Author: "Guillaume Calvez" / Topic: 010405 organic chemistry - Searchworks@Jio Institute Digital Library Search Results

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53 results on '"Guillaume Calvez"'

1. Single-chain magnet behavior in a finite linear hexanuclear molecule†

Author: Kevin Bernot, Matteo Mannini, Frédéric Gendron, Yan Suffren, Felix Houard, Carole Daiguebonne, Vincent Dorcet, Boris Le Guennic, Guillaume Calvez, Olivier Guillou, Thierry Guizouarn, 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), National Interuniversity Consortium of Materials Science and Technology (INSTM ), Università degli Studi di Firenze = University of Florence [Firenze] (UNIFI), Institut Universitaire de France (IUF), Ministère de l'Education nationale, de l’Enseignement supérieur et de la Recherche (M.E.N.E.S.R.), INSA Rennes, Rennes Metropole Region Bretagne, Strategie d'Attractivite Durable [SAD18006], MIUR-Italy Ministry of Education, Universities and Research (MIUR) [96C1700020008], Fondazione Ente Cassa di Risparmio di Firenze Fondazione Cassa Risparmio Firenze [SPINE-2 2020.1634], CNRS Centre National de la Recherche Scientifique (CNRS) European Commission, 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 Firenze = University of Florence (UniFI)
Subjects: Materials science, 010405 organic chemistry, Relaxation (NMR), Linear molecular geometry, General Chemistry, Coercivity, 010402 general chemistry, Magnetic hysteresis, 01 natural sciences, 0104 chemical sciences, 3. Good health, Dipole, Chemistry, Ab initio quantum chemistry methods, Chemical physics, Magnet, TERBIUM(III), RELAXATION, COMPLEXES, STACKING,DYNAMICS, MODEL, [CHIM]Chemical Sciences, Molecule
Abstract: The careful monitoring of crystallization conditions of a mixture made of a TbIII building block and a substituted nitronyl-nitroxide that typically provides infinite coordination polymers (chains), affords a remarkably stable linear hexanuclear molecule made of six TbIII ions and five NIT radicals. The hexanuclear units are double-bridged by water molecules but ab initio calculations demonstrate that this bridge is inefficient in mediating any magnetic interaction other than a small dipolar antiferromagnetic coupling. Surprisingly the hexanuclears, despite being finite molecules, show a single-chain magnet (SCM) behavior. This results in a magnetic hysteresis at low temperature whose coercive field is almost doubled when compared to the chains. We thus demonstrate that finite linear molecules can display SCM magnetic relaxation, which is a strong asset for molecular data storage purposes because 1D magnetic relaxation is more robust than the relaxation mechanisms observed in single-molecule magnets (SMMs) where under-barrier magnetic relaxation can operate., A stable hexanuclear molecule made of a TbIII building block and a substituted nitronyl-nitroxide radical show a single-chain magnet behavior despite being a finite molecule.
Published: 2021
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2. Colloidal suspensions of highly luminescent lanthanide-based coordination polymer molecular alloys for ink-jet printing and tagging of technical liquids

Author: David Jacob, Stéphane Freslon, Yan Suffren, Francois Le Natur, Youenn Pointel, Olivier Guillou, Kevin Bernot, Carole Daiguebonne, Guillaume Calvez, 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), Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES), Institut Universitaire de France (IUF), Ministère de l'Education nationale, de l’Enseignement supérieur et de la Recherche (M.E.N.E.S.R.), Cordouan Technologies, 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 Institut National des Sciences Appliquées (INSA)
Subjects: Lanthanide, Materials science, 010405 organic chemistry, Coordination polymer, Alloy, technology, industry, and agriculture, engineering.material, equipment and supplies, 010402 general chemistry, complex mixtures, 01 natural sciences, 0104 chemical sciences, Inorganic Chemistry, Colloid, chemistry.chemical_compound, [CHIM.POLY]Chemical Sciences/Polymers, chemistry, Chemical engineering, engineering, [CHIM.COOR]Chemical Sciences/Coordination chemistry, Luminescence
Abstract: International audience; Highly luminescent and color-tunable stable colloidal suspensions of molecular alloys are reported. They are produced via a green synthetic route in ethanol medium. The mean hydrodynamic diameter of the colloids is about 140 nm and the colloidal suspensions are stable for more than a month. The optical properties of the molecular alloy suspensions and their bulk counterparts are extremely similar. To the best of our knowledge, this series of suspensions constitutes the first example of hetero-lanthanide coordination polymer molecular alloy (LnCPMA)-based colloidal suspensions with sizeable luminescence intensity and a wide range of accessible colors. This high color tunability paves the road toward tagging of technical liquids. We also demonstrate that they can be used in ink-jet printers for luminescent anti-counterfeiting tagging.
Published: 2021
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3. Self-assembled luminescent Cu(<scp>i</scp>) tetranuclear metallacycles based on 3,3′-bipyridine ligands

Author: Guillaume Calvez, Christophe Lescop, Florent Moutier, Jana Schiller, 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), Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA), Université de Rennes (UR), ANR (ANR PRC SMAC and ANR PRCI SUPRALUM) French National Research Agency (ANR), CNRS Centre National de la Recherche Scientifique (CNRS) European Commission, French 'Ministere de lEnseignement superieur, de la Recherche et de lInnovation', French 'Ministere des Affaires Etrangeres', Alexander von Humboldt Foundation Alexander von Humboldt Foundation, ANR-20-CE92-0012,SUPRALUM,Assemblages supramoléculaires luminescents pilotés par la chimie de coordination basés sur des précurseurs de l'ion Cu(I) pré-organisés et stabilisés par des ligands portant des éléments du groupe principal(2020), ANR-19-CE07-0027,SMAC,Composés avancés multifonctionnels commutables(2019), 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), and Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA)
Subjects: 010405 organic chemistry, Chemistry, Ligand, Organic Chemistry, Supramolecular chemistry, Halide, 010402 general chemistry, 01 natural sciences, 0104 chemical sciences, Ion, Self assembled, Crystallography, Bipyridine, chemistry.chemical_compound, [CHIM]Chemical Sciences, Luminescence, Bimetallic strip
Abstract: International audience; 3,3'-Bipyridine ligand B was reacted with pre-assembled [Cu-2(mu(2)-dppm)(2)] Cu(I) bimetallic flexible precursor A according to coordination-driven supramolecular chemistry synthetic principles. Outcomes obtained revealed the necessity to formally introduce bridging halide X ions (X = Cl, Br or I) in order to conduct selectively and successfully coordination-driven supramolecular syntheses. Therefore, [Cu-2(mu(2)-dppm)(2)(mu(2)-X)] bimetallic connecting nodes presenting a potential coordination angle of ca. 120 degrees are generated, which lead upon reaction with connecting ligand B to the selective formation of new tetranuclear metallacycles C-X. These derivatives are luminescent in the solid-state at room temperature with high emission quantum yields and a study of the temperature dependence of their photophysical properties was conducted, suggesting a ligand B centered triplet origin for their luminescence.
Published: 2021
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4. Rational Design of Dual IR and Visible Highly Luminescent Light-Lanthanides-Based Coordination Polymers

Author: Guillaume Calvez, Stéphane Freslon, Carole Daiguebonne, Kevin Bernot, Francois Le Natur, Yan Suffren, Olivier Guillou, Youenn Pointel, 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: chemistry.chemical_classification, Lanthanide, 010405 organic chemistry, Chemistry, Salt (chemistry), chemistry.chemical_element, Polymer, [CHIM.INOR]Chemical Sciences/Inorganic chemistry, 010402 general chemistry, 01 natural sciences, 0104 chemical sciences, Coordination complex, Inorganic Chemistry, Lanthanum, Physical chemistry, Thermal stability, Physical and Theoretical Chemistry, Isostructural, Luminescence
Abstract: A series of isostructural homo- and heterolanthanide coordination polymers of formula [Ln2(dcpa)3(H2O)]∞ with Ln = La-Gd have been obtained by reactions in water between the lightest lanthanide chlorides and the disodium salt of 4,5-dichlorophthalic acid (H2dcpa). They present particularly high thermal stability for coordination compounds (up to 400 °C). Their luminescent properties have been studied in detail. Interestingly an insensitivity to water coordination as well as a very strong effect of optical dilution is observed. Therefore, molecular alloys with very high lanthanum concentration have been prepared. Some of them present highly tunable and very intense luminescence. For example, to the best of our knowledge, [Sm0.04La1.96(dcpa)3(H2O)]∞ presents one of the highest overall quantum yields measured so far for a Sm3+-based coordination compound (QSmLigand = 9.2%), and [Nd0.03Sm0.14Eu0.03La1.8(dcpa)3(H2O)]∞ is one of the brightest (12 Cd·m-2 under 0.75 mW·cm-2 UV flux) multiemissive visible and near-infrared lanthanide-coordination polymers reported to date.
Published: 2020
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5. Microwave-assisted synthesis of lanthanide coordination polymers with 2-bromobenzoic acid as ligand from hexa-lanthanide molecular precursors

Author: Kevin Bernot, Carole Daiguebonne, Guillaume Calvez, Yan Suffren, Olivier Guillou, Haiyun Yao, 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), China Scholarship Council, CSC, Institut National des Sciences Appliquées de Lyon, INSA Lyon, 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, 2-bromobenzoic acids, 2-bromobenzoic acid, Lanthanide coordination polymer, Molecular precursor, 010402 general chemistry, 01 natural sciences, Microwave assisted, Dysprosium compounds, Analytical Chemistry, As-ligands, General chemicals, Inorganic Chemistry, Polymer chemistry, Chemical formulae, [CHIM]Chemical Sciences, Rare earth elements, Spectroscopy, Microwave-assisted reactions, chemistry.chemical_classification, 1D coordination polymer, 010405 organic chemistry, Chemistry, Ligand, Chelation, Organic Chemistry, Polymer, HEXA, 0104 chemical sciences, Energy transfer, Nuclear complex, Microwave assisted synthesis, Coordination reactions
Abstract: International audience; Microwave-assisted reactions, between 2-bromobenzoic acid (2-bbH) and hexa-lanthanide molecular precursors of general chemical formula Ln6(µ6-O)(µ3-OH)8(NO3)6(H2O)12·2NO3·2H2O [Ln6], lead to iso-structural 1D coordination polymers of general chemical formula [Ln(2-bb)3]∞ with Ln = Eu, Tb or Dy. These compounds crystallize in the monoclinic system, space group P21/c (n°14), with the following cell parameters (for the Dy-derivative): a = 12.3809(10) Å, b = 21.8653(16) Å, c = 7.9119(7) Å, β = 98.709(3)°, V = 2117.2(3) Å3 and Z = 4. The influence of the hexa-nuclear precursors over the final coordination polymer is demonstrated. Indeed, while the hexa-nuclear complexes collapse during the synthetic process their progressive destruction affords a unique 1D coordination polymer that cannot be readily obtained otherwise. Additionally, some iso-structural hetero-lanthanide derivatives with general chemical formulas [EuxTb1-x(2-bb)3]∞ and [YxTb1-x(2-bb)3]∞ with 0 ≤ x ≤ 1 have been prepared from the corresponding hexa-nuclear complexes [Eu6xTb6-6x] and [Y6xTb6-6x], respectively. Luminescent properties have been recorded and colorimetric coordinates have been calculated for all the compounds. These measurements indicate that the molecular chains host strong intermetallic energy transfers. © 2021 Elsevier B.V.
Published: 2022
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6. Intramolecular rearrangements guided by adaptive coordination-driven reactions toward highly luminescent polynuclear Cu(<scp>i</scp>) assemblies

Author: Karine Costuas, Sloane Evariste, Vivian Wing-Wah Yam, Ali Moustafa Khalil, Mehdi Elsayed Moussa, Guillaume Calvez, Christophe Lescop, Vincent Delmas, Boris Le Guennic, Hok-Lai Wong, 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), City University of Hong Kong [Hong Kong] (CUHK), Agence Nationale de la Recherche, ANR Alexander von Humboldt-Stiftung University of Hong Kong, HKUHKU 17334216AoE/P-03/ 08 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: Materials science, Intrinsic luminescence, Adaptive coordination, Supramolecular chemistry, 010402 general chemistry, 01 natural sciences, Fluorescence, Inorganic Chemistry, Metal, Copper alloys, Platinum alloys, [CHIM]Chemical Sciences, Redistribution (chemistry), Scaffolds, Spin orbit coupling, 010405 organic chemistry, Copper compounds, Building blockes, Binary alloys, Metallacycle, Coordination-driven, Combinatorial chemistry, Photophysical properties, 0104 chemical sciences, Thermally activated delayed fluorescences, Heavy metals, visual_art, Intramolecular force, Intramolecular rearrangement, visual_art.visual_art_medium, Science, technology and society, Luminescence, Gold alloys, Coordination reactions, Supramolecular scaffolds
Abstract: International audience; Adaptive coordination-driven supramolecular chemistry based on conformationally flexible pre-organized luminescent Cu(I) precursors paves the way to the ready formation of intricate supramolecular scaffold possessing intrinsic luminescence properties. A formal ring extension of a tetrametallic Cu(I) metallacycle bearing Thermally Activated Delayed Fluorescence (TADF) properties can thus be carried out, affording a new hexametallic Cu(I) metallacycle 1 bearing modulated solid-state TADF properties. Attempts to adapt this ring extension process to the formation of targeted heterometallic Au2Cu4 and Pt2Cu8 assemblies led to the unexpected and ready formation of the Au2Cu10 and Pt4Cu11 derivatives 2 and 3, respectively. These outcomes strengthen the scope and perspectives of adaptive coordination-driven supramolecular chemistry compared to those of conventional coordination-driven supramolecular chemistry. Indeed, it guides concerted intramolecular fragmentation and redistribution of the particular building blocks used, affording selectively supramolecular scaffolds of higher nuclearity and complexity. The study of the solid-state photophysical properties of the assemblies 2 and 3 highlights enhanced and original behaviors, in which the heavy metal spin-orbit coupling values significantly influence the relaxation processes centered on the Cu(I) metal centers.
Published: 2020
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7. A Journey in Lanthanide Coordination Chemistry: From Evaporable Dimers to Magnetic Materials and Luminescent Devices

Author: Yan Suffren, Kevin Bernot, Guillaume Calvez, Olivier Guillou, Carole Daiguebonne, 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), We thank INSA Rennes, CNRS (EMERGENCE@INC program), the Region Bretagne, the Chinese Scholarship Council (CSC), the ERC Advanced Grant MolNanoMaS (project no. 267746), Italian MIUR through PRIN 'Record' (20097X44S7), and the FIRB 'Nano-PlasMag' (RBFR10OAI0) project for funding., European Project: 267746,EC:FP7:ERC,ERC-2010-AdG_20100224,MOLNANOMAS(2011), 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), and Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA)
Subjects: chemistry.chemical_classification, Lanthanide, Materials science, 010405 organic chemistry, Relaxation (NMR), General Medicine, General Chemistry, 010402 general chemistry, 01 natural sciences, 0104 chemical sciences, Coordination complex, Characterization (materials science), chemistry, X-ray photoelectron spectroscopy, Chemical physics, Molecular film, Molecule, [CHIM]Chemical Sciences, Luminescence
Abstract: International audience; Conspectus. Lanthanide ions are prime ingredients for the design of compounds, materials, and devices with unique magnetic and optical properties. Accordingly, coordination chemistry is one of the best tools for building molecular edifices from these ions because it allows careful control of the ions’ environment and of the dimensionality of the final compound.In this Account, we review our results on lanthanide-based dimers. We show how a pure fundamental study on lanthanide coordination chemistry allows the investigation of a full continuum of results from the compound to materials and then to devices. The conversion of molecules into materials is a tricky task because it requires strong molecular robustness toward the surface deposition processes as well as the preservation and detectability of the molecular properties in the material. Additionally, the passage of a material toward a device implies a material with a given function, for example, a tailored response to an external stimulus.To do so, we targeted neutral and isolated molecules whose transfer on surfaces by chemi- or physisorption is much easier than that of charged molecules or extended coordination networks. Then, we focused on molecules with very strong evaporability to avoid wet chemistry deposition processes that are more likely to damage the molecules and/or distort their geometries.We thus designed lanthanide dimers based on fluorinated β-diketonates and pyridine-N-oxide ligands. As expected, they show remarkable evaporability but also strong luminescence and interesting magnetic behavior because they behave as single-molecule magnets (SMMs). Ligand substitutions and stoichiometric modifications allow the optimization of the geometric organization of the dimers in the crystal packing as well as their evaporability, SMM behavior, luminescent properties, or their ability to be anchored on surfaces. Most of all, this family of molecules shows a strong ability to form thick films on various substrates. This allows converting these molecules to magnetic materials and luminescent devices.Magnetic materials can be designed by creating thick films of the dimers deposited on gold. These films have been designed and investigated with the most advanced techniques of on-surface imaging (atomic force microscopy, AFM), on-surface physicochemical characterization (X-ray photoelectron spectroscopy (XPS), time of flight-secondary ion mass spectroscopy (Tof-SIMS)), and on-surface magnetic investigation (low-energy muon spin relaxation (LE-μSR)). Contrary to what was previously observed on other SMM films, no depth dependence of the SMM behavior was observed. This means that the dimers do not suffer from the vacuum or substrate interface and behave similarly, whatever their localization. This exceptional magnetic robustness is a key ingredient in the creation of materials for molecular magnetic data storage.Luminescent devices can be obtained by layering molecular films of the dimers with a copper-rich solid-state electrolyte between ITO/Pt electrodes. The electromigration of Cu(2+) ions into films of Eu(3+), Tb(3+), and Dy(3+) dimers quenches their luminescence. This luminescence tuning by electromigration is reversible, and this setup can be considered to be a proof of concept of full solid-state luminescent device where reversible coding can be tailored by an electric field. It is envisioned for optical data storage purposes. In the future, it could also benefit from the SMM properties of the molecules to pave the way toward multifunctional molecular data storage devices.
Published: 2021
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8. Coordination-driven supramolecular syntheses of new homo- and hetero-polymetallic Cu( i ) assemblies: solid-state and solution characterization

Author: Karine Costuas, Guillaume Calvez, Ali Moustafa Khalil, Christophe Lescop, Chendong Xu, Vincent Delmas, Mohamed Haouas, 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), 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), Centre National de la Recherche Scientifique, China Scholarship Council, Grand Équipement National De Calcul Intensif, ANR-19-CE07-0027,SMAC,Composés avancés multifonctionnels commutables(2019), ANR-20-CE92-0012,SUPRALUM,Assemblages supramoléculaires luminescents pilotés par la chimie de coordination basés sur des précurseurs de l'ion Cu(I) pré-organisés et stabilisés par des ligands portant des éléments du groupe principal(2020), 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), and Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA)
Subjects: Materials science, 010405 organic chemistry, Coordination polymer, Supramolecular chemistry, Quantum yield, 010402 general chemistry, 01 natural sciences, 0104 chemical sciences, Characterization (materials science), Ion, Inorganic Chemistry, [CHIM.THEO]Chemical Sciences/Theoretical and/or physical chemistry, chemistry.chemical_compound, Crystallography, chemistry, Luminophore, [CHIM.COOR]Chemical Sciences/Coordination chemistry, Luminescence, Dicyanamide
Abstract: International audience; Coordination-driven supramolecular (CDS) syntheses between the pre-assembled tetrametallic flexible precursor A and pseudo-halide dicyanamide N(CN)2− (DCM) and azido N3− ions afforded selectively the discrete Cu8 assembly D and the one-dimensional coordination polymer E, respectively. Upon the reaction of E with M′(II) salts (M′ = Cu, Zn, Cd), straightforward self-dissociation/re-organisation processes take place yielding new discrete Cu8 assemblies FM′. Preservation in a solution of polymetallic Cu(I) CDS assemblies is evidenced for the first time. Solid-state luminescence properties of these derivatives are reported, revealing that D is a moderate room temperature luminophore upon UV-vis light excitation (emission quantum yield of 13%) while derivatives E, FZn and FCd are only weakly luminescent in the solid-state at low temperature
Published: 2021
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9. Straightforward coordination-driven supramolecular chemistry preparation of a discrete solid-state luminescent Cu4 polymetallic compact assembly based on conformationally flexible building blocks

Author: Sloane Evariste, Chendong Xu, Guillaume Calvez, Christophe Lescop, 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), Agence Nationale de la Recherche, ANR P-OPTOELECTR-MOLMATAlexander von Humboldt-StiftungCentre National de la Recherche Scientifique, CNRS, ANR-12-IS07-0002,P-OPTOELECTR-MOLMAT,Matériaux pi-conjugués à base de phosphore : conception, synthèse et assemblages supramoléculaires pour l'émission et la collecte de lumière, la communication électronique et le transport de charge.(2012), 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: Flexibility (anatomy), Luminescence, Dimer, Supramolecular chemistry, Solid-state, [CHIM.INOR]Chemical Sciences/Inorganic chemistry, 010402 general chemistry, 01 natural sciences, Conformational flexibility, Inorganic Chemistry, chemistry.chemical_compound, Materials Chemistry, medicine, Coordination-driven Supramolecular Chemistry, [CHIM]Chemical Sciences, Physical and Theoretical Chemistry, Bimetallic strip, Solid-state structures and properties, Cu(I) complexes, 010405 organic chemistry, Chemistry, Dppm ligand, Combinatorial chemistry, 0104 chemical sciences, medicine.anatomical_structure, Linker
Abstract: International audience; The ditopic nitrile-capped 1,4-phenylenediacetonitrile linker L3 featuring partial conformational flexibility was reacted with a flexible pre-assembled Cu(I) dimer stabilized by the bis(diphenyl-phosphino)methane dppm ligand along adaptive coordination-driven supramolecular assembling processes. It resulted in the selective and unexpected formation of a compact tetrametallic assembly associating two bimetallic building blocks with three ditopic linkers. The solid-state photophysical studies of this original Cu(I)-based assembly were analysed and showed its attractive luminescence properties.
Published: 2021
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10. Lanthanide-based molecular alloys with hydroxyterephthalate: A versatile system

Author: Stéphane Freslon, Carole Daiguebonne, Olivier Guillou, Guillaume Calvez, Yan Suffren, Jinzeng Wang, Kevin Bernot, 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), The Chinese Scholarship Council is acknowledged for its financial support in the frame of the Chinese-INSA/UT network., 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), and Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA)
Subjects: Lanthanide, Materials science, Polymers, Solvothermal method, Diffusion, Solvothermal synthesis, Evaporation, Lutetium alloys, Samarium alloys, Crystal growth, Versatile system, 010402 general chemistry, 01 natural sciences, Ion, Dysprosium alloys, General chemicals, Neodymium alloys, Lanthanum alloys, [CHIM]Chemical Sciences, General Materials Science, Lutetium compounds, Rare earth elements, Aqueous solution, Crystalline powder, Optical properties, 010405 organic chemistry, Ligand, General Chemistry, Coordination Polymers, Binary alloys, Condensed Matter Physics, Chemical formula, Chlorine compounds, 0104 chemical sciences, Reactions in water, Holmium alloys, Slow evaporation, Europium alloys, Physical chemistry, Terbium alloys, Coordination reactions
Abstract: International audience; Reactions in water between lanthanide chlorides and the disodium salt of 2-hydroxyterephthalic acid (H2hbdc) lead to six families of lanthanide-based coordination polymers depending on the lanthanide ion and the crystal growth method. Compounds that constitute family F1 have the general chemical formula [Ln(Hhbdc)(hbdc)·9H2O]∞ with Ln = La-Nd and have been obtained by slow evaporation. [Ln2(hbdc)3(H2O)6·4H2O]∞ with Ln = Sm-Eu constitute family F2 and have been obtained by solvothermal synthesis. Family F3 includes compounds, obtained by a solvothermal method, with the general chemical formula [Ln2(hbdc)3(H2O)4·4H2O]∞ with Ln = Ho-Lu plus Y and compounds obtained by slow diffusion through gels with Ln = Eu-Tb. [Ln(Hhbdc)(hbdc)(H2O)3·H2O]∞ with Ln = Tb-Dy have been obtained by solvothermal methods and constitute family F4. [Gd2(hbdc)3(H2O)8·6H2O]∞ (F5) has been obtained by slow evaporation. The last family (F6) includes compounds with the general chemical formula [Ln2(hbdc)3(H2O)8·2H2O]∞ with Ln = Nd-Tb that have been obtained by slow diffusion through gel media. Gd-Based micro-crystalline powders can be obtained by direct mixing of aqueous solutions of Gd3+ and hbdc2-. Unexpectedly, the micro-crystalline powder belongs to F5 when the lanthanide solution is added to the ligand one and to F6 when the opposite occurs. This phenomenon is also observed for the Tb- and/or Eu-based heterolanthanide coordination polymers. Their optical properties have been studied in detail.
Published: 2021
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11. Multi-Emissive Lanthanide-Based Coordination Polymers for Potential Application as Luminescent Bar-Codes

Author: Guillaume Calvez, Stéphane Freslon, Yan Suffren, Kevin Bernot, Laurent Le Pollès, Claire Roiland, Carole Daiguebonne, Jinzeng Wang, Olivier Guillou, 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), Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES), The China Scholarship Council Ph.D. Program and the cooperation program with the French UT & INSA are acknowledged for financial support., 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 Institut National des Sciences Appliquées (INSA)
Subjects: Lanthanide, chemistry.chemical_classification, 010405 organic chemistry, Chemistry, Intermetallic, Polymer, 010402 general chemistry, 01 natural sciences, Chemical formula, 0104 chemical sciences, Ion, Inorganic Chemistry, Physical chemistry, [CHIM.COOR]Chemical Sciences/Coordination chemistry, Emission spectrum, Physical and Theoretical Chemistry, Isostructural, Luminescence, ComputingMilieux_MISCELLANEOUS
Abstract: Isostructural lanthanide-based coordination polymers that are obtained by reactions in water of a lanthanide chloride and the sodium salt of 5-methoxyisophthalate (mip2-) have the general chemical formula [Ln2(mip)3(H2O)8·4H2O]∞ with Ln = Nd-Er except Pm plus Y (symbolized by [Ln2(mip)3]∞). Some of these homo-lanthanide compounds present very high luminescence brightness. The weak intermetallic energy transfer between lanthanide ions observed in these compounds allows the design of hetero-lanthanide coordination polymers with tunable luminescence properties. A molecular alloy that involved six different lanthanide ions (Nd3+, Sm3+, Eu3+, Gd3+, Tb3+, Dy3+) has been prepared and its luminescent properties have been studied. This compound, under a unique irradiation wavelength (λexc = 325 nm), exhibits almost 20 emission peaks in both the visible and the NIR regions at room temperature. This unprecedented richness of the emission spectrum could be of great interest as far as luminescent bar-codes are targeted.
Published: 2019
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12. Microcrystalline Core–Shell Lanthanide-Based Coordination Polymers for Unprecedented Luminescent Properties

Author: Guillaume Calvez, Kevin Bernot, Olivier Guillou, Valérie Demange, Carole Daiguebonne, Ahmad Abdallah, Amandine Rojo, Yan Suffren, 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), Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES), 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 Institut National des Sciences Appliquées (INSA)
Subjects: chemistry.chemical_classification, Lanthanide, 010405 organic chemistry, Intermetallic, Polymer, Crystal structure, 010402 general chemistry, 01 natural sciences, Chemical formula, 0104 chemical sciences, Coordination complex, Inorganic Chemistry, Crystallography, Microcrystalline, chemistry, [CHIM.COOR]Chemical Sciences/Coordination chemistry, Physical and Theoretical Chemistry, Luminescence
Abstract: International audience; Microcrystalline core-shell powders of lanthanide-based coordination polymers with general chemical formula ([Ln(cpbOH)])@([Ln'(cpbOH)]) with Hcpb = 1,4-carboxyphenylboronic acid have been synthesized and structurally characterized. Their luminescent properties have been studied. They are drastically different from those of heterolanthanide coordination polymers, also called "molecular alloys", that present the same crystal structure and chemical composition. Study of the photophysical properties of core-shell lanthanide-based coordination polymers reveals that it is possible to control efficiently the intermetallic energy transfers between lanthanide ions. Furthermore, multiemissive compounds, under unique irradiation, in both visible and infrared regions are easily feasible. Core-shell microstructured lanthanide-based coordination polymers have also been prepared with terephthalic (Hbdc) and trimesic (Htma) acids as ligands for evidencing that lanthanide-ion-based coordination compounds are excellent candidates for 3D molecular epitaxial growth.
Published: 2018
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13. Structural and Luminescence Properties of Anthracene- and Biphenyl-Based Lanthanide Bisphosphonate Ester Coordination Polymers

Author: Guillaume Calvez, Christophe Lescop, Kristijan Krekić, Rudolf Pietschnig, Dieter Klintuch, 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), MASH Program, TESLA Program, 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: Biphenyl, Lanthanide, Anthracene, 010405 organic chemistry, Ligand, Biphenylene, 010402 general chemistry, 01 natural sciences, Phosphonate, 3. Good health, 0104 chemical sciences, Inorganic Chemistry, chemistry.chemical_compound, Crystallography, chemistry, [CHIM.COOR]Chemical Sciences/Coordination chemistry, Physical and Theoretical Chemistry, Luminescence, ComputingMilieux_MISCELLANEOUS, Derivative (chemistry)
Abstract: Coordinative networks containing lanthanide ions attached via phosphonate ester functionalities provide remarkable luminescence properties. On the basis of ditopic phosphonic ester ligands with biphenylene and 9,10-anthracenylene bridges, a series of compounds with formal composition {[M(NO3)3]L}n or {[M(NO3)3]2(L1)3}n (L = C28H40O6P2; L1 = C26H40O6P2) with M = La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, and Y have been synthesized, structurally characterized, and the luminescence behavior was explored in the visible and NIR spectral regions, where applicable. In contrast to closely related networks based on biphenyl bisphosphonate esters from previous work, no evidence for ligand-to-metal energy transfer could be observed, despite strong near-infrared emission in some cases. Unique behavior is found for the Eu derivative with the 9,10-anthracenylene bridge, which is nonemissive, showing neither ligand- nor metal-based emission.
Published: 2018
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14. 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
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15. Lanthanide coordination polymers with 1,2-phenylenediacetate

Author: Guillaume Calvez, Yan Suffren, Stéphane Freslon, Olivier Guillou, Insa Badiane, Carole Daiguebonne, Magatte Camara, Kevin Bernot, Groupe Matériaux Inorganiques:Chimie Douce et Cristallographie (LCPM), Université deZiguinchor, 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), The French Cooperation Agency in Senegal is acknowledged for financial support., 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: Lanthanide, Luminescence, Coordination polymer, Inorganic chemistry, Crystal structure, [CHIM.INOR]Chemical Sciences/Inorganic chemistry, 010402 general chemistry, 01 natural sciences, Inorganic Chemistry, chemistry.chemical_compound, Group (periodic table), Materials Chemistry, [CHIM.COOR]Chemical Sciences/Coordination chemistry, Physical and Theoretical Chemistry, Isostructural, chemistry.chemical_classification, 010405 organic chemistry, Chemistry, Polymer, 0104 chemical sciences, Crystallography, [CHIM.POLY]Chemical Sciences/Polymers, Energy transfer, Monoclinic crystal system
Abstract: The CDIFX of Rennes is acknowledged for single crystal X-ray diffraction data collection.; International audience; Reactions in water between lanthanide chlorides and the di-sodium salt of 1,2-phenylenediacetic acid, Na2(o-pda), lead to two families of coordination polymers with respective chemical formulae [La2(o-pda)3(H2O)4,4H2O]∞ (1) and [Ln2(o-pda)3(H2O)2,2H2O]∞ (2) for Ln = Ce-Nd, Sm-Lu and Y. Compound 1 crystallises in the monoclinic system, space group C2/c (n°15), with a = 28.195(5) Å, b = 12.2305(3) Å, c = 8.7607(1) Å, β = 98.835(1)° and Z = 4. Its crystal structure and thermal properties are described. Compounds of family 2 are isostructural to a previously reported crystal structure. Luminescence properties of Eu- and Tb-based compounds have been studied.
Published: 2017
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16. Chiral supramolecular nanotubes of single-chain magnets

Author: Thierry Guizouarn, Olivier Guillou, Matteo Mannini, Vincent Dorcet, Yan Suffren, Boris Le Guennic, Frédéric Gendron, Felix Houard, Kevin Bernot, Guillaume Calvez, Carole Daiguebonne, Quentin Evrard, 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), Università degli Studi di Firenze = University of Florence [Firenze] (UNIFI), Institut Universitaire de France, SAD18006, Région Bretagne, 2018-2022, MUIR, 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 Università degli Studi di Firenze = University of Florence (UniFI)
Subjects: Materials science, Lanthanides, Nanotubes, Radicals, Single-Chain Magnets, Supramolecular, Supramolecular chemistry, chemistry.chemical_element, chirality, Terbium, 010402 general chemistry, 01 natural sciences, Catalysis, [CHIM]Chemical Sciences, Superstructure, 010405 organic chemistry, General Chemistry, General Medicine, Coercivity, 0104 chemical sciences, Crystallography, Magnetic anisotropy, chemistry, Remanence, Magnet, Ising model
Abstract: International audience; We report a Single-Chain Magnet (SCM) made of a Terbium(III) building block and a nitronyl-nitroxide radical (NIT) functionalized with an aliphatic chain. This substitution is targeted to induce a long range distortion of the polymeric chain and accordingly it gives rise to chains that are curled with almost 20 nm helical pitch. They self-organize as a chiral tubular superstructure made of 11 chains wound around each other. The supramolecular tubes have a 4.5 nm internal diameter. Overall, this forms a porous chiral network with almost 44% porosity. Ab-initio calculations highlight that each Tb III ion possesses high magnetic anisotropy. Indeed, notwithstanding the supramolecular arrangement each chain behaves as a SCM. Magnetic relaxation with both finite and infinite-size regimes is observed and confirms the validity of the Ising approximation. This is associated with quite strong coercive field and magnetic remanence (Hc = 2400 Oe MR = 2.09 µB at 0.5 K) for this class of compounds.
Published: 2020
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17. Sonocrystallization as an Efficient Way to Control the Size, Morphology, and Purity of Coordination Compound Microcrystallites: Application to a Single-Chain Magnet

Author: Yan Suffren, Matteo Mannini, Olivier Guillou, Carole Daiguebonne, Quentin Evrard, Kevin Bernot, Felix Houard, Guillaume Calvez, 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), National Interuniversity Consortium of Materials Science and Technology (INSTM ), Institut Universitaire de France (IUF), Ministère de l'Education nationale, de l’Enseignement supérieur et de la Recherche (M.E.N.E.S.R.), INSA Rennes, MIUR-Italy ('Progetto Dipartimenti di Eccellenza 2018-2022' allocated to Department of Chemistry 'Ugo Schiff'), CNRS (PICS No. 07925 FloRennes), Region Bretagne (Boost’ERC RECoord No. 1122)., 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: Sonication, Dispersity, [CHIM.INOR]Chemical Sciences/Inorganic chemistry, 010402 general chemistry, 01 natural sciences, Coordination complex, law.invention, Purity control, Inorganic Chemistry, law, AFM, terre rare, sonicazione, superficie, cristalli, [CHIM]Chemical Sciences, Sonocrystallization, Physical and Theoretical Chemistry, Crystallization, chemistry.chemical_classification, 010405 organic chemistry, Aspect ratio (image), 0104 chemical sciences, Micromixing, Characterization (materials science), chemistry, Chemical engineering, Single-Chain Magnet, Crystallite, Coordination compound, Morphology control
Abstract: International audience; The size, morphology, and purity control of coordination compound powders is a key stage for their conversion into materials and devices. In particular, surface science techniques require highly pure bulk materials with a narrow crystallite-size distribution together with straightforward, scalable, and reproducible crystallization procedures. In this work we demonstrate how sonocrystallization, i.e. the application of ultrasound during the crystallization process, can afford very quickly powders made of crystallites with controlled size, morphology, and purity. We show that this process drastically diminishes the crystallite-size distribution (low polydispersity indexes, PDI) and crystallite aspect ratio. By comparing sonicated samples with samples obtained by various silent crystallization conditions, we unambiguously show that the improvement in the crystallite morphology and size distribution is not due to any thermal effect but to the sonication of the crystallizing media. The application of sonocrystallization on crystallization batches of single-chain magnets (SCMs) maintains the chemical integrity of the SCMs together with their original magnetic behavior. Moreover, luminescent measurements show that sonocrystallization induces an efficient micromixing that drastically enhances the purity of the SCM powders. We thus propose that sonocrystallization, which is already used on organic or MOF compounds, can be applied to (magnetic) coordination compounds to readily afford bulk powders for characterization or shaping techniques that require pure, morphology- and crystallite-size-controlled powder samples.
Published: 2020
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18. Luminescent vapochromic single crystal to single crystal transition in one-dimensional coordination polymer featuring the first Cu(i) dimer bridged by an aqua ligand

Author: Sebastien Kerneis, Karine Costuas, Ali Moustafa Khalil, Chendong Xu, Guillaume Calvez, Christophe Lescop, Sloane Evariste, 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), ANR (P-OPTOELECTR-MOLMAT) French National Research Agency (ANR), French Research MinistryMinistry of Research, France, CNRSCentre National de la Recherche Scientifique (CNRS), Alexander von Humboldt FoundationAlexander von Humboldt Foundation, Chinese Scholarship CouncilChina Scholarship Council, GENCI-CINES/IDRIS [A0060800649, A0080800649], ANR-12-IS07-0002,P-OPTOELECTR-MOLMAT,Matériaux pi-conjugués à base de phosphore : conception, synthèse et assemblages supramoléculaires pour l'émission et la collecte de lumière, la communication électronique et le transport de charge.(2012), 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), and Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA)
Subjects: Materials science, 010405 organic chemistry, Coordination polymer, Ligand, Supramolecular chemistry, Crystal structure, 010402 general chemistry, 01 natural sciences, 0104 chemical sciences, law.invention, Inorganic Chemistry, chemistry.chemical_compound, Crystallography, Molecular solid, [CHIM.POLY]Chemical Sciences/Polymers, chemistry, law, [CHIM.COOR]Chemical Sciences/Coordination chemistry, Crystallization, Luminescence, Single crystal
Abstract: International audience; The reaction of the pre-assembled bimetallic Cu(i) [Cu-2(mu(2)-dppm)(2)](2+) fragment with the ligand 1,4-dicyanobenzeneB(0)in non-distilled CH(2)Cl(2)allowed the characterisation of an unexpected one-dimensional coordination polymerD, while no reaction occurred when dry CH(2)Cl(2)was used as the solvent. The X-ray crystal structure resolution performed on air-stable single crystals ofDrevealed that this coordination polymer contained the first reported bridging aqua ligand coordinated on Cu(i) bimetallic units connected byB(0)ligands within zig-zag chains. Consequently,Dwas obtained in very good yield when the synthesis was conducted in dry CH2Cl2, in which water was added as a reactant in excess. In the solid state at room temperature under UV lamp excitation,Dpresented blue-cyan eye-perceived luminescence that contrasted with the green-yellow eye-perceived luminescence emitted by single crystals ofDin the crystallisation solution. Related to this property, reversible luminescent vapochromic behaviour was observed upon the exposure of dry single crystals ofDto vapors of CH2Cl2, EtOH, CH(3)NO(2)and THF solvents. The X-ray crystal structure resolution analysis revealed that this vapochromic response occursviasingle crystal to single crystal transitions, along which the volatile solvent molecules are taken up in the very low porous dry single crystals ofD, leading to the formation of one-dimensional channels of included solvent molecules, which are mobile in the crystalline solid at room temperature. The detailed temperature -dependent photophysical studies suggest that this mobility impacts the relaxation processes within these molecular solids, resulting in luminescence vapochromic effects. The results also highlight the complexity of the relaxation processes that can take place in these heteroleptic polymetallic Cu(i) supramolecular assemblies, which are based on highly easy, affordable and quick synthetic procedures.
Published: 2020
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19. 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
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20. High Luminance of Heterolanthanide-Based Molecular Alloys by Phase-Induction Strategy

Author: Felix Houard, Stéphane Freslon, Kevin Bernot, Carole Daiguebonne, Yan Suffren, Guillaume Calvez, Youenn Pointel, Olivier Guillou, François Le Natur, 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, chemistry.chemical_classification, 010405 organic chemistry, Chemistry, Polymer, [CHIM.INOR]Chemical Sciences/Inorganic chemistry, 010402 general chemistry, 01 natural sciences, Chemical formula, 0104 chemical sciences, High luminance, Ion, Inorganic Chemistry, Crystallography, Phase (matter), Physical and Theoretical Chemistry, Isostructural, Luminescence, ComputingMilieux_MISCELLANEOUS
Abstract: Reactions in water of lanthanide chlorides with the sodium salt of 4,5-dichlorophthalate (dcpa2-) lead to two families of isostructural coordination polymers: family F1 that gathers compounds with the general chemical formula [Ln2(dcpa)3(H2O)]∞ with Ln = La-Gd (except Pm) and family F2 that gathers compounds with general chemical formula [Ln2(dcpa)3(H2O)5·3H2O]∞ with Ln = Tb-Lu plus Y. Heterolanthanide molecular alloys that contain both Eu3+ and Tb3+ ions have been prepared in both structural families. Their luminescence properties have been studied, especially from the brightness point of view. This study revealed that structural family F1 provides molecular alloys that are much more luminescent than those of structural family F2. Therefore, a phase-induction strategy was followed that allowed the design of some molecular alloys (La/Tb/Eu and La/Dy) that are, to the best of our knowledge, among the most luminescent coordination polymers reported so far. This study opens the way to bright luminescent bar codes as well as to bright white luminescent lanthanide-based coordination polymers.
Published: 2020
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21. Rational engineering of dimeric Dy-based Single-Molecule Magnets for surface grafting

Author: Guillaume Calvez, Carole Daiguebonne, Boris Le Guennic, Fabrice Pointillart, Julie Jung, Xiaohui Yi, Kevin Bernot, Olivier Guillou, Ningbo Institute of Technology (NIT), 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), Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES), INSA Rennes, CNRS, Université de Rennes 1, Region Bretagne, Rennes Métropole, China Scholarship Council (CSC) and the Agence Nationale de la Recherche (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), 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 Institut National des Sciences Appliquées (INSA)
Subjects: Lanthanide, 010405 organic chemistry, Anchoring, 010402 general chemistry, Ring (chemistry), Electrostatics, 01 natural sciences, 0104 chemical sciences, Characterization (materials science), Inorganic Chemistry, Surface, chemistry.chemical_compound, Crystallography, Single-Molecule Magnets, chemistry, Magnet, Pyridine, Lanthanides, Materials Chemistry, Molecule, [CHIM.COOR]Chemical Sciences/Coordination chemistry, Physical and Theoretical Chemistry, Dimers
Abstract: International audience; Dedicated to Professor Miguel Julve on the occasion of his 65 th birthday, and for its outstanding contribution to the field of coordination chemistry and molecular magnetism. Abstract The deposition of Single-Molecule Magnets (SMMs) on surfaces is a mandatory step toward their possible use as data-storage units or qubits. In this study we report the structural and magnetic characterization of two parent compounds of a well-known SMM called DyPyNO, ([Dy(hfac) 3 (PyNO)] 2 with hfac = hexafluoroacetylacetonate and PyNO = pyridine-N-oxide), that are targeted to be deposited on gold surfaces. Thio-substitution of the pyridine ring of these dimers is expected to provide good anchoring group toward deposition on gold. We have investigated two significantly different geometries of the anchoring groups in dimers 1 and 2. Interestingly, despite these strong differences, SMM behavior is remarkably well-preserved in the polycrystalline material offering possibilities to graft these SMMs on surface.
Published: 2019
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22. A new family of lanthanide-based coordination polymers with azoxybenzene-3,3′,5,5′-tetracarboxylic acid as ligand

Author: Kevin Bernot, Stéphane Freslon, Jinzeng Wang, Guillaume Calvez, Yan Suffren, Thierry Roisnel, Carole Daiguebonne, Olivier Guillou, 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), Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES), The China Scholarship Council Ph.D. Program, a cooperation program with the French UT & INSA, is acknowledged for financial support., 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 Institut National des Sciences Appliquées (INSA)
Subjects: Lanthanide, 010405 organic chemistry, Ligand, Chemistry, Lanthanide coordination polymers, Crystal structure, Triclinic crystal system, 010402 general chemistry, 01 natural sciences, Chemical formula, 0104 chemical sciences, Inorganic Chemistry, azoxybenzene-3 3’ 5 5’-tetracarboxylic acid, Crystallography, Materials Chemistry, Crystal structureLuminescent properties, [CHIM.COOR]Chemical Sciences/Coordination chemistry, Thermal analysis, Physical and Theoretical Chemistry, Isostructural, Luminescence
Abstract: International audience; Reactions by solvothermal methods of lanthanide nitrates and azoxybenzene-3,3′,5,5′-tetracarboxylic acid (H4aobtc) lead to a family of isostructural lanthanide-based coordination polymers with general chemical formula [Ln(Haobtc)(H2O)2·2H2O]∞ with Ln = Nd − Er plus Y. The crystal structure has been solved on the basis of the Y3+-derivative. It crystallizes in the triclinic system, space group P-1 (n°2) with the following cell parameters: a = 6.6890(18) Å, b = 10.052(3) Å, c = 13.879(4) Å,α = 75.756(9)°, β = 77.551(9)°, γ = 83.964(9)° and Z = 2. The crystal structure is two-dimensional (2D). Thermal properties and luminescent properties of the Nd3+-containing compound have been studied.
Published: 2019
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23. Lanthanide-Based Coordination Polymers With 1,4-Carboxyphenylboronic Ligand: Multiemissive Compounds for Multisensitive Luminescent Thermometric Probes

Author: Guillaume Calvez, Stéphane Freslon, Yan Suffren, Thierry Roisnel, Carole Daiguebonne, Amandine Rojo, Olivier Guillou, Kevin Bernot, Ahmad Abdallah, Xiao Fan, 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 Génie Civil et Génie Mécanique (LGCGM), Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), China Scholarship Council, 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 Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)
Subjects: chemistry.chemical_classification, Lanthanide, 010405 organic chemistry, Ligand, Polymer, 010402 general chemistry, 01 natural sciences, 0104 chemical sciences, Sodium salt, Inorganic Chemistry, [CHIM.POLY]Chemical Sciences/Polymers, chemistry, Polymer chemistry, [CHIM.COOR]Chemical Sciences/Coordination chemistry, Physical and Theoretical Chemistry, Isostructural, Luminescence, ComputingMilieux_MISCELLANEOUS
Abstract: Reactions in water of lanthanide chlorides with the sodium salt of 1,4-carboxyphenylboronic acid lead to two series of isostructural compounds with respective general chemical formulas [Ln(cpb)3(H2O)2]∞ for Ln = La or Ce and [Ln(cpbOH)(H2O)2·(cpb)]∞ for Ln = Pr–Lu (except Pm) plus Y. Heterolanthanide coordination polymers that are isostructural to the second series have been synthesized, and their photophysical properties have been studied. This study evidences that it is possible to design multiemissive lanthanide-based coordination polymers that could find their application as multigauge luminescent thermometric probes.
Published: 2019
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24. Hetero-hexalanthanide Complexes: A New Synthetic Strategy for Molecular Thermometric Probes

Author: Olivier Guillou, Carole Daiguebonne, Haiyun Yao, Guillaume Calvez, 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), China Scholarship Council, 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: 010405 organic chemistry, Chemistry, Solution state, Energy transfer, Solid-state, Intermetallic, 010402 general chemistry, 01 natural sciences, 0104 chemical sciences, Inorganic Chemistry, Crystallography, [CHIM]Chemical Sciences, Physical and Theoretical Chemistry, Isostructural, Luminescence
Abstract: Reactions in solvothermal or microwave-assisted conditions between a hexanuclear rare-earth entity ([Ln6] with Ln = Eu-Dy) and m-halogeno-benzoic acids lead to three series of isostructural complexes with respective chemical formulas [Ln6(μ3-OH)2(H2O)2(NO3)2(3-cb)14]·4CH3CN, [Ln6(μ3-OH)2(H2O)2(NO3)2(3-bb)14]·6CH3CN, and [Ln6(μ3-OH)2(H2O)2(NO3)2(3-ib)14]·6CH3CN, where 3-cb-, 3-bb-, and 3-ib- represent 3-chloro-, 3-bromo-, and 3-iodo-benzoate, respectively. These three series of compounds are almost isostructural. Their luminescent properties, in the solid and solution states, have been studied in detail and compared. This study shows that hexanuclear complexes own strong intermetallic energy transfers. This makes these complexes good candidates for thermometric probes in solid state or in solution state.
Published: 2019
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25. A supramolecular chain of dimeric Dy single molecule magnets decorated with azobenzene ligands

Author: Kevin Bernot, Boris Le Guennic, Frédéric Gendron, Carole Daiguebonne, Yan Suffren, Olivier Guillou, Guillaume Calvez, Thierry Guizouarn, Gang Huang, Xiaohui Yi, 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), Centre National de la Recherche Scientifique, China Scholarship Council, Institut Universitaire de France, SAD18006, Région Bretagne, 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, Ligand, Supramolecular chemistry, 010402 general chemistry, 01 natural sciences, 0104 chemical sciences, Inorganic Chemistry, Physics::Fluid Dynamics, chemistry.chemical_compound, Crystallography, Azobenzene, chemistry, Ab initio quantum chemistry methods, Excited state, Molecule, Antiferromagnetism, [CHIM]Chemical Sciences, Magnetic dipole–dipole interaction
Abstract: International audience; We report the synthesis, ab initio calculations, magnetic and optical characterization of a Dy-based dimeric compound named DyAZO. The dimers self-organize into a supramolecular chain decorated with photo-isomerizable azobenzene ligands. DyAZO displays single-molecule magnet (SMM) behavior. However, ab initio calculations highlight a quite strong admixture of M states of the H level of Dy ions, the presence of low-lying excited M states and antiferromagnetic Dy-Dy dipolar coupling. This favors zero-field fast tunneling. Accordingly the Dy-doped analogue YDyAZO (5.5% Dy doping) displays enhanced magnetic relaxation with a hysteresis that is observed at 0.5 K. The influence of the cis- to trans-isomerization of the decorating azobenzene ligand on magnetic properties has been tested for both solid samples and solutions of DyAZO and YDyAZO. This provides hints for the synthesis of future Dy-based photo-isomerizable molecules.
Published: 2019
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26. Do the bridging angle affect the luminescent properties of [(CO)3(phen)Re(µ-OH)Re(phen)(CO)3]+?. An experimental and computational study on three polymorphs

Author: Guillaume Calvez, Jean René Hamon, Jean Yves Saillard, Marianela Saldías, Nancy Pizarro, Poldie Oyarzún, Carolina Muñoz, Andrés Vega, Universidad Andrés Bello [Santiago] (UNAB), 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), FB0807ACT Government, ACTFondo Nacional de Desarrollo Científico y Tecnológico, FONDECYT 1160546, 1160749, ACTFondo Nacional de Desarrollo Científico y Tecnológico, FONDECYT 1160546, 1160749, FONDECYT 1160546, 1160749, 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: Luminescence, Dimer, Phenanthroline, chemistry.chemical_element, Triclinic crystal system, 010402 general chemistry, 01 natural sciences, Inorganic Chemistry, Bridging angle, chemistry.chemical_compound, Materials Chemistry, [CHIM.COOR]Chemical Sciences/Coordination chemistry, Physical and Theoretical Chemistry, Polymorphism, Diimine, 010405 organic chemistry, Chemistry, Rietveld refinement, Rhenium, 0104 chemical sciences, [CHIM.THEO]Chemical Sciences/Theoretical and/or physical chemistry, Crystallography, Density functional calculations, Molecular geometry, Orthorhombic crystal system
Abstract: International audience; The reaction of [ReIBr(CO)3(THF)]2 with phenanthroline in solution leads to the diimine rhenium(I)tricarbonyl [(phen)Re(CO)3Br] and the dimer [(CO)3(phen)Re(µ-OH)(phen)Re(CO)3]+Br− (1+Br−) as a by-product (~5% yield). This latter bimetallic compound crystallizes as a mixture of three polymorphs, with variable amount of solvent 1+Br−·CHCl3 (triclinic and orthorhombic) and 1+Br−·2(CHCl3) (triclinic). Rietveld analysis showed 38, 54 and 8% of 1+Br−·CHCl3 (triclinic), 1+Br−·CHCl3 (orthorhombic) and 1+Br−·2(CHCl3) (triclinic) respectively. The 1+ cation shows two [ReI(phen)(CO)3]+ units connected by means of a central hydroxyl group. Noteworthy, the bridging Re–O–Re angle varies between 130.9(7)° to 140.7(2)° along the polymorphic series. UV–Vis spectrum for the 1+ shows a broad absorption band around 390 nm in CH2Cl2 which has been attributed to has MLCT character (Re(dπ) → π*(phen)) as confirmed by DFT. Excitation at 405 nm in solution leads to emission at 595 nm (DCM), 605 nm (DMF) and 625 nm (CH3CN). The emission follows a mono-exponential law of decay and has lifetime of 405.8 ns (DCM). The solid-state polymorphic mixture absorbs around 460 nm. Excitation of the solid at 320 nm leads to emission with a maximum at 575 nm, which follow a bi-exponential law of decay with two components, a short one τ1 of 27.0 ns and longer one τ2 of 178.5 ns. These results suggest that the emitting state does not vary as function of the molecular geometry.
Published: 2019
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27. Adaptive Coordination-Driven Supramolecular Syntheses toward New Polymetallic Cu(I) Luminescent Assemblies

Author: Ali Moustafa Khalil, Eugene Yau-Hin Hong, Sloane Evariste, Mehdi Elsayed Moussa, Vivian Wing-Wah Yam, Hok-Lai Wong, Boris Le Guennic, Guillaume Calvez, Christophe Lescop, Karine Costuas, Alan Kwun-Wa Chan, 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), The University of Hong Kong (HKU), Agence Nationale de la Recherche, HKU 17334216, Research Grants Council, University Grants Committee, University of Hong Kong, University Research Committee, University of Hong Kong, Ministère de l'Enseignement Supérieur et de la Recherche, AoE/P-03/08, University Grants Committee, Centre National de la Recherche Scientifique, Alexander von Humboldt-Stiftung, ANR-12-IS07-0002,P-OPTOELECTR-MOLMAT,Matériaux pi-conjugués à base de phosphore : conception, synthèse et assemblages supramoléculaires pour l'émission et la collecte de lumière, la communication électronique et le transport de charge.(2012), 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: 010405 organic chemistry, Chemistry, Coordination polymer, Supramolecular chemistry, General Chemistry, Metallacycle, 010402 general chemistry, 01 natural sciences, Biochemistry, Fluorescence, Catalysis, 0104 chemical sciences, Metal, chemistry.chemical_compound, Crystallography, Colloid and Surface Chemistry, visual_art, visual_art.visual_art_medium, [CHIM]Chemical Sciences, Luminescence
Abstract: International audience; A thermally activated delayed fluorescence (TADF) tetrametallic Cu(I) metallacycle A behaves as a conformationally adaptive preorganized precursor to afford, through straightforward and rational coordination-driven supramolecular processes, a variety of room-temperature solid-state luminescent polymetallic assemblies. Reacting various cyano-based building blocks with A, a homometallic Cu(I) 1D-helical coordination polymer C and CuM discrete circular heterobimetallic assemblies D (M = Ni, Pd, Pt) are obtained. Their luminescence behaviors are studied, revealing notably the crucial impact of the spin-orbit coupling offered by the central M metal center on the photophysical properties of the heterobimetallic D derivatives.
Published: 2018
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28. Strong Magnetic Coupling and Single-Molecule-Magnet Behavior in Lanthanide-TEMPO Radical Chains

Author: Guillaume Calvez, Olivier Cador, Carole Daiguebonne, Yan Suffren, Boris Le Guennic, Gang Huang, Kevin Bernot, Thierry Guizouarn, Olivier Guillou, 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), China Scholarship Council, Institut Universitaire de France, Rennes M?tropole, 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, magneto-luminescent correlations, 010405 organic chemistry, Chemistry, Radical, Relaxation (NMR), Ab initio, magnetic coupling, [CHIM.INOR]Chemical Sciences/Inorganic chemistry, 010402 general chemistry, radicals, 01 natural sciences, Inductive coupling, 0104 chemical sciences, Inorganic Chemistry, Crystallography, Lanthanides, Antiferromagnetism, Single-molecule magnet, [CHIM.COOR]Chemical Sciences/Coordination chemistry, Physical and Theoretical Chemistry, Isostructural, TEMPO, magnetic chains
Abstract: The rational design of molecular chains made of 4f ions and substituted 2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO) radical is presented. The reaction of Ln(hfac)3·2H2O (hfac- = hexafluoroacetylacetonate) and the 4-cyano-2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO-CN) radical affords air- and moisture-stable isostructural molecular chains of the formula [Ln(hfac)3TEMPO-CN] n for Ln = GdIII and TbIII, whereas zero-dimensional complexes of the formula [Dy(hfac)3(TEMPO-CN)2][Dy(hfac)3(H2O)2]2 are obtained for Ln = DyIII. To the best of our knowledge, the Gd derivative, Gd-TEMPO-CN, shows one of the strongest antiferromagnetic (AF) couplings for Gd-radical pairs ever reported with JGd-rad/ kB = -21.18 K, 14.72 cm-1 ( H = - JSrad SGd spin Hamiltonian convention). The TbIII derivative, Tb-TEMPO-CN, also shows strong Tb-radical AF coupling, which has been rationalized using the ab initio CASSCF approach ( JTb-rad = -23.02 K, -16.7 cm-1) and confirmed by luminescence measurements. Tb-TEMPO-CN shows remarkable properties for a Tb-radical-based single-molecule magnet ( Ueff = 69.3 ± 1 K; τ0 = 1.3 × 10-7 s) and two different relaxation processes triggered by interchain magnetic coupling.
Published: 2018
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29. Lanthanide-based hexa-nuclear complexes and their use as molecular precursors

Author: Carole Daiguebonne, Guillaume Calvez, Yan Suffren, Olivier Guillou, François Le Natur, Kevin Bernot, Institut des Sciences Chimiques de Rennes (ISCR), 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), 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, chemistry.chemical_classification, 010405 organic chemistry, Chemistry, DABCO, Crystal structure, Molecular precursor, 010402 general chemistry, HEXA, 01 natural sciences, Combinatorial chemistry, 0104 chemical sciences, Coordination complex, Photophysical properties, Inorganic Chemistry, Hexa-nuclear complexes, chemistry.chemical_compound, Crystal structures, Materials Chemistry, Organic chemistry, Coordination compounds, [CHIM.COOR]Chemical Sciences/Coordination chemistry, Physical and Theoretical Chemistry
Abstract: International audience; The use of lanthanide-based poly-nuclear complexes as molecular precursor for the design of extended molecular frameworks is still an innovative synthesis strategy. Oxo-hydroxo poly-nuclear complexes are generally obtained by controlling pH conditions during reaction process. After a short description of the lanthanide hydrolysis phenomenon and a non-exhaustive inventory of existing complexes with increasing nuclearity, the present review focuses on lanthanide-based hexa-nuclear oxo-hydroxo complexes. Their syntheses and crystal structures are described and their interest as building blocks for the design of new coordination compounds with unprecedented physical properties is highlighted.
Published: 2017
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30. High Brightness and Easy Color Modulation in Lanthanide-Based Coordination Polymers with 5-Methoxyisophthalate as Ligand: Toward Emission Colors Additive Strategy

Author: Stéphane Freslon, Guillaume Calvez, Insa Badiane, Carole Daiguebonne, Magatte Camara, Kevin Bernot, Olivier Guillou, Yan Suffren, 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), Groupe Matériaux Inorganiques:Chimie Douce et Cristallographie (LCPM), Université deZiguinchor, French Cooperation Agency in Senegal, 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 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: Lanthanide, chemistry.chemical_classification, 010405 organic chemistry, Coordination polymer, Ligand, Additive color, Inorganic chemistry, Intermetallic, General Chemistry, Polymer, 010402 general chemistry, Condensed Matter Physics, 01 natural sciences, Chemical formula, 0104 chemical sciences, Crystallography, chemistry.chemical_compound, [CHIM.POLY]Chemical Sciences/Polymers, chemistry, [CHIM.CRIS]Chemical Sciences/Cristallography, General Materials Science, [CHIM.COOR]Chemical Sciences/Coordination chemistry, Luminescence
Abstract: International audience; Reactions in water between lanthanide chlorides and the disodium salt of 5-methoxyisophthalic acid, Na2(mip)·7H2O, lead to the first three series of lanthanide-based coordination polymers based on this ligand. The first series contains only one compound with chemical formula [Ce(mip)3/2(H2O)5·2H2O]∞. The second series has general chemical formula [Ln(mip) (Hmip)(H2O)5·H2O]∞ with Ln = La–Ce. The last family is constituted by compounds with general chemical formula [Ln2(mip)3(H2O)8·4H2O]∞ with Ln = Sm–Er plus Y. Luminescent properties of the compounds that belong to this family have been studied. The Tb-based compound presents one of the brightest luminescences reported to date for a lanthanide-based coordination polymer. The weak intermetallic energy transfer evidenced on the third family of compounds allows easy and predictable color modulation of the heterobimetallic powders through additive colors strategy.
Published: 2017
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31. A Long Journey in Lanthanide Chemistry: From Fundamental Crystallogenesis Studies to Commercial Anticounterfeiting Taggants

Author: Guillaume Calvez, Olivier Guillou, Carole Daiguebonne, Kevin Bernot, Institut des Sciences Chimiques de Rennes (ISCR), 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)-Centre National de la Recherche Scientifique (CNRS)
Subjects: Lanthanide, 010405 organic chemistry, Chemistry, Structural diversity, [CHIM]Chemical Sciences, Applied research, Nanotechnology, General Medicine, General Chemistry, 010402 general chemistry, 01 natural sciences, 0104 chemical sciences, Organic molecules
Abstract: International audience; Lanthanide ions have unique physical properties and are essential for numerous technological devices. Indeed, much research has been undertaken in order to understand and optimize their luminescent behavior. From a chemical and more specific point of view, lanthanides can be used to build coordination polymers (CPs). CPs are materials in which metal ions are associated with organic molecules (ligands) to form extended networks. They present great structural diversity and a wide range of unique properties such as great porosity, strong catalytic activities, and original magnetic and luminescent behaviors. In this Account, we highlight recent research advances obtained by our team in the field of lanthanide-based CPs. However, rather than present a simple chronological description of successive investigations, we have chosen present our own experience in order to show how standard academic studies can be successfully turned into applied research and finally into a viable startup that commercializes these products as anticounterfieting taggants. A taggant is a compound that can be dispersed in a host matrix at parts per million rates for it to be labeled. Its economic advantages over traditional anticounterfeiting techniques (labels, chips, etc.) are its very low cost and its ability to label a raw material at every stage of its processing, unlike traditional techniques that label only the final product. It thus permits traceability of a given material over a wide range of suppliers/subcontractors/sellers or customers at every step of its life. After 15 years of fundamental crystallogenesis research, we identified a very stable phase of lanthanide-based CPs in which strong lanthanide luminescence can be observed. We investigated this phase further and showed that a heteronuclear approach can give access to billions of different compositions and makes it possible to turn these powders into taggants. After the creation of a startup, we refocused on fundamental studies in order to ensure its future development. This permitted the design of future generations of taggants and provided brightness- or color-tunable compounds as well as temperature-sensitive and soluble taggants. We hope to demonstrate here that strong fundamental research is a very effective tool to create a technological breakthrough that allows the development of efficient applicative research and competitive products and finally contributes to economic growth
Published: 2016
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32. Magnetic Anisotropy and Spin-Parity Effect Along the Series of Lanthanide Complexes with DOTA

Author: Olivier Cador, Javier Luzon, Guillaume Calvez, Marie-Emmanuelle Boulon, Roberta Sessoli, Alessio Milanesi, MAURO PERFETTI, GIUSEPPE CUCINOTTA, Kevin Bernot, Andrea Caneschi, Department of Chemistry 'Ugo Schiff', 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), Italian MIUR, Spanish research project, Région Bretagne, Rennes Métropole [MAT2011-27233-C02-02], Italian CINECA [HP10AI85MB], European Project, 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), European Commission, Ministero dell'Istruzione, dell'Università e della Ricerca, European Research Council, and Région Bretagne
Subjects: Lanthanide, Luminescence, [CHIM.INOR]Chemical Sciences/Inorganic chemistry, 010402 general chemistry, 01 natural sciences, Catalysis, Ion, Magnetization, chemistry.chemical_compound, Nuclear magnetic resonance, Lanthanides, luminescence, Molecule, DOTA, lanthanides, Spin (physics), Crystal field, crystal field, 010405 organic chemistry, Chemistry, Relaxation (NMR), General Medicine, General Chemistry, ab initio calculations, 0104 chemical sciences, 3. Good health, Crystallography, Magnetic anisotropy, Magnetic properti, magnetic properties
Abstract: Spotting trends: Upon going from TbIII to YbIII centers in the complexes of the DOTA4- ligand, a reorientation of the easy axis of magnetization from perpendicular to parallel to the Ln-O bond of the apical water molecule is experimentally observed and theoretically predicted (see picture; SMM = single-molecule magnet). Only ions with an odd number of electrons show slow relaxation of the magnetization. © 2013 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim., This work was supported by the European Research Council through the AdG “NoINanoMaS” (grant number 267746), by the Italian MIUR (PRIN 2008), Spanish research project MAT2011-27233-C02-02, Région Bretagne, Rennes Métropole, and by the Italian CINECA through the award number HP10AI85MB, 2011.
Published: 2012
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33. Unprecedented Lanthanide-Containing Coordination Polymers Constructed from Hexanuclear Molecular Building Blocks: {[Ln6O(OH)8](NO3)2(bdc)(Hbdc)2·2NO3·H2bdc}∞

Author: Carole Daiguebonne, Guillaume Calvez, and Olivier Guillou
Subjects: Lanthanide, Terephthalic acid, 010405 organic chemistry, Stereochemistry, Protonation, Crystal structure, Triclinic crystal system, 010402 general chemistry, 01 natural sciences, 0104 chemical sciences, Inorganic Chemistry, chemistry.chemical_compound, Crystallography, chemistry, Physical and Theoretical Chemistry, Isostructural, Acetonitrile, Powder diffraction
Abstract: Reactions in acetonitrile between 1,4-benzene-dicarboxylic acid (C8H6O4) and a hexanuclear complex of lanthanide [Ln6O(OH)8(NO3)6·2NO3] with Ln = Y or Tb lead to 1D-coordination polymers with the general chemical formula {[Ln6O(OH)8](NO3)2(bdc)(Hbdc)2·2NO3·H2bdc}∞ where H2bdc stands for 1,4-benzene-dicarboxylic acid (or terephthalic acid). These two compounds are isostructural. The crystal structure has been solved on the basis of the X-ray powder diffraction diagram of the Y-containing compound. This compound crystallizes in the triclinic system, space group P1 (no. 2) with a = 10.4956(6) A, b = 11.529(2) A, c = 12.357(2) A, α = 86.869(9)°, β = 114.272(6)°, γ = 71.624(7)°, V = 1264.02 A3, and Z = 2. The crystal structure can be described as the juxtaposition of linear chains of hexanuclear entities linked to each other by terephthalate ligands. Two additional partially protonated terephthalate ligands spreading laterally to the chain are bound to each hexanuclear entity. Another diprotonated terephthali...
Published: 2011
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34. Closing the Circle of the Lanthanide-Murexide Series: Single-Molecule Magnet Behavior and Near-Infrared Emission of the NdIII Derivative

Author: Kevin Bernot, Guillaume Calvez, Carole Daiguebonne, Yan Suffren, Stéphane Freslon, Gang Huang, Olivier Guillou, Software Engineering Institute [Peking], Peking University [Beijing], 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), 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), and Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA)
Subjects: Lanthanide, neodymium single-molecule magnets, Materials science, Crystal structure, 010402 general chemistry, 01 natural sciences, Murexide, Ion, lcsh:Chemistry, chemistry.chemical_compound, Materials Chemistry, [CHIM.COOR]Chemical Sciences/Coordination chemistry, lanthanides, Single-molecule magnet, bifunctionality, ComputingMilieux_MISCELLANEOUS, Series (mathematics), 010405 organic chemistry, Near-infrared spectroscopy, 0104 chemical sciences, 3. Good health, Electronic, Optical and Magnetic Materials, Crystallography, lcsh:QD1-999, chemistry, Chemistry (miscellaneous), Anhydrous, near-infrared emission
Abstract: Up to now, even if murexide-based complexometric studies are performed with all 3d or 4f ions, the crystal structures of the light-lanthanide derivatives of the lanthanide-murexide series are unknown. In this work, we report the crystal structure of the NdIII derivative named NdMurex. Contrary to all known complexes of the 3d or 4f series, a dimeric compound was obtained. As for its already reported DyIII and YbIII parents, the NdIII complex responsible for the color-change behaves as a single-molecule magnet (SMM). This behavior was observed on both the crystalline (NdMurex: Ueff = 6.20(0.80) K, 4.31 cm−1, τ0 = 2.20(0.92) × 10−5 s, Hdc = 1200 Oe) and anhydrous form (NdMurexAnhy: Ueff = 6.25(0.90) K, 4.34 cm−1, τ0 = 4.85(0.40) × 10−5 s, Hdc = 1200 Oe). The SMM behavior is reported also for the anhydrous CeIII derivative (CeMurexAnhy: Ueff = 5.40(0.75) K, 3.75 cm−1, τ0 = 3.02(1.10) × 10−5 s, Hdc = 400 Oe). The Near-Infrared Emission NIR emission was observed for NdMurexAnhy and highlights its bifunctionality.
Published: 2018
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35. Lanthanide-based hexanuclear complexes usable as molecular precursors for new hybrid materials

Author: Olivier Guillou, Tanja Pott, Philippe Méléard, Guillaume Calvez, Carole Daiguebonne, and Florence Le Dret
Subjects: Lanthanide, 010405 organic chemistry, Stereochemistry, Chemistry, General Chemical Engineering, General Chemistry, Crystal structure, 010402 general chemistry, 01 natural sciences, Chemical formula, 0104 chemical sciences, Crystallography, Octahedron, Polymorphism (materials science), Transition metal, X-ray crystallography, Hybrid material
Abstract: Lanthanide containing octahedral hexanuclear complexes with general chemical formula [Ln6O(OH)8(NO3)6(H2O)x].2NO3.yH2O where Ln = Ce-Lu (except Pm) or Y, x = 0, 6, 12, 14 or 16 and y = 0, 2, 4 or 5 constitute a great family of polymorphic compounds. The synthesis and the crystal structures of all these compounds are overviewed. The hydration/dehydration processes that allow the structural transitions from one compound to another are described. The crystal structure of compounds with general chemical formula [Ln6O(OH)8(NO3)6(H2O)6].2NO3 where Ln = Ce-Lu (except Pm) or Y is described. It has been solved on the basis of a powder XRD diagram. The use of such hexanuclear complexes as molecular precursors for new materials is also discussed.
Published: 2010
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36. New Family of Porous Lanthanide-Containing Coordination Polymers: [Ln2(C2O4)3(H2O)6,12H2O]∞ with Ln = La−Yb or Y

Author: Stéphane Freslon, Olivier Guillou, Guillaume Calvez, Nicolas Kerbellec, Carole Daiguebonne, Doddy Kustaryono, Sciences Chimiques de Rennes / Matériaux Inorganiques: Chimie Douce et Réactivité (MICDR), 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)-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)-Centre National de la Recherche Scientifique (CNRS)
Subjects: Lanthanide, chemistry.chemical_classification, 010405 organic chemistry, Inorganic chemistry, General Chemistry, Polymer, Crystal structure, [CHIM.INOR]Chemical Sciences/Inorganic chemistry, 010402 general chemistry, Condensed Matter Physics, 01 natural sciences, Chemical formula, 0104 chemical sciences, law.invention, Crystallography, chemistry, law, Molecule, [CHIM.COOR]Chemical Sciences/Coordination chemistry, General Materials Science, Crystallization, Isostructural, Luminescence
Abstract: International audience; Reactions at low temperature in a mixture benzene/water between dimethyloxalate and a lanthanide chloride lead to a family of 3D-coordination polymers with general chemical formula [Ln2(C2O4)3(H2O)6 3 12H2O]¥, where Ln=La-Yb (except Pm) or Y. All these compounds are isostructural to the already described [Er2(C2O4)3(H2O)6 3 12H2O]¥. Their crystal structure can be described as the juxtaposition of channels with hexagonal cross-section. The channels are filled with crystallization water molecules. Their thermal dehydration produces a collapse of the molecular skeleton leading to amorphous compounds.On the opposite, their dehydration by freeze-drying is possible and the twelve crystallization water molecules can be removed without destruction of the molecular skeleton. The porosity of the dehydrated compounds has been estimated by computational methods to 483 m2 g-1. The luminescence properties of the Eu-containing and Tb-containing compounds are also briefly described.
Published: 2009
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37. Highly axial magnetic anisotropy in a N3O5 dysprosium(III) coordination environment generated by a merocyanine ligand

Author: Guillaume Calvez, Thierry Guizouarn, Guglielmo Fernandez-Garcia, Gang Huang, Lucie Norel, Stéphane Rigaut, Federico Totti, Boris Le Guennic, Thierry Roisnel, Pramila Selvanathan, Kevin Bernot, 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), Department of Chemistry 'Ugo Schiff', Università degli Studi di Firenze = University of Florence (UniFI), This work was supported by the Universit8 de Rennes 1, theCNRS,and the AgenceNationale de la Recherche (RuOxLux -ANR-12-BS07-0010-0 1).G.F.G. and F.T. gratefully acknowledgesthe European Commission throughthe ERC-AdG 267746 Mol-NanoMas(project n. 26774 6) and the ANR (ANR-13-BS0 7-0022 -01) for financial support. B.L.G. and G.F.G. thank the FrenchGENCI/IDRIS-CINES center for high-performance computing re-sources, ANR-12-BS07-0010,RuOxLux,Modulation redox de la luminescence à l'aide de complexes organométalliques du ruthénium associés à une unité luminescente(2012), 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), 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), and Università degli Studi di Firenze = University of Florence [Firenze] (UNIFI)
Subjects: Lanthanide, Coordination sphere, single-mole cule magnets, merocyanine, chemistry.chemical_element, 010402 general chemistry, Photochemistry, 01 natural sciences, Catalysis, chemistry.chemical_compound, axial anisotropy, Ab initio quantum chemistry methods, Merocyanine, [CHIM.COOR]Chemical Sciences/Coordination chemistry, Spiropyran, 010405 organic chemistry, Ligand, ab initio calculations, Organic Chemistry, General Chemistry, 0104 chemical sciences, 3. Good health, Magnetic anisotropy, chemistry, hysteresis, Dysprosium
Abstract: International audience; A spiropyran-based switchable ligand isomerizes upon reaction with lanthanide(III) precursors to generate complexes with an unusual N3O5 coordination sphere. The air-stable dysprosium(III) complex shows a hysteresis loop at 2 K and a very strong axial magnetic anisotropy generated by the merocyanine phenolate donor.
Published: 2016
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38. Brightness and Color Tuning in a Series of Lanthanide-Based Coordination Polymers with Benzene-1,2,4,5-tetracarboxylic Acid as a Ligand

Author: Stéphane Freslon, Yun Luo, Guillaume Calvez, Carole Daiguebonne, Olivier Guillou, Kevin Bernot, Institut des Sciences Chimiques de Rennes (ISCR), 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), China Scholarship Council, 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: chemistry.chemical_classification, Lanthanide, Brightness, 010405 organic chemistry, Inorganic chemistry, Polymer, 010402 general chemistry, 01 natural sciences, Chemical formula, 0104 chemical sciences, Ion, Inorganic Chemistry, Crystallography, chemistry.chemical_compound, chemistry, [CHIM]Chemical Sciences, Physical and Theoretical Chemistry, Isostructural, Benzene, Luminescence
Abstract: International audience; Reactions in water between the sodium salt of benzene-1,2,4,5-tetracarboxylic acid (H4btec) and lanthanide ions (Sm-Dy) led to a series of isostructural lanthanide-based coordination polymers with the general chemical formula [Ln4(btec)3(H2O)12·20H2O]∞ with Ln = Sm-Dy. The family has been structurally characterized. From a luminescent point of view, the heterodinuclear strategy has been successfully applied and allows significant brightness enhancement (+35%) and color tuning from green to yellow to orange to red
Published: 2016
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39. A family of lanthanide-based coordination polymers with boronic Acid as ligand

Author: Stéphane Freslon, Xiaohui Yi, Olivier Guillou, Carole Daiguebonne, Laurent Le Pollès, Xiao Fan, Kevin Bernot, Gang Huang, Guillaume Calvez, 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), Software Engineering Institute [Peking], Peking University [Beijing], China Scholarship Council, 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), and Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA)
Subjects: chemistry.chemical_classification, Lanthanide, 010405 organic chemistry, Ligand, Nuclear magnetic resonance spectroscopy, Polymer, 010402 general chemistry, Photochemistry, 01 natural sciences, Chemical formula, 0104 chemical sciences, Inorganic Chemistry, Crystallography, chemistry.chemical_compound, chemistry, [CHIM]Chemical Sciences, Physical and Theoretical Chemistry, Phosphorescence, Luminescence, Boronic acid
Abstract: International audience; Reactions in water between the sodium salt of 4-carboxyphenylboronic acid (Hcpb) and lanthanide ions (Pr-Nd, Sm-Lu, and Y) led to a family of lanthanide-based coordination polymers with general chemical formula \[Ln(cpbOH)(H2O)2](cpb)\∞. Structural characterizations were ensured by single-crystal X-ray diffraction and solid-state NMR spectroscopy ((11)B, (13)C, and (89)Y). This family of compounds constitutes the first example of lanthanide-based coordination polymers involving 4-carboxyphenylboronic acid as ligand. To evaluate their potential usefulness, luminescent and magnetic properties of some of the compounds that constitute this family were explored. From a magnetic point of view, the Yb(III) compound is the more promising. On the other hand, upon UV irradiation (λexc = 303 nm) ligand phosphorescence is quite intense and offers a sizable blue component to emission spectra. This is quite unusual and can constitute an asset as far as white emission is targeted. Moreover, luminescence properties of these compounds are highly temperature-dependent, and some of them seem promising as molecular thermometers.[on SciFinder (R)]
Published: 2015
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40. Analysis of the electrostatics in Dy(III) single-molecule magnets: the case study of Dy(Murex)3

Author: Olivier Cador, Thierry Roisnel, Kevin Bernot, Guillaume Calvez, Andrea Caneschi, Julie Jung, B. Le Guennic, Xiaohui Yi, G. Huang, Olivier Guillou, Carole Daiguebonne, Centre de recherche en neurosciences de Lyon (CRNL), Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-Université Jean Monnet [Saint-Étienne] (UJM)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS), Chercheur indépendant, 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), 2Dipartimento di Chimica, and INSTM (UdR Firenze), Università degli Studi di Firenze = University of Florence [Firenze] (UNIFI), Centre de recherche en neurosciences de Lyon - Lyon Neuroscience Research Center (CRNL), Université de Lyon-Université de Lyon-Université Jean Monnet - Saint-Étienne (UJM)-Institut National de la Santé et de la Recherche Médicale (INSERM)-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), Dipartimento di Chimica, and INSTM (UdR Firenze), and Università degli Studi di Firenze = University of Florence (UniFI)
Subjects: 010405 organic chemistry, Chemistry, equipment and supplies, 010402 general chemistry, Electrostatics, 01 natural sciences, Molecular physics, 0104 chemical sciences, 3. Good health, Physics::Fluid Dynamics, Inorganic Chemistry, Dipole, Magnetization, Crystallography, Magnetic anisotropy, Ab initio quantum chemistry methods, Magnet, Molecular symmetry, [CHIM]Chemical Sciences, Anisotropy, human activities, ComputingMilieux_MISCELLANEOUS
Abstract: A Dy(III)-based single-molecule magnet is reported. Ab initio calculations highlight that molecular symmetry plays a predominant role over site symmetry in determining the shape and orientation of Dy(III) magnetic anisotropy. Moreover the dipolar component of the electrostatic potential created by the surrounding ligands is shown to be the driving force of its magnetic behaviour.
Published: 2015
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41. Unraveling the Crystal Structure of Lanthanide-Murexide Complexes: Use of an Ancient Complexometry Indicator as a Near-Infrared-Emitting Single-Ion Magnet

Author: Julie Jung, Boris Le Guennic, Kevin Bernot, Thierry Roisnel, Olivier Maury, Virginie Placide, Carole Daiguebonne, Guillaume Calvez, Olivier Cador, Vincent Le Corre, Yannick Guyot, Xiaohui Yi, Fabrice Pointillart, Olivier Guillou, 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 de Chimie - UMR5182 (LC), École normale supérieure de Lyon (ENS de Lyon)-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 Lumière Matière [Villeurbanne] (ILM), Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-Centre National de la Recherche Scientifique (CNRS), 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), 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 Université de Lyon-Université de Lyon
Subjects: Lanthanide, Analytical chemistry, Infrared spectroscopy, Crystal structure, [CHIM.INOR]Chemical Sciences/Inorganic chemistry, 010402 general chemistry, 01 natural sciences, Murexide, Catalysis, Crystal, chemistry.chemical_compound, lanthanides, Emission spectrum, ComputingMilieux_MISCELLANEOUS, 010405 organic chemistry, Chemistry, ligands, Organic Chemistry, Relaxation (NMR), General Chemistry, 0104 chemical sciences, X-ray diffraction, 13. Climate action, IR spectroscopy, magnetic properties, Luminescence
Abstract: Herein, we provide some structural evidence of the complexation color-change of murexide solutions in presence of lanthanide, which has been used for decades in complexometric studies. For Ln = Sm to Lu and Y, the com- pounds crystallize as monomeric (Ln(Murex)3)·11 H 2O with an N3O6 tricapped square-antiprism environment, which are stable up to 2508C. Single-ion magnet (SIM) behavior is then observed on the Yb III derivative in an original nine-coordinat- ed environment. In-field slow relaxation (D = (15.6 � 1) K; t0 = 2.73 � 10 � 6 s) is observed with a very narrow distribution of the relaxation time (amax = 0.09). Magnetic and photophys- ical properties can be correlated. On one hand the analysis of NIR emission spectrum permits to have access to crystal field parameters and to compare them with those extracted from dc measurements. On the other hand, magnetic meas- urements permit to identify the nature of the MJ states in- volved in the 2 F5/2! 2 F7/2 luminescence spectrum. The gap between the low-lying states is in agreement with the energy barrier obtained from magnetic slow-relaxation mea- surement.
Published: 2014
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42. Temperature identification on two 3D Mn(II) metal- organic frameworks: syntheses, adsorption and magnetism

Author: Guillaume Calvez, Lu Lu, Jian-Qiang Liu, Jian Wu, Matthias Zeller, Ng Seik Weng, Hiroshi Sakiyama, Carole Daiguebonne, Olivier Guillou, Jun Wang, 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: 010405 organic chemistry, Chemistry, Magnetism, General Chemical Engineering, Inorganic chemistry, General Chemistry, [CHIM.INOR]Chemical Sciences/Inorganic chemistry, 010402 general chemistry, Kinetic energy, 01 natural sciences, Decomposition, 0104 chemical sciences, Adsorption, Molecule, Physical chemistry, Desolvation, Metal-organic framework, Porosity
Abstract: International audience; Two new 3-D NaCl-type frameworks of [AmineH+][Mn(HCOO)3] (AmineH+ ¼ N(CH3)4 + for 1 and AmineH+ ¼ NH4 + for 2) have been synthesized at different temperatures. The N(CH3)4 + cation was generated in situ by the decomposition of a large number of DMF molecules. The potential porosity of the coordination framework of 1 has been estimated using a computational method based on Connolly's algorithm, indicating that compound 1 presents a kinetic radius greater than 1.61 °A. Because unremovable guest cations are clogged in the channels, 1 presents no significant adsorption for CO2 gas upon desolvation by long-duration thermal activation. In addition, the magnetic behavior of the two compounds was explored.
Published: 2014
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43. A new 3D four-fold interpenetrated dia-like polymer: gas sorption and computational analyses

Author: Zhen-Bin Jia, Qing-Lin Li, Carole Daiguebonne, Kai-Bang Li, Guillaume Calvez, Hao Li, Olivier Guillou, Jian Wu, Jian-Qiang Liu, Centre de Recherches Historiques (CRH), École des hautes études en sciences sociales (EHESS)-Centre National de la Recherche Scientifique (CNRS), Institute of Analysis of Change in Contemporary and Historical Societies (IACCHOS), Université Catholique de Louvain = Catholic University of Louvain (UCL), Laboratoire de l'intégration, du matériau au système (IMS), Université Sciences et Technologies - Bordeaux 1-Institut Polytechnique de Bordeaux-Centre National de la Recherche Scientifique (CNRS), Laboratoire d’Électrotechnique et d’Électronique de Puissance - ULR 2697 (L2EP), Centrale Lille-Haute Etude d'Ingénieurs-Université de Lille-Arts et Métiers Sciences et Technologies, HESAM Université (HESAM)-HESAM Université (HESAM), 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), Guangxi University [Nanning], School of Pharmacy, Guangdong Medical College, 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: chemistry.chemical_classification, Denticity, 010405 organic chemistry, chemistry.chemical_element, Sorption, Butane, General Chemistry, Polymer, [CHIM.INOR]Chemical Sciences/Inorganic chemistry, 010402 general chemistry, Condensed Matter Physics, 01 natural sciences, Nitrogen, 0104 chemical sciences, Metal, Crystallography, chemistry.chemical_compound, Adsorption, chemistry, visual_art, visual_art.visual_art_medium, Organic chemistry, General Materials Science, Luminescence
Abstract: International audience; A new metal–organic framework, namely, {ĳCuĲbib) 2 ]·NO 3 ·4H 2 O} n (1) (bib = 2,3-bis(4-pyridyl)butane), was synthesized and characterized. In the structure of 1, nitrogen atoms of four bib ligands bind to the tetrahedrally coordinated metal ion. The bib ligands act as linear bidentate linkers to form a four-fold interpenetrated 3D framework with a dia-like topology. The H 2 uptake of the dehydrated coordination framework of 1 was estimated using a computational method based on Connolly's algorithm, which indicated that adsorbed H 2 is predominantly located around the outer surface of the pore through multipoint interactions with the inner surface of dehydrated 1′. The material has no significant adsorption for CO 2 or N 2 gas upon desolvation by long-time thermal activation, indicating that access to the void space is blocked by the large and immobile anions. The luminescence properties of sample 1 and dehydrated sample 1′ were also explored.
Published: 2014
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44. Coordination polymers based on heterohexanuclear rare earth complexes: toward independent luminescence brightness and color tuning

Author: Laurent Le Pollès, Guillaume Calvez, James Ledoux, Kevin Bernot, François Le Natur, Olivier Guillou, Carole Daiguebonne, Claire Roiland, 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), Institut de Recherche Mathématique de Rennes (IRMAR), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-École normale supérieure - Rennes (ENS Rennes)-Université de Rennes 2 (UR2)-Centre National de la Recherche Scientifique (CNRS)-INSTITUT AGRO Agrocampus Ouest, Institut national d'enseignement supérieur pour l'agriculture, l'alimentation et l'environnement (Institut Agro)-Institut national d'enseignement supérieur pour l'agriculture, l'alimentation et l'environnement (Institut Agro), 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), AGROCAMPUS OUEST, Institut national d'enseignement supérieur pour l'agriculture, l'alimentation et l'environnement (Institut Agro)-Institut national d'enseignement supérieur pour l'agriculture, l'alimentation et l'environnement (Institut Agro)-Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Université de Rennes 2 (UR2), Université de Rennes (UNIV-RENNES)-École normale supérieure - Rennes (ENS Rennes)-Centre National de la Recherche Scientifique (CNRS)-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)
Subjects: Lanthanide, Models, Molecular, Luminescence, Luminescent Measurements, Coordination polymer, Polymers, Inorganic chemistry, Color, [CHIM.INOR]Chemical Sciences/Inorganic chemistry, 010402 general chemistry, Crystallography, X-Ray, 01 natural sciences, Lanthanoid Series Elements, Inorganic Chemistry, Metal, chemistry.chemical_compound, Organometallic Compounds, Physical and Theoretical Chemistry, Terephthalic acid, 010405 organic chemistry, [CHIM.MATE]Chemical Sciences/Material chemistry, Chemical formula, 0104 chemical sciences, Crystallography, Solid-state nuclear magnetic resonance, chemistry, visual_art, visual_art.visual_art_medium
Abstract: International audience; Reactions in solvothermal conditions between hexanuclear rare earth complexes and H2bdc, where H2bdc symbolizes terephthalic acid, lead to a family of monodimensional coordination polymers in which hexanuclear complexes act as metallic nodes. The hexanuclear cores can be either homometallic with general chemical formula [Ln6O(OH)8(NO3)6](2+) (Ln = Pr-Lu plus Y) or heterometallic with general chemical formula [Ln6xLn'6-6xO(OH)8(NO3)6](2+) (Ln and Ln' = Pr-Lu plus Y). Whatever the hexanuclear entity is, the resulting coordination polymer is iso-structural to [Y6O(OH)8(NO3)2(bdc)(Hbdc)2.2NO3.H2bdc]infinity, a coordination polymer that we have previously reported. The random distribution of the lanthanide ions over the six metallic sites of the hexanuclear entities is demonstrated by (89)Y solid state NMR, X-ray diffraction (XRD), and luminescent measurements. The luminescent and colorimetric properties of selected compounds that belong to this family have been studied. These studies demonstrate that some of these compounds exhibit very promising optical properties and that there are two ways of modulating the luminescent properties: (i) playing with the composition of the heterohexanuclear entities or (ii) playing with the relative ratio between two different hexanuclear entities. This enables the independent tuning of luminescence intensity and color.
Published: 2013
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45. Influence of ferromagnetic connection of Ising-type Dy(III)-based single ion magnets on their magnetic slow relaxation

Author: Carole Daiguebonne, Xiaohui Yi, Javier Luzón, Kevin Bernot, Olivier Guillou, Olivier Cador, Guillaume Calvez, 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), Ministerio de Economía y Competitividad (España), Centre National de la Recherche Scientifique (France), China Scholarship Council, European Commission, L'Institut National des Sciences Appliquées de Rennes, Région Bretagne, 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: Condensed matter physics, 010405 organic chemistry, Chemistry, Magnetometer, Relaxation (NMR), [CHIM.CATA]Chemical Sciences/Catalysis, 010402 general chemistry, Condensed Matter::Mesoscopic Systems and Quantum Hall Effect, 01 natural sciences, 3. Good health, 0104 chemical sciences, Ion, law.invention, Inorganic Chemistry, Ferromagnetism, law, Magnet, Ising model, Single-molecule magnet, Condensed Matter::Strongly Correlated Electrons, Quantum tunnelling
Abstract: et al., Two DyIII ions can be water bridged to form a textbook example of ferromagnetic short-bridged Dy-dimers where strong Ising anisotropy can be evidenced by single-crystal rotating magnetometry. The dimers present both single ion and single molecule magnet behaviour. Magnetic dilution evidences the influence of the ferromagnetic coupling on magnetic relaxation and especially quantum tunnelling. © The Royal Society of Chemistry 2013., This work was supported by Région Bretagne, Rennes Métropole, INSA Rennes, China Scholarship Council (CSC), CNRS, Université de Rennes 1, FEDER and Spanish research program MAT2011-27233-C02-02.
Published: 2013
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46. 1,2,4,5-Benzene-tetra-carboxylic acid : a versatile ligand for high dimensional lanthanide-based coordination polymers

Author: Guillaume Calvez, Nicolas Kerbellec, Kevin Bernot, Thierry Roisnel, Carole Daiguebonne, Olivier Guillou, Stéphane Freslon, Yun Luo, 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, Materials science, Carboxylic acid, Inorganic chemistry, Crystal structure, 010402 general chemistry, 01 natural sciences, HYDROTHERMAL SYNTHESIS, chemistry.chemical_compound, METAL-ORGANIC FRAMEWORK, [CHIM.CRIS]Chemical Sciences/Cristallography, Hydrothermal synthesis, General Materials Science, CRYSTAL-STRUCTURE, Benzene, chemistry.chemical_classification, biology, 010405 organic chemistry, Ligand, POROSITY, General Chemistry, Condensed Matter Physics, biology.organism_classification, 0104 chemical sciences, Crystallography, chemistry, Tetra, Metal-organic framework, COMPLEXES, GIANT PORES, 5-BENZENETETRACARBOXYLIC ACID, STORAGE
Abstract: International audience; Reactions in water between 1,2,4,5-benzene-tetra-carboxylate and lanthanide ions lead to seven families of lanthanide-containing coordination polymers with respective chemical formulae {[Tm-4(btec)(3)(H2O)(10)]center dot 7H(2)O}(infinity) (Family 1), {[Ln(4)(btec)(3)(H2O)(10)]center dot 16H(2)O}(infinity) with Ln = Ho and Tm (Family 2), {[Ln(4)(btec)(3)(H2O)(12)]center dot 12H(2)O}(infinity) with Ln = Er, Tm and Y (Family 3), {[Ln(4)(btec)(3)(H2O)(12)]center dot 11H(2)O}(infinity) with Ln = Er, Tm and Y (Family 4), {[Gd-4(btec)(3)(H2O)(14)]center dot 14H(2)O}(infinity) (Family 5), {[Ln(5)(btec)(3)(Hbtec)(H2O)(12)]}(infinity) with Ln = Eu and Gd (Family 6) and {[KGd5(btec)(4)(H2O)(13)]center dot 11H2O}(infinity) (Family 7). All these compounds have been obtained by slow diffusion through water or gel media. They have been structurally characterized. Six out of the seven families are three-dimensional and their potential porosities have been estimated by a computational method. Compounds that belong to families 2, 4 and 6 present a potential porosities of 1281 m(-1), 1156 m(2) g(-1) and 836 m(2) g(-1), respectively.
Published: 2013
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47. Corrigendum: A Luminescent and Sublimable DyIII-Based Single-Molecule Magne

Author: Roberta Sessoli, Guillaume Calvez, Giordano Poneti, Fabrice Pointillart, Xiaohui Yi, Kevin Bernot, Carole Daiguebonne, Olivier Guillou, 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), Department of Chemistry 'Ugo Schiff', Università degli Studi di Firenze = University of Florence [Firenze] (UNIFI), Department of Applied Sciences and Technology, Guglielmo Marconi University, 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 Firenze = University of Florence (UniFI)
Subjects: Lanthanide, 010405 organic chemistry, Chemistry, Organic Chemistry, General Chemistry, [CHIM.INOR]Chemical Sciences/Inorganic chemistry, 010402 general chemistry, 01 natural sciences, Catalysis, 0104 chemical sciences, Physical chemistry, Single-molecule magnet, Thermal stability, Luminescence, ComputingMilieux_MISCELLANEOUS, Nuclear chemistry
Abstract: International audience
Published: 2013
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48. A luminescent and sublimable Dy(III)-based single-molecule magnet

Author: Roberta Sessoli, Giordano Poneti, Guillaume Calvez, Olivier Guillou, Fabrice Pointillart, Kevin Bernot, Carole Daiguebonne, Xiaohui Yi, Institut des Sciences Chimiques de Rennes (ISCR), 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), Department of Chemistry 'Ugo Schiff', Università degli Studi di Firenze = University of Florence [Firenze] (UNIFI), CNRS, FEDER, European Commission, 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 Firenze = University of Florence (UniFI)
Subjects: Lanthanide, 010405 organic chemistry, Chemistry, Organic Chemistry, Relaxation (NMR), Quantum yield, General Chemistry, [CHIM.INOR]Chemical Sciences/Inorganic chemistry, 010402 general chemistry, 01 natural sciences, Catalysis, thermal stability, 3. Good health, 0104 chemical sciences, Crystallography, Magnetization, Nuclear magnetic resonance, luminescence, Antiferromagnetism, Single-molecule magnet, lanthanides, magnetic properties, Isostructural, single-molecule magnets, Luminescence
Abstract: International audience; The reaction of [Ln(hfac)(3)]*2H(2)O and pyridine-N-oxide (PyNO) leads to isostructural dimers of the formula [Ln(hfac)(3)(PyNO)](2) (Ln=Eu, Gd, Tb, Dy). The Dy derivative shows a remarkable single-molecule magnet behavior with complex hysteresis at 1.4 K. The dynamics of the magnetization features are two relaxation regimes: a thermally activated one at high temperature (τ(0)=(5.62±0.4)×10(-11) s and Δ=(167±1) K) and a quantum tunneling regime at low temperature with a tunneling frequency of 0.42 Hz. The analysis of the Gd derivative evidences intradimer antiferromagnetic interactions (J=(-0.034±0.001) cm(-1)). Moreover, the Eu, Tb, and Dy derivatives are luminescent with quantum yield of 51, 53, and 0.1%, respectively. The thermal investigation of [Dy(hfac)(3)(PyNO)](2) shows that the dimers can be sublimated intact, suggesting their possible exploit as active materials for surface-confined nanostructures to be investigated by fluorimetry methods.
Published: 2012
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49. Magnetic anisotropy in a dysprosium/DOTA single-molecule magnet: Beyond simple magneto-structural correlations

Author: Giuseppe Cucinotta, Andrea Caneschi, Roberta Sessoli, Javier Luzón, Mauro Perfetti, Mael Etienne, Pierre-Emmanuel Car, Kevin Bernot, Guillaume Calvez, Department of Chemistry 'Ugo Schiff', 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), Università degli Studi di Firenze = University of Florence (UniFI), 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, chemistry.chemical_element, [CHIM.INOR]Chemical Sciences/Inorganic chemistry, 010402 general chemistry, 01 natural sciences, Catalysis, Heterocyclic Compounds, 1-Ring, Magnetics, chemistry.chemical_compound, Nuclear magnetic resonance, Ab initio quantum chemistry methods, luminescence, DOTA, Molecule, dysprosium, Single-molecule magnet, Physics::Atomic Physics, Anisotropy, Magneto, ComputingMilieux_MISCELLANEOUS, Molecular Structure, Condensed matter physics, 010405 organic chemistry, General Medicine, General Chemistry, equipment and supplies, 3. Good health, 0104 chemical sciences, Magnetic anisotropy, chemistry, Dysprosium, Ab initio calculations, magnetic properties, human activities
Abstract: Magnetic moments: The orientation of the title single-molecule magnet was investigated by magnetic single crystal and luminescence characterization, supported by ab initio calculations, and was found to be governed by the position of the hydrogen atoms of the apical water molecules. This finding suggests that simple magneto-structural correlations can give misleading clues for research in molecular magnetism as well as in the design of MRI contrast agents., This work was supported by the European Research Council through ERC-AdG “MolNanoMaS”.
Published: 2012
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50. A New Series of Anhydrous Lanthanide-Based Octahedral Hexanuclear Complexes

Author: Guillaume Calvez, Carole Daiguebonne, Olivier Guillou, Florence Le Dret, Sciences Chimiques de Rennes / Matériaux Inorganiques: Chimie Douce et Réactivité (MICDR), 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)-Centre National de la Recherche Scientifique (CNRS), 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)-Centre National de la Recherche Scientifique (CNRS)
Subjects: Lanthanide, 010405 organic chemistry, Chemistry, Inorganic chemistry, Crystal structure, Triclinic crystal system, [CHIM.INOR]Chemical Sciences/Inorganic chemistry, 010402 general chemistry, Heterogeneous catalysis, 01 natural sciences, 0104 chemical sciences, Inorganic Chemistry, Crystallography, Octahedron, Polymorphism (materials science), Anhydrous, Isostructural, ComputingMilieux_MISCELLANEOUS
Abstract: The synthesis of hexanuclear lanthanide oxido/hydroxido complexes by direct hydrolysis has been reinvestigated and optimized. Lanthanide oxido/hydroxido complexes of the general formula [Ln6O(OH)8(NO3)6(H2O)x]2NO3·2H2O (with x = 12 for Ln = Sm–Yb or Y, x = 14 for Ln = Pr or Nd, and x = 16 for Ln = Ce) have been obtained and characterized. The dehydration of all these complexes leads to isostructural anhydrous compounds with the general formula [Ln6O(OH)8(NO3)8]∞. The crystal structure has been solved on the basis of powder X-ray diffraction of the Y-containing compound. This compound crystallizes in the triclinic system, and the crystal structure can be described as the juxtaposition of infinite chains of hexanuclear complexes linked to each other by nitrate groups. These anhydrous compounds are readily soluble in most organic solvents and can be used as molecular precursors for further chemistry. When exposed to moisture, they rehydrate reversibly, which leads to their initial hydrated phase. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009)
Published: 2009
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