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1. Fully Oxidized and Mixed-Valent Polyoxomolybdates Structured by Bisphosphonates with Pendant Pyridine Groups: Synthesis, Structure and Photochromic Properties

Author

Olivier Oms, Tarik Benali, Jérome Marrot, Pierre Mialane, Marin Puget, Hélène Serier-Brault, Philippe Deniard, Rémi Dessapt, and Anne Dolbecq

Subjects
bisphosphonate, hydrogen bonds, molybdenum, photochromism, polyoxometalate, Inorganic chemistry, QD146-197
Abstract

Hybrid organic-inorganic polyoxometalates (POMs) were synthesized in water by the reaction of a MoVI precursor with bisphosphonate ligands functionalized by pyridine groups. The fully oxidized POM [(MoVI3O8)2(O)(O3PC(O)(C3H6NH2CH2C5H4NH)PO3)2]4− has been isolated as water insoluble pure Na salt (NaMo6(Ale-4Py)2) or mixed Na/K salt (NaKMo6(Ale-4Py)2) and their structure solved using single-crystal X-ray diffraction. The mixed-valent complex [(MoV2O4)(MoVI2O6)2{O3PC(O)(C3H6N(CH2C5H4N)2(MoVIO3))PO3}2]8− was obtained as an ammonium salt (NH4Mo6(AlePy2Mo)2), in the presence of a reducing agent (hydrazine). 31P NMR spectroscopic studies in aqueous media have allowed determining the pH stability domain of NH4Mo6(AlePy2Mo)2. NaMo6(Ale-4Py)2 and NaKMo6(Ale-4Py)2 exhibit remarkable solid-state photochromic properties in ambient conditions. Under UV excitation, they develop a very fast color-change from white to deep purple and proved to be the fastest photochromic organoammonium/POM systems. The coloration kinetics has been fully quantified for both salts and is discussed in light of the hydrogen-bonding networks.

Published
2015
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2. Enhanced reversible solid-state photoswitching of a cationic dithienylethene assembled with a polyoxometalate unit

Author

Véronique Guerchais, Tsuyoshi Kawai, Marin Puget, Hélène Serier-Brault, Shohei Katao, Julien Boixel, Rémi Dessapt, Florent Boucher, Clotilde Menet, Patricia Bolle, Institut des Matériaux Jean Rouxel (IMN), Université de Nantes - UFR des Sciences et des Techniques (UN UFR ST), Université de Nantes (UN)-Université de Nantes (UN)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Ecole Polytechnique de l'Université de Nantes (EPUN), Université de Nantes (UN)-Université de Nantes (UN), Nara Institute of Science and Technology - Graduate School of Information Science (NAIST), Nara Institute of Science and Technology, 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), This work was supported by the CNRS, the Université de Nantes, the Université de Rennes 1, the Ministère de l'Enseignement Supérieur et de la Recherche, the Japan Society for the Promotion of Science and the LUMOMAT project supported by the Région des Pays de la Loire., Université de Nantes (UN)-Université de Nantes (UN)-Ecole Polytechnique de l'Université de Nantes (EPUN), Université de Nantes (UN)-Université de Nantes (UN)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), 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
Steric effects, Materials science, 010405 organic chemistry, Cationic polymerization, General Chemistry, Electronic structure, Crystal structure, 010402 general chemistry, Photochemistry, 01 natural sciences, 0104 chemical sciences, Supramolecular assembly, Photochromism, Polyoxometalate, [PHYS.COND.CM-MS]Physics [physics]/Condensed Matter [cond-mat]/Materials Science [cond-mat.mtrl-sci], Materials Chemistry, Electronic effect
Abstract

International audience; The first photochromic supramolecular assembly of a dithienylethene (DTE) cation with a polyoxometalate (POM) is elaborated. The POM unit modifies the photoswitching of the DTE in the solid state, via both steric and electronic effects, resulting in an increase of its cycloreversion rate, and an almost complete re-opening process. The crystal structure after exposure to UV light reveals a remarkable photocyclization yield of almost 28%. The structural model was greatly improved by theoretical calculations, and the absorption properties were nicely modeled from electronic structure calculations.

Published
2021

3. Polymorphism and Structural Filiations in Five New Organic–Inorganic Hybrid Salts of the Heteroleptic Cationic Iridium(III) Complex and Polyoxometalates

Author

Clotilde Menet, Jérôme Marrot, Anne Dolbecq, Patricia Bolle, Amandine Boulmier, Rémi Dessapt, Pierre Mialane, Olivier Oms, Marin Puget, Hélène Serier-Brault, Chimie Et Interdisciplinarité : Synthèse, Analyse, Modélisation (CEISAM), Université de Nantes - UFR des Sciences et des Techniques (UN UFR ST), Université de Nantes (UN)-Université de Nantes (UN)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC), Institut des Matériaux Jean Rouxel (IMN), Université de Nantes (UN)-Université de Nantes (UN)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Ecole Polytechnique de l'Université de Nantes (EPUN), Université de Nantes (UN)-Université de Nantes (UN), Institut Lavoisier de Versailles (ILV), Université de Versailles Saint-Quentin-en-Yvelines (UVSQ)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Institut Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier (ICGM ICMMM), and 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)

Subjects
Chemistry, Cationic polymerization, chemistry.chemical_element, 02 engineering and technology, General Chemistry, 010402 general chemistry, 021001 nanoscience & nanotechnology, Condensed Matter Physics, 01 natural sciences, 0104 chemical sciences, 3. Good health, Polymorphism (materials science), Organic inorganic, Polymer chemistry, [PHYS.COND.CM-MS]Physics [physics]/Condensed Matter [cond-mat]/Materials Science [cond-mat.mtrl-sci], General Materials Science, Iridium, 0210 nano-technology, Phosphorescence, ComputingMilieux_MISCELLANEOUS
Abstract

Five new hybrid compounds ionically associating the phosphorescent heteroleptic cationic iridium(III) complex [IrIII(ppy)2(bpy)]+ ([Ir]+) (ppy = 2-phenylpyridine, bpy = 2,2′-bipyridine) and anionic...

Published
2018

4. Reaction Mechanisms of the Degradation of Fluoroethylene Carbonate, an Additive of Lithium-Ion Batteries, Unraveled by Radiation Chemistry

Author

Sergey A. Denisov, Viacheslav Shcherbakov, Philippe Moreau, Marin Puget, Sophie Le Caër, Jean-Pierre Dognon, and Mehran Mostafavi

Subjects
Reaction mechanism, 010405 organic chemistry, Organic Chemistry, Solvation, chemistry.chemical_element, General Chemistry, Electrolyte, Radiation chemistry, 010402 general chemistry, Photochemistry, 01 natural sciences, Catalysis, 0104 chemical sciences, Ion, chemistry, Radiolysis, Oxidizing agent, Lithium
Abstract

Numerous additives are used in the electrolytes of lithium-ion batteries, especially for the formation of an efficient solid electrolyte interphase at the surface of the electrodes. Understanding the degradation processes of these compounds is thus important; they can be seen through radiolysis. In the case of fluoroethylene carbonate (FEC), picosecond pulse radiolysis experiments evidenced the formation of FEC.- . This radical is stabilized in neat FEC, whereas the ring opens to form more stable radical anions when FEC is a solute in other solvents, as confirmed by quantum chemistry calculations. In neat FEC, pre-solvated electrons primarily undergo attachment rather than solvation. On long timescales, the gases produced (H2 , CO, and CO2 ) were quantified. A reaction scheme for both the oxidizing and reducing pathways at stake in irradiated FEC is proposed. This work shows that the nature of the primary species formed in FEC depends on the amount of FEC in the solution.

Published
2021

5. Reaction Mechanisms of Fluoroethylene Carbonate Degradation, an Additive of Lithium-Ion Batteries, Unraveled by Radiation Chemistry

Author

Marin Puget, Viacheslav Shcherbakov, Sergey Denisov, Moreau, P., Jean-Pierre Dognon, Mehran Mostafavi, Sophie Le Caer, Laboratoire Interdisciplinaire sur l'Organisation Nanométrique et Supramoléculaire (LIONS), Nanosciences et Innovation pour les Matériaux, la Biomédecine et l'Energie (ex SIS2M) (NIMBE UMR 3685), Institut Rayonnement Matière de Saclay (IRAMIS), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut Rayonnement Matière de Saclay (IRAMIS), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Institut de Chimie Physique (ICP), Institut de Chimie du CNRS (INC)-Université Paris-Saclay-Centre National de la Recherche Scientifique (CNRS), Institut des Matériaux Jean Rouxel (IMN), Université de Nantes - UFR des Sciences et des Techniques (UN UFR ST), Université de Nantes (UN)-Université de Nantes (UN)-Ecole Polytechnique de l'Université de Nantes (EPUN), Université de Nantes (UN)-Université de Nantes (UN)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Laboratoire Structure et Dynamique par Résonance Magnétique (LCF) (LSDRM), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-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)-Institut Rayonnement Matière de Saclay (IRAMIS), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-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), Université de Nantes (UN)-Université de Nantes (UN)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Ecole Polytechnique de l'Université de Nantes (EPUN), Université de Nantes (UN)-Université de Nantes (UN), Fondation Maison de la Chimie, French EMIR&A network, Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Nantes université - UFR des Sciences et des Techniques (Nantes univ - UFR ST), Nantes Université - pôle Sciences et technologie, Nantes Université (Nantes Univ)-Nantes Université (Nantes Univ)-Nantes Université - pôle Sciences et technologie, Nantes Université (Nantes Univ)-Nantes Université (Nantes Univ)-Nantes Université - Ecole Polytechnique de l'Université de Nantes (Nantes Univ - EPUN), and Nantes Université (Nantes Univ)-Nantes Université (Nantes Univ)

Subjects
[CHIM.THEO]Chemical Sciences/Theoretical and/or physical chemistry, [CHIM.MATE]Chemical Sciences/Material chemistry
Abstract

International audience; Numerous additives are used in electrolytes of lithium-ion batteries, especially for the formation of efficient solid electrolyteinterphase at the surface of the electrodes. It is, therefore, necessary to elucidate the degradation processes of these compoundssince it directly affects the lifetime of the battery. These mechanisms can be obtained through radiolysis. In this work, weinvestigated the degradation mechanisms induced by irradiation in fluoroethylene carbonate (FEC), a cyclic carbonate, whichis an additive commonly used in lithium-ion batteries. The first reaction steps were studied by pulse radiolysis. At longtimescales, the radiolytic yields of produced gases (H$_2$, CO, and CO$_2$) were quantified. Pulse radiolysis experimentsevidenced the formation of the FEC$^{●-}$ radical anion, characterized by an absorption band centered ca. 430 nm. The radicalanion is not detected when FEC is solubilized in other solvents: ethanol, diethylcarbonate, etc. This radical is indeed stabilizedin neat FEC, whereas the ring opens to form more stable radical anions when FEC is a solute in other solvents, as confirmedby calculations. A multi-species deconvolution of the spectrum measured in pure FEC revealed a small absorption bandcentered around 560 nm, attributed to the solvated electron, decaying in ca. 100 ps. In neat FEC, excess electrons primarilyundergo attachment compared to solvation. Together with gas chromatography coupled to mass spectrometry measurements,all these observations have allowed us to propose a reaction scheme for both the oxidizing and reducing pathways at stake inirradiated FEC. This work gives clues for the reaction mechanisms undergone by FEC present in electrolytes of lithium-ionbatteries and evidences that the nature of the primary species formed in FEC depends on the amount of FEC in the solution

Published
2021

6. Tailoring the Solid-State Fluorescence of BODIPY by Supramolecular Assembly with Polyoxometalates

Author

Olivier Oms, Patricia Bolle, Pierre Mialane, Hélène Serier-Brault, Eric Faulques, Anne Dolbecq, Tarik Benali, Marin Puget, Rémi Dessapt, Jérôme Marrot, Clotilde Menet, Institut des Matériaux Jean Rouxel (IMN), Université de Nantes - UFR des Sciences et des Techniques (UN UFR ST), Université de Nantes (UN)-Université de Nantes (UN)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Ecole Polytechnique de l'Université de Nantes (EPUN), Université de Nantes (UN)-Université de Nantes (UN), Institut Lavoisier de Versailles (ILV), Université de Versailles Saint-Quentin-en-Yvelines (UVSQ)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), This work was supported by the Ministère de l’Enseignement Supérieur et de la Recherche, the CNRS, the Université de Versailles Saint Quentin en Yvelines, the Université de Nantes, the LUMOMAT project supported by the Région des Pays de la Loire and a public grant overseen by the French National Research Agency (ANR) as part of the400 500 600 700 800 900 Fluorescence Intensity (a. u.) Wavelength (nm) 'Investissements d’Avenir' program n°ANR-11-IDEX-0003-02 and CHARMMMAT ANR-11-LABX-0039., ANR-11-IDEX-0003,IPS,Idex Paris-Saclay(2011), and ANR-11-LABX-0039,CHARMMMAT,CHimie des ARchitectures MoléculairesMultifonctionnelles et des MATériaux(2011)

Subjects
Photoluminescence, Quenching (fluorescence), Supramolecular chemistry, Stacking, 02 engineering and technology, [CHIM.INOR]Chemical Sciences/Inorganic chemistry, 010402 general chemistry, 021001 nanoscience & nanotechnology, 01 natural sciences, Fluorescence, 0104 chemical sciences, Supramolecular assembly, Inorganic Chemistry, chemistry.chemical_compound, Crystallography, chemistry, Luminophore, Physical and Theoretical Chemistry, BODIPY, 0210 nano-technology
Abstract

International audience; A cationic boron dipyrromethene (BODIPY) derivative (1(+)) has been successfully combined with two polyoxometalates (POMs), the Lindqvist-type [W6O19](2-) and the beta-[Mo8O26](4-) units, into three new supramolecular fluorescent materials (1)(2)[W6O19]center dot 2CH(3)CN, (1)(2)[W6O19], and (1)(4)[Mo8O26]center dot DMF center dot H2O. The resulting hybrid compounds have been fully characterized by a combination of single-crystal X-ray diffraction, IR and UV-vis spectroscopies, and photoluminescence analyses. This self-assembly approach prevents any pi-pi stacking interactions not only between the BODIPY units, responsible for aggregation-caused quenching (ACQ) effects, but also between the BODIPY and the POMs, avoiding intermolecular charge-transfer effects. Noticeably, the POM units do not only act as bulky spacers, but their negative charge density drives the molecular arrangement of the luminophore, strongly modifying its fluorescence in the solid state. As a consequence, the 1(+) cations are organized into dimers in (1)(2)[W6O19]center dot 2CH(3)CN and (1)(2)[W6O19], which are weakly emissive at room temperature, and in a more compact layered assembly in (1)(4)[Mo8O26]center dot DMF center dot H2O, which exhibits a red-shifted and intense emission upon similar photoexcitation.

Published
2021

7. A new series of lanthanide-based complexes with a bis(hydroxy)benzoxaborolone ligand Synthesis, crystal structure, and magnetic and optical properties

Author

Guillaume Calvez, Ahmad Abdallah, Marin Puget, Carole Daiguebonne, Olivier Guillou, Yan Suffren, Kevin Bernot, 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 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
Lanthanide, Luminescence, Crystal structure, Triclinic crystal system, 010402 general chemistry, Ligands, 01 natural sciences, Dysprosium compounds, Luminescence properties, Chemical formulae, [CHIM.CRIS]Chemical Sciences/Cristallography, Molecule, Orthorhombic systems, General Materials Science, [CHIM.COOR]Chemical Sciences/Coordination chemistry, Terbium compounds, Single-molecule magnet, Rare earth elements, Optical properties, 010405 organic chemistry, Ligand, Chemistry, Chelation, Sodium, General Chemistry, Magnetic and optical properties, Molecules, Condensed Matter Physics, Chemical formula, Chlorine compounds, 0104 chemical sciences, Crystallography, Triclinic systems, Synthesis (chemical), Hydrothermal conditions, Orthorhombic crystal system, Salts, Synthetic process
Abstract

International audience; Reactions, under hydrothermal conditions, between lanthanide chlorides and the sodium salt of 2-carboxyphenylboronic acid lead to a series of lanthanide-based complexes with general chemical formula [Ln2(C7H5O2)4(C7O4H6B)2·4H2O] with Ln = Eu–Dy. During the synthetic process, the 2-carboxyphenylboronate ligand decomposes leading to benzoate (C7H5O2) and bis(hydroxy)benzoxaborolone (C7O2H6B). The crystal structure was solved on the basis of the Tb-derivative. It crystalizes in the triclinic system, space group P[1 with combining macron] (n° 2) with a = 9.3329(13) Å, b = 16.012(2) Å, c = 16.212(2) Å, α = 107.789(5)°, β = 90.226(5)°, γ = 97.585(5)°, V = 2284.16(52) Å3 and Z = 2. Its crystal structure can be described on the basis of di-lanthanides entities surrounded by ligands. Compounds that constitute this series are thermally stable up to 190 °C. Solid-state luminescence properties have been studied in detail. The magnetic properties of the Dy-derivative have also been explored. It exhibits single molecule magnet behavior. Single crystals of the sodium salt of 2-carboxyphenylboronic acid with chemical formula [Na(C7O4H6B)(H2O)]∞ have also been obtained during this study. This compound crystallizes in the orthorhombic system, space group P212121 (n° 19) with a = 4.5881(13) Å, b = 6.5905(16) Å, c = 29.644(8) Å, V = 897.0(4) Å3 and Z = 4. Its crystal structure is 2D and can be described as zigzag chains of sodium 2-carboxyphenylboronate bound to each other by coordination water molecules.

Published
2020

8. Hexalanthanide Complexes as Molecular Precursors: Synthesis, Crystal Structure, and Luminescent and Magnetic Properties

Author

Olivier Guillou, Marin Puget, Carole Daiguebonne, Kevin Bernot, Yan Suffren, Haiyun Yao, Guillaume Calvez, Christophe Lescop, 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), China Scholarship Council, Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), and Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-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
010405 organic chemistry, Chemistry, Ligand, Inorganic chemistry, Crystal structure, [CHIM.INOR]Chemical Sciences/Inorganic chemistry, 010402 general chemistry, 01 natural sciences, Chemical formula, 0104 chemical sciences, Inorganic Chemistry, Crystallography, chemistry.chemical_compound, Octahedron, [CHIM.COOR]Chemical Sciences/Coordination chemistry, Physical and Theoretical Chemistry, Isostructural, Solubility, Luminescence, Acetonitrile
Abstract

International audience; Reaction of hexanuclear octahedral molecular precursors with a 3-chlorobenzoate ligand affords an unprecedented family of isostructural polylanthanide complexes via solvothermal and microwave-assisted syntheses in an acetonitrile medium. The general chemical formula of the compounds that constitute this series is {[Ln(μ-OH)(HO)(NO)(3-cb)]·(CHCN)}, where 3-cb stands for 3-chlorobenzoate and Ln = Eu, Tb, Dy, Ho, Er, or Y. The crystal structure, solubility, and magnetic and luminescent properties of these complexes have been studied. The luminescent properties evidence that the composition of the hexalanthanide precursor is preserved during the synthetic process that is of particular interest for cases in which heterolanthanide complexes are targeted.

Published
2017

9. Chemical tailoring of Single Molecule Magnet behavior in films of Dy(III) dimers

Author

Boris Le Guennic, Marin Puget, Matteo Mannini, Agnese Magnani, Xiaohui Yi, Kevin Bernot, Thierry Guizouarn, Irene Cimatti, Roberta Sessoli, Julie Jung, Università degli Studi di Firenze = University of Florence [Firenze] (UNIFI), 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), University of Siena (University of Siena), We acknowledge financial support from ERC through the Advanced Grant 'MolNanoMas' (267746) and PRIN project 'RECORD' (20097 × 44S7)., Università degli Studi di Firenze = University of Florence (UniFI), 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), and Università degli Studi di Siena = University of Siena (UNISI)

Subjects
X-ray photoelectron spectroscopy, Materials science, Ultra-high vacuum, General Physics and Astronomy, chemistry.chemical_element, Dysprosium, Magnetic bistability, OMBD, Single Molecule Magnet, Thin film, ToF-SIMS, Surfaces, Coatings and Films, Nanotechnology, 02 engineering and technology, 010402 general chemistry, 01 natural sciences, Coatings and Films, Molecule, [CHIM]Chemical Sciences, Single-molecule magnet, Spintronics, Surfaces and Interfaces, General Chemistry, 021001 nanoscience & nanotechnology, Condensed Matter Physics, 0104 chemical sciences, Surfaces, chemistry, Magnet, Sublimation (phase transition), 0210 nano-technology
Abstract

International audience; The insertion of Single Molecule Magnets (SMMs) in spintronic devices has drawn much attention thanks to their fascinating quantum and classical magnetic properties. Although many efforts have been done in this direction, we are still in search of optimal molecules, which preserve intact the magnetic bistability at the nanoscale. In this frame, we have synthesized a new dysprosium-based dimer characterized by SMM behavior and a double-butterfly-shape hysteresis. The complex has been successfully deposited by sublimation in high vacuum and the peculiar SMM behavior of the complex is fully retained at the nanoscale demonstrating that a modification of the dimer structure aimed for enhancing the SMM character is compatible with nanostructuration purposes.

Published
2018

10. Analysis of the Magnetic Exchange Interactions in Yttrium(III) Complexes Containing Nitronyl Nitroxide Radicals

Author

Carmen J. Calzado, Kevin Bernot, Marin Puget, Olivier Cador, Boris Le Guennic, Julie Jung, Universidad de Sevilla. Departamento de Química Física, Ministerio de Economía y Competitividad (MINECO). España, 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), Departamento de Quimica Fisica, Universidad de Sevilla, CTQ-2015-69019-P, European Regional Development Fund, CTQ-2015-69019-P, Ministerio de Econom?a y Competitividad, Rennes M?tropole, 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 (ENSCR)-Institut de Chimie du CNRS (INC)-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), and Universidad de Sevilla / University of Sevilla

Subjects
Nitroxide mediated radical polymerization, Stereochemistry, Radical, Supramolecular chemistry, chemistry.chemical_element, 02 engineering and technology, Yttrium, 010402 general chemistry, 021001 nanoscience & nanotechnology, 01 natural sciences, 0104 chemical sciences, Magnetic exchange, law.invention, Inorganic Chemistry, [CHIM.THEO]Chemical Sciences/Theoretical and/or physical chemistry, Crystallography, chemistry, law, Intramolecular force, [CHIM.COOR]Chemical Sciences/Coordination chemistry, Physical and Theoretical Chemistry, Crystallization, 0210 nano-technology, Wave function
Abstract

We report a combined theoretical and experimental investigation of the exchange interactions governing the magnetic behavior of a series of nitronyl nitroxide (NIT)-based Y(III) complexes, i.e., Y(hfac)3(NIT-R)2 with R = PhOPh (1), PhOEt (2), and PhOMe (3a, 3b). Even though some of these complexes or their Dy(III) parents were previously described in the literature [ Zhao et al. Transition Met. Chem. 2006, 31, 593; Bernot et al. J. Am. Chem. Soc. 2009, 131, 5573 ], their synthesis procedure as well as their structural and magnetic properties were completely reconsidered. Depending on the nature of R and the crystallization conditions, Y(hfac)3(NIT-R)2 units can be organized as supramolecular dimers or linear or orthogonal chains. Such structural diversity within the series induces extremely different magnetic behaviors. The observed behaviors are rationalized by state-of-the-art wave function-based quantum-chemical approaches (CASSCF/DDCI) that demonstrate the existence of not only effective intramolecular interactions between the NIT-R radical ligands of an isolated Y(hfac)3(NIT-R)2 molecule but also intermolecular interactions between NIT-R moieties belonging to different Y(hfac)3(NIT-R)2 units. These results are supported by the use of spin Hamiltonian models going beyond the basic Bleaney-Bowers formalism to properly fit the experimental magnetic data. Finally, the microscopic mechanisms behind the evidenced intramolecular exchange interactions are elucidated through the inspection of the calculated wave functions. In particular, whereas the role of Y orbitals was already proposed, we herein demonstrate the contribution of the hfac- ancillary ligands in mediating the magnetic interactions between the NIT radicals. Ministerio de Economía y Competitividad CTQ-2015-69019-P

Published
2017

11. Photo-physical properties of donor-acceptor-radical triad based on functionalized tetrathiafulvalene and nitronyl nitroxide radical

Author

Kevin Bernot, Abdelkrim Gouasmia, Marin Puget, Olivier Cador, Boris Le Guennic, Lahcène Ouahab, Haiet Douib, Yan Suffren, Fabrice Pointillart, laboratoire de chimie des matériaux, Université Larbi Tébessi [Tebessa], 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), Region Bretagne, Rennes Metropole, CNRS, Universite de Rennes 1, INSA of Rennes, FEDER, ANR [ANR-13-BS07-0022-01], Algerian ministry of education and research, 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 Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), and Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-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
endocrine system, Nitroxide mediated radical polymerization, Absorption spectroscopy, General Chemical Engineering, Radical, 010402 general chemistry, Photochemistry, 01 natural sciences, chemistry.chemical_compound, tetrathiafulvalene, medicine, photo-physical properties, nitronyl nitroxide radical, 010405 organic chemistry, Ligand, [CHIM.ORGA]Chemical Sciences/Organic chemistry, Process Chemistry and Technology, Triad (anatomy), respiratory system, 0104 chemical sciences, triads, Crystallography, medicine.anatomical_structure, chemistry, electrochemistry, Intramolecular force, Cyclic voltammetry, Tetrathiafulvalene
Abstract

International audience; An acceptor-donor-radical triad based on tetrathiafulvalene (TTF)-fused (benzimidazol-2-yl)-pyridine (bzip) which is alkylated with a nitronyl nitroxide (NIT) radical derivative, has been designed and synthetized. Its X-ray structure has been refined showing a complex arrangement of head-to-tail dimers of the TTF-bzip moieties and a 1D network of short contacts between the NIT radicals. Its electrochemical behavior has been studied by cyclic voltammetry (CV) showing that the TTF and NIT moieties can be reversibly and independently oxidized. The occurrence of intramolecular ligand charge transfers (ILCT) of both TTF -> bzip and TTF -> NIT nature has been evidenced by UV-visible electronic absorption spectroscopy coupled to TD-DFT calculations. Moreover, these calculations and RPE measurements confirmed the radical form (S = 1/2) of the compound as well as the spin density mainly localized on the methyl-benzo-[1-oxy1-3-oxide-4,4,5,5-tetramethylimidazolin-2-yl] unit. Both emissions of the NIT radical and TTF-based molecular skeleton have been observed with a tunable intensity ratio depending on the irradiation energy. Finally, this new triad may be a valuable candidate for the construction of multi-property compounds by coordination of metallic ions either on the TTT-based molecular skeleton or on the NIT moieties.

Published
2017

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