique Luneau, Laboratoire des Multimatériaux et Interfaces (LMI), Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Département de chimie [UdeM-Montréal], Université de Montréal (UdeM), Laboratoire de Chimie - UMR5182 (LC), Centre National de la Recherche Scientifique (CNRS)-Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-École normale supérieure - Lyon (ENS Lyon)-Institut de Chimie du CNRS (INC), and École normale supérieure de Lyon (ENS de Lyon)-Université Claude Bernard Lyon 1 (UCBL)

Subjects
Nitroxide mediated radical polymerization, 010405 organic chemistry, Chemistry, Hydrogen bond, Radical, Intermolecular force, [CHIM.MATE]Chemical Sciences/Material chemistry, 010402 general chemistry, 01 natural sciences, Tautomer, 0104 chemical sciences, law.invention, Inorganic Chemistry, Crystallography, law, Intramolecular force, [CHIM.CRIS]Chemical Sciences/Cristallography, Molecule, [CHIM]Chemical Sciences, Electron paramagnetic resonance
Abstract

International audience; Manganese(III) complexes were synthesized by one-electron transfer from a Mn(II) ion to the imino nitroxide radical 2-(2-imidazolyl)-4,4,5,5-tetramethylimidazoline-1-oxyl (IMImH) in methanol. After the manganese ions attained the +III oxidation state, the imino nitroxide radicals were found to be irreversibly reduced in the complexes. Depending on the synthesis conditions, two complexes differing by their counter-anions were isolated as single crystals. These are [Mn(IMHIm)2(MeOH)2]ClO4·H2O (1) and [Mn(IMHIm)2(MeOH)2]PF6 (2), which crystallize in the monoclinic P21/n and triclinic P1 space groups, respectively. The two complexes show Jahn–Teller distortions typical of Mn(III) centres and only reduced radicals are coordinated, as indicated by the N–O bond lengths and electroneutrality. In addition, the crystal structure analyses reveal two intermolecular hydrogen bonding networks. One involves counter-anions, water molecules and reduced radicals, and the other involves coordinated methanol molecules and imidazole moieties. These intermolecular interactions are driving forces that stabilize the two complexes. They also suggest that the tautomer is in the amino imine-oxide form after reduction of the radical and reveal the deprotonation of the imidazole ring, which is required for electroneutrality. This assessment is supported by single-crystal X-ray diffraction, EPR and Raman spectroscopy as well as magnetic and electrochemical studies.

Published
2019

33. Coordination polymers of zinc(II) and manganese(II) made by complexation of calix[4]arene functionalized with carboxylates afford alveolar materials

Author

Isabelle Gautier-Luneau, Rym Abidi, Marwa Boutar, Dominique Luneau, Mohamed Habib Noamane, Nabila Mattoussi, Cédric Desroches, Laurence Bois, Laboratoire des Multimatériaux et Interfaces (LMI), Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Faculté des Sciences de Bizerte [Université de Carthage], Université de Carthage - University of Carthage, Optique et Matériaux (OPTIMA ), Institut Néel (NEEL), and Institut polytechnique de Grenoble - Grenoble Institute of Technology (Grenoble INP )-Centre National de la Recherche Scientifique (CNRS)-Université Grenoble Alpes [2016-2019] (UGA [2016-2019])-Institut polytechnique de Grenoble - Grenoble Institute of Technology (Grenoble INP )-Centre National de la Recherche Scientifique (CNRS)-Université Grenoble Alpes [2016-2019] (UGA [2016-2019])

Subjects
Coordination polymer, chemistry.chemical_element, Zinc, Crystal structure, Manganese, Triclinic crystal system, 010402 general chemistry, 01 natural sciences, Coordination complex, Inorganic Chemistry, chemistry.chemical_compound, Materials Chemistry, [CHIM.CRIS]Chemical Sciences/Cristallography, Porous materials, [CHIM.COOR]Chemical Sciences/Coordination chemistry, Carboxylate, Physical and Theoretical Chemistry, Isostructural, chemistry.chemical_classification, 010405 organic chemistry, 0104 chemical sciences, Coordination polymers, Crystallography, chemistry, Calixarene
Abstract

International audience; 25,27-bis(methoxycarboxylic acid)-26,28-dihydroxycalix[4]arene (calixH2), so call here calix[4]arene dimethoxycarboxylic acid, was investigated for its ability to build metal–organic frameworks. When reacted with zinc or manganese chloride in DMF and deprotonated with trimethylamine it gives Zn (1) and Mn (2) coordination compounds. These crystallize in the triclinic P-1 space group and are isostructural as shown by X-ray diffraction on single crystals. The crystal structures evidence the coordination of calix[4]arenedimethoxycarboxylic acid through the carboxylate groups. This makes a 1D coordination polymer running along the c axis direction in which [MII2(calix)2(H2O)3(DMF)2] (M = Zn or Mn) neutral units are connected. Last step refinements of the crystal structure reveal a lot of residual electron density which was ascribed to uncoordinated disordered water and DMF molecules. This was treated with the SQUEEZE routine of the program PLATON from which the solvent accessible voids per unit cell volume was calculated to be 24.5% for compound 1 (Zn) and 24.9% for compound 2 (Mn). Complementary differential thermal analyses (DTA) combined with thermogravimety analysis (TGA) and mass spectrometry (MS) are in agreement with large amount of incorporated and non-coordinated water and DMF molecules. Adsorption isotherms of N2 measured for compound 1 do not show any significant porosity. The temperature dependence of the magnetic susceptibility (χ) of compound 2 evidences antiferromagnetic interactions and was best fitted with a weak antiferromagnetic exchange coupling between the manganese(II) ions J = − 1.5 cm−1 and small antiferromagnetic inter-dinuclear interactions zJ = − 1.2 cm−1 (g = 2.02).

Published
2019

34. Tetra(n-butyl)ammonium salt of a ferrimagnetic complex based on mixed-valent dinuclear ruthenium pivalate and octacyanidotungstate(V)

Author

Dariusz Matoga, Masahiro Mikuriya, Janusz Szklarzewicz, Dominique Luneau, Makoto Handa, Daisuke Yoshioka, Shun Kawauchi, Kwansei Gakuin University, Laboratoire des Multimatériaux et Interfaces (LMI), Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Uniwersytet Jagielloński w Krakowie = Jagiellonian University (UJ), and Shimane University

Subjects
crystal structure, Pivalic acid, Materials science, carboxylate, heterometallic compounds, General Chemical Engineering, Cyanide, chemistry.chemical_element, Infrared spectroscopy, Crystal structure, 010402 general chemistry, 01 natural sciences, Ruthenium, Tungsten, chemistry.chemical_compound, Magnetization, Carboxylate, Magnetic properties, Heterometallic compounds, Ferrimagnetism, [CHIM.CRIS]Chemical Sciences/Cristallography, Moiety, [CHIM.COOR]Chemical Sciences/Coordination chemistry, biology, 010405 organic chemistry, General Chemistry, biology.organism_classification, 0104 chemical sciences, Crystallography, chemistry, Tetra, magnetic properties
Abstract

International audience; A tetra (n-butyl)ammonium (n-Bu4N+) salt of Ru2–W complex consisting of dinuclear ruthenium (II,III) pivalate, ([RuIIRuIII(piv)4]+) (Hpiv = pivalic acid), and octacyanidotungstate(V), [n-Bu4N][{RuIIRuIII(piv)4}2(H2O){WV(CN)8}] (1), was synthesized and characterized by elemental analysis, infrared spectra, and temperature dependence of magnetic susceptibilities (2–300 K). The crystal structure of 1 revealed a zigzag one-dimensional chain molecule along the c axis with alternating arrangement of [RuIIRuIII(piv)4]+ and [WV(CN)8]3−, where another [RuIIRuIII(piv)4]+ unit is dangled from the [WV(CN)8]3− moiety. The magnetic susceptibilities and zero-field-cooled and field-cooled magnetization data showed that the present complex is ferrimagnetic with a Tc value of 5.5 K. The field dependence of magnetization exhibited a hysteresis with a coercive field of 150 Oe at 2 K.

Published
2019

35. Synthesis and Straightforward Quantification Methods of Imino Nitroxide-Based Hexaradical Architecture on a Cyclotriphosphazene Scaffold

Author

Vefa Ahsen, Emel Önal, Catherine Hirel, Yusuf Yerli, Ismail Fidan, Dominique Luneau, Department of chemistry - Gebze Technical University, Gebze Teknik Üniversitesi [Gebze], Yildiz Technical University (YTU), Laboratoire des Multimatériaux et Interfaces (LMI), Université Claude Bernard Lyon 1 (UCBL), and Université de Lyon-Université de Lyon-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)

Subjects
Scaffolds, Nitroxide mediated radical polymerization, Quantification methods, Absorption spectroscopy, 010405 organic chemistry, Chemistry, Condensation, [CHIM.MATE]Chemical Sciences/Material chemistry, 010402 general chemistry, Electrochemistry, 01 natural sciences, 0104 chemical sciences, law.invention, Inorganic Chemistry, law, Covalent bond, Oxidation, Polymer chemistry, [CHIM]Chemical Sciences, Redox reactions, Physical and Theoretical Chemistry, Electron paramagnetic resonance, Spectroscopy, Molecular structure, Electron paramagnetic resonance spectroscopy
Abstract

International audience; The synthesis of a homogeneous neutral hexaradical architecture consisting of six imino nitroxide radical moieties covalently bonded on a cyclotriphosphazene scaffold was reported. The synthesis of hexaradical imino nitroxide compounds follows the Ullman procedure involving the condensation of 2,3-bis(hydroxylamino)-2,3-dimethylbutane with hexa-(4-formylphenoxy)cyclotriphosphazene (3) followed by oxidation of the condensation product hexa-[4-(1-hydroxy-4,4,5,5-tetramethyl-2-imidazoline-2-yl)phenoxy]cyclotriphosphazene (2) by NaIO4. Characterization of hexaradical was performed by X-ray and SQUID in solid state and by EPR, absorption spectroscopy, and electrochemistry in solution. CV of 1 shows an oxidation peak at 1.184 V (vs SCE) and a reduction peak at −0.883 V, both characteristics of the presence of phenyl imino nitroxide (7) moieties, suggesting that the contribution of the cyclotriphosphazene core is negligible. Attention was particularly focused on developing methods, UV–vis spectroscopy and square-wave voltammetry, to quantify the number of radicals in a way to confirm easily and rapidly the polyradicals’ structure.

Published
2016

36. 1-Formyl-3-phenyl-5-(4-isopropylphenyl)-2-pyrazoline: Synthesis, characterization, antimicrobial activity and DFT studies

Author

Ponnadurai Ramasami, Nadide Kazanci, Assia Sid, Amel Messai, Ibrahim A. Alswaidan, Lydia Rhyman, Gürkan Keşan, Cemal Parlak, Dominique Luneau, Université Larbi-Ben-Mhidi [Oum-El-Bouaghi] (OEB), Lab Ingn & Sci Mat Avances ISMA, Universite Abbes Laghrour Khenchela, Ege University - EGE (Izmir, Turkey), Laboratoire des Multimatériaux et Interfaces (LMI), Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Faculty of Sciences, University of South Bohemia, České Budějovice (Budweis), University of Mauritius, and King Saud University [Riyadh] (KSU)

Subjects
Stereochemistry, Pyrazoline, Crystal structure, Antimicrobial activity, Triclinic crystal system, 010402 general chemistry, 01 natural sciences, Analytical Chemistry, Inorganic Chemistry, chemistry.chemical_compound, [CHIM.CRIS]Chemical Sciences/Cristallography, [CHIM]Chemical Sciences, Fourier transform infrared spectroscopy, Pyrazolines, Spectroscopy, Hydrogen-bonding, 010405 organic chemistry, Chemistry, Hydrogen bond, Organic Chemistry, [CHIM.MATE]Chemical Sciences/Material chemistry, 0104 chemical sciences, Crystallography, Single crystal, Cis–trans isomerism
Abstract

International audience; The structure of 1-formyl-3-phenyl-5-(4-isopropylphenyl)-2-pyrazoline synthesized as single crystal was investigated by FTIR, NMR, XRD. Experimental data were complemented by quantum mechanical calculations. XRD data show that the compound crystallizes in the triclinic system (P−1) via trans isomer (a = 6.4267(4) Å, b = 10.9259(12) Å, c = 12.4628(9) Å and α = 102.894(8)°, β = 102.535(6)°, γ = 101.633(7)°). Anti-microbial screening results indicate that the compound shows promising activity. The theoretically predicted and experimentally obtained parameters reveal further insight into pyrazoline systems.

Published
2016

37. Nano‐Nonanuclear Mixed‐Lanthanide Clusters [Eu 9– x Tb x ] Featuring Tunable Dual Luminescence Properties

Author

Christian Reber, Alexandra Fateeva, Florian Lepoivre, Ylane Malicet, Cristina M. Balogh, Guillaume Pilet, Djamila Guettas, Dominique Luneau, Emel Önal, Olivier Maury, and Camille Sonneville

Subjects
Lanthanide, 010405 organic chemistry, Chemistry, 010402 general chemistry, 01 natural sciences, 7. Clean energy, 0104 chemical sciences, 3. Good health, Ion, Inorganic Chemistry, Crystal, Crystallography, Nano, Inductively coupled plasma, Spectroscopy, Luminescence, Powder diffraction
Abstract

Five Tb3+/Eu3+ mixed nonanuclear clusters with the general formula [Eu9–xTbx(acac)16(µ3-OH)8(µ4-O)(µ4-OH)] ([Eu9–xTbx], x = 0.9–8.1, acac = acetylacetonate) were synthesized. Characterization by powder X-ray diffraction (PXRD), energy-dispersive X-ray spectroscopy (EDS) and inductively coupled plasma optical emission spectroscopy (ICP-OES) highlight a near-perfect match between the amounts of Tb3+ and Eu3+ ions input in the reaction mixture and the amounts in the clusters. The luminescence properties of these [Eu9–xTbx] clusters were investigated thoroughly in the solid state, and a strong energy transfer from the Tb3+ to Eu3+ emitters was evidenced. Thus, these nano-nonanuclear 4f clusters, which can be viewed as square pyramids that share one top, exhibit dual luminescence that can be adjusted by controlling the ratio of the lanthanide ions within the crystal architecture.

Published
2016

38. Towards the first theoretical scale of the trans effect in octahedral complexes

Author

Christophe Morell, Frédéric Guégan, Laurent Joubert, Dominique Luneau, Henry Chermette, Vincent Tognetti, Laboratoire des Multimatériaux et Interfaces (LMI), Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Chemometrics and Theoretical Chemistry - Chimiométrie et chimie théorique, Institut des Sciences Analytiques (ISA), Université de Lyon-Université de Lyon-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université Claude Bernard Lyon 1 (UCBL), Chimie Organique et Bioorganique : Réactivité et Analyse (COBRA), Institut Normand de Chimie Moléculaire Médicinale et Macromoléculaire (INC3M), Institut de Chimie du CNRS (INC)-École Nationale Supérieure d'Ingénieurs de Caen (ENSICAEN), Normandie Université (NU)-Normandie Université (NU)-Institut national des sciences appliquées Rouen Normandie (INSA Rouen Normandie), Institut National des Sciences Appliquées (INSA)-Normandie Université (NU)-Institut National des Sciences Appliquées (INSA)-Université Le Havre Normandie (ULH), Normandie Université (NU)-Université de Rouen Normandie (UNIROUEN), Normandie Université (NU)-Centre National de la Recherche Scientifique (CNRS)-Université de Caen Normandie (UNICAEN), Normandie Université (NU)-Institut de Chimie du CNRS (INC)-École Nationale Supérieure d'Ingénieurs de Caen (ENSICAEN), Normandie Université (NU)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie Organique Fine (IRCOF), Université de Rouen Normandie (UNIROUEN), and Institut National des Sciences Appliquées (INSA)-Normandie Université (NU)-Institut National des Sciences Appliquées (INSA)-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS)

Subjects
Ligand field theory, Trans effect, VALENCE, General Physics and Astronomy, 010402 general chemistry, 01 natural sciences, DENSITY-FUNCTIONAL THEORY, [CHIM.ANAL]Chemical Sciences/Analytical chemistry, Computational chemistry, 0103 physical sciences, CHEMICAL-REACTIVITY, Physical and Theoretical Chemistry, CISPLATIN BINDING, Valence (chemistry), CRYSTAL, 010304 chemical physics, Chemistry, Ligand, DUAL DESCRIPTOR, 0104 chemical sciences, [CHIM.THEO]Chemical Sciences/Theoretical and/or physical chemistry, Octahedron, METAL-COMPLEXES, LIGANDS, Density functional theory, BOND, NATURAL ORBITALS, [CHIM.CHEM]Chemical Sciences/Cheminformatics
Abstract

International audience; In this paper, we show that trans effects in octahedral complexes can primarily be related to differences in the ability, for a given ligand, to cede electron density to the metal cation under the influence of the ligand at the trans position. Using tools from conceptual DFT or from related paradigms, we highlight these effects on a set of representative examples and further provide the basis for a computational trans effect scale. This quantification notably retrieves the experimental trans orienting series.

Published
2016

39. Modeling of magnetic properties of iron thin films deposited by RF magnetron sputtering using Preisach model

Author

Hak Abaidia Seddik El, A. Bendjerad, Sebti Boukhtache, Kaddour Benyahia, A. Benhaya, and Dominique Luneau

Subjects
thin layer, Materials science, Computer Networks and Communications, Magnetometer, XRD, RF magnetron, Energy Engineering and Power Technology, 02 engineering and technology, Substrate (electronics), 01 natural sciences, Iron (Fe), law.invention, Condensed Matter::Materials Science, Nuclear magnetic resonance, law, 0103 physical sciences, Electrical and Electronic Engineering, Thin film, 010302 applied physics, Thin layers, Condensed matter physics, VSM, Mechanical Engineering, Hysteresis, Sputter deposition, 021001 nanoscience & nanotechnology, Magnetic hysteresis, Magnetic field, Hardware and Architecture, Control and Systems Engineering, lcsh:Electrical engineering. Electronics. Nuclear engineering, 0210 nano-technology, lcsh:TK1-9971, Preisach model
Abstract

Iron thin films were deposited on glass substrates using RF magnetron sputtering and their optimal deposition conditions were determined. The structure properties were analyzed using x-ray diffraction (XRD) and their magnetic hysteresis loops were obtained by Vibrating Sample Magnetometer (VSM) at room temperature. In this situation, the magnetic field is either parallel or perpendicular to the substrate plane. The main contribution of this work is to characterize the thin layers and present a mathematical model that can get best fit of the characteristics B(H). By using Preisach model, good agreement was obtained between theoretical and experimental results in both cases.

Published
2016

40. Unconventional field induced phases in a quantum magnet formed by free radical tetramers

Author

Michael Nicklas, Jochen Wosnitza, Reza Moosavi Askari, Andrea Bianchi, Christian Reber, Michel Côté, E. L. Green, Thierry Maris, Andrés Saúl, Dominique Luneau, Adrian E. Feiguin, Anthony Lannes, Nicolas Gauthier, Joseph M. Law, Centre Interdisciplinaire de Nanoscience de Marseille (CINaM), Aix Marseille Université (AMU)-Centre National de la Recherche Scientifique (CNRS), Département de Physique [Montréal], Université de Montréal (UdeM), Inorganic Chemistry Laboratory-Faculty of Chemistry, University of Bucharest (UniBuc), Laboratoire des Multimatériaux et Interfaces (LMI), Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Centre de résonance magnétique des systèmes biologiques (CRMSB), Université de Bordeaux (UB)-Centre National de la Recherche Scientifique (CNRS), Department of Physics, Northeastern University, Northeastern University [Boston], Centre National de la Recherche Scientifique (CNRS)-Aix Marseille Université (AMU), and Centre National de la Recherche Scientifique (CNRS)-Université de Bordeaux (UB)

Subjects
Physics, Condensed Matter::Quantum Gases, Strongly Correlated Electrons (cond-mat.str-el), Spins, Field (physics), Density matrix renormalization group, FOS: Physical sciences, 02 engineering and technology, 021001 nanoscience & nanotechnology, 01 natural sciences, Molecular physics, 3. Good health, Magnetic field, Condensed Matter - Strongly Correlated Electrons, Magnetization, Magnet, 0103 physical sciences, Density functional theory, [PHYS.COND]Physics [physics]/Condensed Matter [cond-mat], 010306 general physics, 0210 nano-technology, Phase diagram
Abstract

We report experimental and theoretical studies on the magnetic and thermodynamic properties of NIT-2Py, a free radical-based organic magnet. From magnetization and specific heat measurements we establish the temperature versus magnetic field phase diagram which includes two Bose-Einstein condensates (BEC) and an infrequent half magnetization plateau. Calculations based on density functional theory demonstrates that magnetically this system can be mapped to a quasi-two-dimensional structure of weakly coupled tetramers. Density matrix renormalization group calculations show the unusual characteristics of the BECs where the spins forming the low-field condensate are different than those participating in the high-field one., Comment: 12 pages, 12 figures

Published
2018

41. Teaching an old molecule new tricks Evidence and rationalisation of the slow magnetisation dynamics in [DyTp2Acac]

Author

Julie Jung, Christophe Morell, François Riobé, Boris Le Guennic, Frédéric Guégan, Dominique Luneau, Olivier Maury, Chemometrics and Theoretical Chemistry - Chimiométrie et chimie théorique, Institut des Sciences Analytiques (ISA), Institut de Chimie du CNRS (INC)-Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-Centre National de la Recherche Scientifique (CNRS), Laboratoire des Multimatériaux et Interfaces (LMI), Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Laboratoire de chimie théorique (LCT), Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS), Laboratoire de Chimie - UMR5182 (LC), Centre National de la Recherche Scientifique (CNRS)-Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-École normale supérieure - Lyon (ENS Lyon)-Institut de Chimie du CNRS (INC), Institut des Sciences Chimiques de Rennes (ISCR), Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA), ANR-15-CE29-0019-02, SCOSIMLIGHT ANR-13-BS07-0022-01, ANR-13-BS07-0022,SCOSIMLIGHT,Effet d'une irradiation lumineuse sur des ions aimants à transition de spin incorporant des ligands redox(2013), Chemometrics and theoretical chemistry. - Chimiométrie et chimie théorique, Université de Lyon-Université de Lyon-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université Claude Bernard Lyon 1 (UCBL), École normale supérieure de Lyon (ENS de Lyon)-Université Claude Bernard Lyon 1 (UCBL), Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), and Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)

Subjects
Materials science, 010405 organic chemistry, Dynamics (mechanics), [CHIM.INOR]Chemical Sciences/Inorganic chemistry, 010402 general chemistry, 01 natural sciences, Molecular physics, 0104 chemical sciences, Inorganic Chemistry, Magnetization, Ab initio quantum chemistry methods, Molecule, Static field, [CHIM]Chemical Sciences, Luminescence
Abstract

International audience; We report the luminescence and magnetic properties of the mononuclear Dy(iii) complex [DyTp2Acac] (Tp = tris-pyrazolylborohydride and Acac = 2,4-pentanedionate). This complex displays peculiar slow magnetisation dynamics at low temperature in the absence of a static field, which we managed to interpret using its resolved luminescence spectrum and ab initio calculations.

Published
2018

42. New model of metalloantibiotic: synthesis, structure and biological activity of a zinc( ii ) mononuclear complex carrying two enrofloxacin and sulfadiazine antibiotics

Author

Fatma Zohra Cherchali, Maggy Hologne, Corinne Sanglar, Nina Attik, Amina Boughougal, Jean Bernard Tommasino, Dominique Luneau, Dominique Decoret, Amel Messai, Guillaume Pilet, Laboratoire des Multimatériaux et Interfaces (LMI), Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Lab Ingn & Sci Mat Avances ISMA, Universite Abbes Laghrour Khenchela, LEPCMAE, Université des Sciences et de la Technologie Houari Boumediene [Alger] (USTHB), Université de Lyon, Biophysics of complex systems, Institut des Sciences Analytiques (ISA), Institut de Chimie du CNRS (INC)-Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-Centre National de la Recherche Scientifique (CNRS), and The authors acknowledge the French-Algerian Tassili PHC Programme No 15MDU940 for the financial support

Subjects
chemistry.chemical_classification, 010405 organic chemistry, chemistry.chemical_element, Biological activity, General Chemistry, Zinc, 010402 general chemistry, 01 natural sciences, Catalysis, 0104 chemical sciences, Sulfonamide, chemistry.chemical_compound, Minimum inhibitory concentration, Sulfadiazine, chemistry, [CHIM.ANAL]Chemical Sciences/Analytical chemistry, Materials Chemistry, medicine, Enrofloxacin, [CHIM]Chemical Sciences, Carboxylate, Antibacterial activity, medicine.drug, Nuclear chemistry
Abstract

A new model of the Zn-based complex, [Zn(LH)(Erx)(ErxH)]ClO4 (sulfadiazine: LH and enrofloxacin ErxH), has been synthesised with two different, but complementary antibiotics (sulfonamide and quinolon) following an easy procedure. To evaluate the synergetic effect of this multicomponent molecule, the mononuclear complexes [Zn(L)2(H2O)(NH3)] and [Zn(Erx)3]− which each include only one of the two antibiotics (sulfadiazine: LH or enrofloxacin ErxH) were synthesized. All three compounds were characterized, including crystal structure determination by single-crystal X-ray diffraction. For all of the complexes, enrofloxacin is coordinated to Zn(II) by pyridinone and one oxygen atom of the carboxylate group in a monodente mode. The antibacterial activity, determined by the minimum inhibitory concentration on specific bacteria, has been studied on free ligands, on the corresponding mononuclear complexes and on our model.

Published
2018

43. Les rayons X et les neutrons se combinent pour révéler la densité électronique résolue enspin

Author

M. Deutsch, Jean-Michel Gillet, Béatrice Gillon, Dominique Luneau, Nicolas Claiser, Mohamed Souhassou, and Claude Lecomte

Subjects
General Medicine
Abstract

La distribution des electrons dans un cristal peut etre reconstruite avec une grande precision au moyen de la diffraction des rayons X a haute resolution, alors que la diffraction des neutrons polarises en spin permet de retrouver la densite d’aimantation. Bien que les grandeurs ainsi mesurees soient toutes deux une traduction du comportement des electrons, ces deux types d’experience de diffusion sont de nos jours interpretees par des modeles differents. Nous retracons ici les etapes ayant conduit a la premiere determination experimentale de la densite d’electrons resolue en spin par un traitement combine des donnees de diffraction de rayons X et de neutrons polarises.

Published
2015

44. Osmium–Nitrosyl Oxalato‐Bridged Lanthanide‐Centered Pentanuclear Complexes – Synthesis, Crystal Structures and Magnetic Properties

Author

Ghenadie Novitchi, Jean Bernard Tommasino, Paul-Steffen Kuhn, Nicolas Claiser, Dominique Luneau, Anatolie Gavriluta, Olga Iasco, Vadim Druta, Vladimir B. Arion, Laboratoire des sciences de l'ingénieur, de l'informatique et de l'imagerie (ICube), École Nationale du Génie de l'Eau et de l'Environnement de Strasbourg (ENGEES)-Université de Strasbourg (UNISTRA)-Institut National des Sciences Appliquées - Strasbourg (INSA Strasbourg), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Institut National de Recherche en Informatique et en Automatique (Inria)-Les Hôpitaux Universitaires de Strasbourg (HUS)-Centre National de la Recherche Scientifique (CNRS)-Matériaux et Nanosciences Grand-Est (MNGE), Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut National de la Santé et de la Recherche Médicale (INSERM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut National de la Santé et de la Recherche Médicale (INSERM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Réseau nanophotonique et optique, Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA)-Centre National de la Recherche Scientifique (CNRS), Cristallographie, Résonance Magnétique et Modélisations (CRM2), Université de Lorraine (UL)-Centre National de la Recherche Scientifique (CNRS), University of Vienna [Vienna], Laboratoire des Multimatériaux et Interfaces (LMI), Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Universität Wien, Université de Lyon-Université de Lyon-Centre National de la Recherche Scientifique (CNRS), Laboratoire national des champs magnétiques intenses - Grenoble (LNCMI), Centre National de la Recherche Scientifique (CNRS)-Université Toulouse III - Paul Sabatier (UPS), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Institut National des Sciences Appliquées - Toulouse (INSA Toulouse), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Université Joseph Fourier - Grenoble 1 (UJF)-Université Grenoble Alpes (UGA), Institut National des Sciences Appliquées - Strasbourg (INSA Strasbourg), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Université de Strasbourg (UNISTRA)-Centre National de la Recherche Scientifique (CNRS)-École Nationale du Génie de l'Eau et de l'Environnement de Strasbourg (ENGEES)-Réseau nanophotonique et optique, Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Matériaux et nanosciences d'Alsace (FMNGE), and Institut de Chimie du CNRS (INC)-Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Strasbourg (UNISTRA)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS)

Subjects
Lanthanide, Materials science, Coordination number, FOS: Physical sciences, chemistry.chemical_element, Infrared spectroscopy, Heterometallic complexes, Crystal structure, 010402 general chemistry, 01 natural sciences, Drug design, Coordination complex, Inorganic Chemistry, Magnetic properties, Lanthanides, [CHIM.CRIS]Chemical Sciences/Cristallography, [CHIM]Chemical Sciences, [CHIM.COOR]Chemical Sciences/Coordination chemistry, Osmium, ComputingMilieux_MISCELLANEOUS, chemistry.chemical_classification, Condensed Matter - Materials Science, 010405 organic chemistry, Materials Science (cond-mat.mtrl-sci), Yttrium, Magnetic susceptibility, 0104 chemical sciences, Crystallography, chemistry, Anticancer agents, [PHYS.COND.CM-MS]Physics [physics]/Condensed Matter [cond-mat]/Materials Science [cond-mat.mtrl-sci]
Abstract

International audience; A series of pentanuclear heterometallic coordination compounds of the general formula (Bu4N)(5)[Ln\Os(NO)(mu-ox)-Cl-3\(4)(H2O)(n)] [Ln = Y (for 2) and Dy (for 3') when n = 0; Ln = Dy (for 3), Tb (for 4), and Gd (for 5) when n = 1] were synthesized by the reaction of the precursor (Bu4N)(2)[Os(NO)(ox)-Cl-3] (1) with the respective lanthanide(III) (Gd, Tb, Dy) or yttrium(III) chloride. For the five new complexes, the coordination numbers eight or nine are found for the central metal ion. The compounds were fully characterized by elemental analysis, IR spectroscopy, single-crystal X-ray diffraction analysis, magnetic susceptibility measurements, and ESI mass spectrometry. In addition, compound 1 was studied by UV/Vis spectroscopy and cyclic voltammetry. The X-ray diffraction analyses revealed that the anionic complexes consist of a lanthanide or yttrium core bridged through oxalato ligands to four octahedral osmium-nitrosyl moieties. This picture, in which the central ion is eight-coordinate, holds for lanthanide ions with an ionic radius smaller than that of the dysprosium(III) ion. For larger ionic radii, the central metal ion is nine-coordinate, as the coordination sphere is completed by one molecule of water. Only in the case of dysprosium-(III), it was possible to obtain complexes with both coordination numbers 8 and 9. This implies that dysprosium(III) is the tilt limit between the two coordination numbers in this series. The bond length Ln-O decreases from Dy to Gd. The nine-coordinate complexes are energetically more favored for lanthanide ions with a radius larger than that of the dysprosium-(III) ion, and the eight-coordinate complexes are favored for smaller ions. Magnetic studies of the series of compounds showed that the osmium precursor 1 as well as the yttrium compound 2 are diamagnetic, whereas the magnetism of the gadolinium, terbium, and dysprosium complexes is due to isolated lanthanide ions.

Published
2015

45. Magneto-chiral dichroism of CsCuCl 3

Author

Satoshi Toyoda, Nobuyuki Abe, Katsuya Inoue, Masafumi Sera, Jun Akimitsu, Shojiro Kimura, A. Sera, Dominique Luneau, Yusuke Tokunaga, Isabelle Gautier-Luneau, Taka-hisa Arima, Yusuke Kousaka, Julien Zaccaro, Nakagawa Naoyuki, Department of Advanced Materials Sciences, The University of Tokyo (UTokyo), Institute for Materials Research, Tohoku University [Sendai], Optique et Matériaux (OPTIMA ), Institut Néel (NEEL), Institut polytechnique de Grenoble - Grenoble Institute of Technology (Grenoble INP )-Centre National de la Recherche Scientifique (CNRS)-Université Grenoble Alpes [2016-2019] (UGA [2016-2019])-Institut polytechnique de Grenoble - Grenoble Institute of Technology (Grenoble INP )-Centre National de la Recherche Scientifique (CNRS)-Université Grenoble Alpes [2016-2019] (UGA [2016-2019]), Laboratoire des Multimatériaux et Interfaces (LMI), Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Research Institute for Interdisciplinary Science, Okayama University, Graduate School of Science [Higashi-Hiroshima], Hiroshima University, Department of Quantum Matter/ADSM (ADSM), and Center for Chiral Science

Subjects
Physics, Condensed matter physics, 02 engineering and technology, Dichroism, 021001 nanoscience & nanotechnology, 01 natural sciences, Magnetic field, Ion, Magnetization, Attenuation coefficient, 0103 physical sciences, Vibrational circular dichroism, Cluster (physics), [PHYS.COND.CM-MS]Physics [physics]/Condensed Matter [cond-mat]/Materials Science [cond-mat.mtrl-sci], 010306 general physics, 0210 nano-technology, Magneto, ComputingMilieux_MISCELLANEOUS
Abstract

In this Rapid Communication, we investigate the magneto-chiral dichroism (MChD) of right- and left-handed ${\mathrm{CsCuCl}}_{3}$ crystals in a strong magnetic field up to 14.5 T. We perform near-infrared optical measurements, and the results show a change in the absorption coefficient of an intra-atomic $d\text{\ensuremath{-}}d$ transition in a ${\mathrm{Cu}}^{2+}$ ion at approximately 1.5 eV. The magnitude of MChD was found to be proportional to the magnetization, which depends on the magnetic field and temperature. We verify this relation by developing a simple ${\mathrm{CuCl}}_{6}$ cluster model.

Published
2017

46. Structural effects in octahedral carbonyl complexes: an atoms-in-molecules study

Author

Vincent Tognetti, Dominique Luneau, Laurent Joubert, Christophe Morell, Frédéric Guégan, Henry Chermette, Chimie Organique et Bioorganique : Réactivité et Analyse (COBRA), Institut Normand de Chimie Moléculaire Médicinale et Macromoléculaire (INC3M), Institut de Chimie du CNRS (INC)-École Nationale Supérieure d'Ingénieurs de Caen (ENSICAEN), Normandie Université (NU)-Normandie Université (NU)-Institut national des sciences appliquées Rouen Normandie (INSA Rouen Normandie), Institut National des Sciences Appliquées (INSA)-Normandie Université (NU)-Institut National des Sciences Appliquées (INSA)-Université Le Havre Normandie (ULH), Normandie Université (NU)-Université de Rouen Normandie (UNIROUEN), Normandie Université (NU)-Centre National de la Recherche Scientifique (CNRS)-Université de Caen Normandie (UNICAEN), Normandie Université (NU)-Institut de Chimie du CNRS (INC)-École Nationale Supérieure d'Ingénieurs de Caen (ENSICAEN), Normandie Université (NU)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie Organique Fine (IRCOF), Université de Rouen Normandie (UNIROUEN), Institut National des Sciences Appliquées (INSA)-Normandie Université (NU)-Institut National des Sciences Appliquées (INSA)-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS), Laboratoire des Multimatériaux et Interfaces (LMI), Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Chemometrics and Theoretical Chemistry - Chimiométrie et chimie théorique, Institut des Sciences Analytiques (ISA), Institut de Chimie du CNRS (INC)-Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université Claude Bernard Lyon 1 (UCBL), and Université de Lyon-Université de Lyon-Centre National de la Recherche Scientifique (CNRS)

Subjects
Electron density, Trans effect, Cis effect, chemistry.chemical_element, 010402 general chemistry, 01 natural sciences, Rhodium, Computational chemistry, [CHIM.ANAL]Chemical Sciences/Analytical chemistry, Carbonyl complexes, 0103 physical sciences, Physics::Atomic and Molecular Clusters, Physical and Theoretical Chemistry, Quantum theory of atoms-in-molecules (QTAIM), Energy decompositions, 010304 chemical physics, Atoms in molecules, Atomic descriptors, 0104 chemical sciences, Bond length, [CHIM.THEO]Chemical Sciences/Theoretical and/or physical chemistry, Crystallography, chemistry, Octahedron, Conceptual DFT, Cobalt, Metal-ligand bonds
Abstract

We gratefully acknowledge the CRIANN computational center for providing HPC resources, and LABEX SynOrg for support. VT thanks the Centre National de la Recherche Scientifique (CNRS) for a half-time "delegation".; International audience; In this paper, we assess the ability of descriptors defined within the framework of the quantum theory of atoms-in-molecules to retrieve trans and cis structural effects in 42 d(6) octahedral carbonyl organometallic complexes involving cobalt and rhodium atoms. More specifically, correlations between bond lengths in trans or cis position with respect to common orienting ligands and both local (such as molecular electrostatic potential values or the properties of critical points of the electron density Laplacian field) and integrated (over the metal atomic basin, such as multipolar moments, various energy contributions, condensed conceptual DFT quantities) properties are investigated, casting some light on the physicochemical features that drive this fundamental structural effect.

Published
2017

47. Switchable Mesomorphic Materials Based on the Ferrocene−Ferrocenium Redox System: Electron-Transfer-Generated Columnar Liquid-Crystalline Phases

Author

Dimitri Hautot, Anne-Marie Levelut, Gary J. Long, Maria-Teresa Vilches, Martin Schweissguth, Dominique Luneau, and Robert Deschenaux

Subjects
Magnetic moment, Organic Chemistry, Relaxation (NMR), Inorganic Chemistry, chemistry.chemical_compound, Paramagnetism, Crystallography, Electron transfer, Ferrocene, chemistry, Phase (matter), Organic chemistry, Physical and Theoretical Chemistry, Columnar phase, Hyperfine structure
Abstract

Oxidation of the non-mesomorphic ferrocene derivative 1 with silver toluene-4-sulfonate gave the ferrocenium derivative 2, which showed a monotropic columnar phase. The latter two-dimensional phase is composed of ribbons, in which derivative 2 is organized into bilayers, and has a centered rectangular symmetry with a = 318.3 Å and c = 94.9 Å. The Mössbauer spectra of the ferrocene derivative 1 yields hyperfine parameters that are typical of these derivatives and are, as expected, virtually independent of temperature. In a similar fashion, the hyperfine parameters of the ferrocenium derivative 2 are typical of these derivatives, but in this case at both 78 and 4.2 K slow paramagnetic relaxation of the magnetic moment associated with the rather well isolated paramagnetic ferrocenium ion is observed. The temperature-dependent magnetic susceptibilities of 2 are in agreement with those expected for weakly interacting ferrocenium cores. No magnetic-field-induced orientation was observed upon cooling the sample from the isotropic phase down to the columnar phase. Ferrocene and ferrocenium are valuable units for the design of liquid-crystalline switches.

Published
2017

48. RF magnetron sputtering deposition of NiO/Ni bilayer and approach of the Magnetic behavior using the Preisach model

Author

Abdelilah Lahmar, A. Bendjerad, A. Benhaya, M. Zergoug, Sebti Boukhtache, Dominique Luneau, Laboratoire d'Electrotechnique de Batna (LEB), Université Hadj Lakhdar Batna 1, Laboratoire de Physique de la Matière Condensée - UR UPJV 2081 (LPMC), Université de Picardie Jules Verne (UPJV), Centre de recherche scientifique et technique en soudage et contrôle (CSC), Centre de recherche, Laboratoire des Multimatériaux et Interfaces (LMI), Université Claude Bernard Lyon 1 (UCBL), and Université de Lyon-Université de Lyon-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)

Subjects
Materials science, chemistry.chemical_element, 01 natural sciences, Condensed Matter::Materials Science, Nuclear magnetic resonance, 0103 physical sciences, Magnetic properties, [CHIM]Chemical Sciences, Thin film, [PHYS.COND]Physics [physics]/Condensed Matter [cond-mat], 010306 general physics, 010302 applied physics, Condensed matter physics, Bilayer, Nickel oxide, Non-blocking I/O, [CHIM.MATE]Chemical Sciences/Material chemistry, Sputter deposition, Condensed Matter Physics, Magnetic hysteresis, Electronic, Optical and Magnetic Materials, Magnetic anisotropy, Nickel, Ni/NiO bilayer, chemistry, Preisach model
Abstract

International audience; Bilayer of nickel and nickel oxide were deposited on glass substrates using RF magnetron sputtering technique. The magnetic properties of the prepared thin films were carried out at room temperature in both parallel and perpendicular magnetic field to the sample. The Preisach model was applied to provide a mathematical model of the magnetic hysteresis loop in the case of parallel geometry, along the easy axis of the bi-layer NiO / Ni. Good agreement was obtained between the theoretical and experimental results.

Published
2017

49. Mn(iv) and Mn(v)-radical species supported by the redox non-innocent bis(2-amino-3,5-di-tert-butylphenyl)amine pincer ligand

Author

Christian Philouze, Dominique Luneau, Tim Storr, Fabrice Thomas, Ryan M. Clarke, Khrystyna Herasymchuk, Jules Moutet, Nicolas Leconte, Département de Chimie Moléculaire - Chimie Inorganique Redox Biomimétique (DCM - CIRE ), Département de Chimie Moléculaire (DCM), Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université Grenoble Alpes [2016-2019] (UGA [2016-2019])-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université Grenoble Alpes [2016-2019] (UGA [2016-2019]), Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université Grenoble Alpes [2016-2019] (UGA [2016-2019]), Laboratoire des Multimatériaux et Interfaces (LMI), Université Claude Bernard Lyon 1 (UCBL), and Université de Lyon-Université de Lyon-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)

Subjects
010405 organic chemistry, Radical, Metals and Alloys, chemistry.chemical_element, General Chemistry, Manganese, 010402 general chemistry, Photochemistry, 01 natural sciences, Redox, Catalysis, 0104 chemical sciences, Surfaces, Coatings and Films, Electronic, Optical and Magnetic Materials, Octahedron, chemistry, Polymer chemistry, Materials Chemistry, Ceramics and Composites, [CHIM]Chemical Sciences, Chelation, Amine gas treating, Pincer ligand, ComputingMilieux_MISCELLANEOUS
Abstract

The electron-rich pincer ligand 1 has been synthesized and chelated to manganese, affording 2 in high yield. Complex 2 comprises two iminosemiquinone radicals coordinated to a Mn(iv) ion. Its two electron oxidation produces 22+, which is a stable Mn(v)-iminosemiquinone radical complex.

Published
2017

50. Magnetic relaxation in mononuclear Tb complex involving a nitronyl nitroxide ligand

Author

Zan Sun, Dai-Zheng Liao, Xiufeng Wang, Peng Hu, Licun Li, and Dominique Luneau

Subjects
Lanthanide, Nitroxide mediated radical polymerization, Denticity, Ligand, Chemistry, Radical, General Chemistry, Photochemistry, Nitroxide radical, Catalysis, Ion, Crystallography, Materials Chemistry, Magnetic relaxation
Abstract

Two new lanthanide complexes with nitronyl nitroxide radicals [Ln(hfac)3(NIT-C3H5)(H2O)] (LnIII = Gd 1, Tb 2; NIT-C3H5 = 2-cyclopropyl-4,4,5,5-tetramethylimidazoline-1-oxyl-3-oxide) have been synthesized. The two complexes possess a mononuclear structure in which the nitronyl nitroxide radical is coordinated to a Ln ion as a monodentate ligand through the NO group. Magnetic studies show that the lanthanide ion interacts ferromagnetically with the nitronyl nitroxide radical. Moreover, ac measurements show that the Tb complex exhibits frequency-dependent out-of-phase signals suggesting single-molecule magnet behavior.

Published
2014

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