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59 results on '"Guillaume Calvez"'

1. Self-assembly of a terbium(III) 1D coordination polymer on mica

Author: Quentin Evrard, Giuseppe Cucinotta, Felix Houard, Guillaume Calvez, Yan Suffren, Carole Daiguebonne, Olivier Guillou, Andrea Caneschi, Matteo Mannini, and Kevin Bernot
Subjects: atomic force microscopy (afm), luminescence, nanostructuration, polymer, self-assembly, surface, terbium complexes, Technology, Chemical technology, TP1-1185, Science, Physics, QC1-999
Abstract: The terbium(III) ion is a particularly suitable candidate for the creation of surface-based magnetic and luminescent devices. In the present work, we report the epitaxial growth of needle-like objects composed of [Tb(hfac)3·2H2O]n (where hfac = hexafluoroacetylacetonate) polymeric units on muscovite mica, which is observed by atomic force microscopy. The needle-like shape mimics the structure observed in the crystalline bulk material. The growth of this molecular organization is assisted by water adsorption on the freshly air-cleaved muscovite mica. This deposition technique allows for the observation of a significant amount of nanochains grown along three preferential directions 60° apart from another. The magnetic properties and the luminescence of the nanochains can be detected without the need of surface-dedicated instrumentation. The intermediate value of the observed luminescence lifetime of the deposits (132 µs) compared to that of the bulk (375 µs) and the CHCl3 solution (13 µs) further reinforces the idea of water-induced growth.
Published: 2019
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2. Crystal structure of [Y6(μ6-O)(μ3-OH)8(H2O)24]I8·8H2O

Author: François Le Natur, Guillaume Calvez, Olivier Guillou, Carole Daiguebonne, and Kevin Bernot
Subjects: crystal structure, hexanuclear compounds, lanthanide compound, three-dimensional hydrogen-bonded network, Crystallography, QD901-999
Abstract: The crystal structure of the title compound {systematic name: octa-μ3-hydroxido-μ6-oxido-hexakis[tetraaquayttrium(III)] octaiodide octahydrate}, is characterized by the presence of the centrosymmetric molecular entity [Y6(μ6-O)(μ3-OH)8(H2O)24]8+, in which the six Y3+ cations are arranged octahedrally around a μ6-O atom at the centre of the cationic complex. Each of the eight faces of the Y6 octahedron is capped by an μ3-OH group in the form of a distorted cube. In the hexanuclear entity, the Y3+ cations are coordinated by the central μ6-O atom, the O atoms of four μ3-OH and of four water molecules. The resulting coordination sphere of the metal ions is a capped square-antiprism. The crystal packing is quite similar to that of the orthorhombic [Ln6(μ6-O)(μ3-OH)8(H2O)24]I8·8H2O structures with Ln = La—Nd, Eu—Tb, Dy, except that the title compound exhibits a slight monoclinic distortion. The proximity of the cationic complexes and the lattice water molecules leads to the formation of a three-dimensional hydrogen-bonded network of medium strength.
Published: 2014
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3. Closing the Circle of the Lanthanide-Murexide Series: Single-Molecule Magnet Behavior and Near-Infrared Emission of the NdIII Derivative

Author: Gang Huang, Guillaume Calvez, Yan Suffren, Carole Daiguebonne, Stéphane Freslon, Olivier Guillou, and Kevin Bernot
Subjects: lanthanides, neodymium single-molecule magnets, near-infrared emission, bifunctionality, Chemistry, QD1-999
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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4. Lanthanide-Based Coordination Polymers Molecular Alloys Stability: A Thermochemical Approach

Author: Chloé Blais, Thibaut Morvan, Carole Daiguebonne, Yan Suffren, Guillaume Calvez, Kevin Bernot, Olivier Guillou, Institut des Sciences Chimiques de Rennes (ISCR), 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: Inorganic Chemistry, [CHIM]Chemical Sciences, Physical and Theoretical Chemistry
Abstract: International audience; In this study, we investigate the thermodynamics of lanthanide-based coordination polymer molecular alloys. We demonstrate that if lanthanide ions have many chemical similarities, the solubility of homo-lanthanide-based coordination polymers can vary significantly from one lanthanide ion to another. Indeed, we experimentally determine the solubility constants of a series of isostructural homo-lanthanide coordination polymers, with general chemical formula [Ln2(bdc)3(H2O)4]infinity with Ln = La-Er plus Y and where bdc2- symbolizes 1,4-benzene-di-carboxylate. Then, we extend the study to two series of isostructural molecular alloys with general chemical formula [Ln2xLn ' 2 -2x(bdc)3(H2O)4]infinity with 0
Published: 2023
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5. Metallogels: a novel approach for the nanostructuration of single-chain magnets

Author: Felix Houard, Guiseppe Cucinotta, Thierry Guizouarn, Yan Suffren, Guillaume Calvez, Carole Daiguebonne, Olivier Guillou, Franck Artzner, Matteo Mannini, 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), National Interuniversity Consortium of Materials Science and Technology (INSTM ), Università degli Studi di Firenze = University of Florence (UniFI), Institut de Physique de Rennes (IPR), Université de Rennes (UR)-Centre National de la Recherche Scientifique (CNRS), and This work was supported by the French ministry of high education and research (MESRI), Region Bretagne, Rennes Metropole, INSA PPI program, CNRS via Florennes PICS Program. The authors acknowledge M. Dallon (CDIFX) for crystal structure refinement, K. B. acknowledges Institut Universitaire de France. F. H. acknowledges SATT Ouest Valorisation for funding. M. M. and G. C. acknowledge the Italian MIUR, through the Project 'Dipartimenti di Eccellenza 2018-2022 (ref. no. B96C1700020008) and Fondazione Cassa di Risparmio di Firenze (Project SPINE-2 2020.1634) for the financial support. Surface depositions have been carried out at the surface science laboratories of the MatchLab Interdepartmental Research Unit, University of Florence.
Subjects: [PHYS]Physics [physics], Mechanics of Materials, Process Chemistry and Technology, [CHIM]Chemical Sciences, General Materials Science, Electrical and Electronic Engineering
Abstract: International audience; In this study we demonstrate that single-chain magnets (SCMs) can be assembled in gel phase and transferred intact on surface. We take advantage of a family of SCMs based on Tb(III) ions and nitronyl-nitroxides radicals functionalized with short alkyl chains known to form crystalline supramolecular nanotubes interacting with heptane acting as crystallizing solvent. When the radicals are functionalized with long aliphatic chains a robust gel is formed with similar structural and functional properties respect to its crystalline parent. Indeed, a small-angle X-ray scattering (SAXS) study unambiguously demonstrates that the gel is made of supramolecular nanotubes: the high stability of the gel allows the determination from SAXS data of precise nanotube metrics such as diameter, helical pitch and monoclinic cell of the folded 2D crystal lattice along the tube direction. Additionally, static and dynamic magnetic investigations show the persistence of the SCM behavior in the metallogel. Last, on-surface gelation provides thick films as well as sub-monolayer deposits of supramolecular nanotubes on surface as evidenced by atomic force microscopy (AFM) observations. This paves the road toward magnetic materials and devices made of SCMs profiting of their isolation on surface as individual chains.
Published: 2023
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6. 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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7. Investigation of Intermetallic Energy Transfers in Lanthanide Coordination Polymers Molecular Alloys: Case Study of Trimesate-Based Compounds

Author: Chloé Blais, Carole Daiguebonne, Yan Suffren, Kevin Bernot, Guillaume Calvez, Laurent Le Pollès, Claire Roiland, Stéphane Freslon, Olivier Guillou, Institut des Sciences Chimiques de Rennes (ISCR), 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: Inorganic Chemistry, [CHIM]Chemical Sciences, Physical and Theoretical Chemistry
Abstract: International audience; Reactions in water at ambient temperature and pressure between a lanthanide ion and benzene-1,3,5-tricarboxylate (or trimesate) lead to two series of iso-structural coordination polymers. Their general chemical formula is [Ln(tma)(H(2)O)(6)](∞) for the lightest lanthanide ions (Ln = La-Dy except Pm), while it is [Ln(tma)(H(2)O)(5)·3.5H(2)O](∞) for the heaviest ones (Ho-Lu plus Y). For the heaviest lanthanide ions, reactions at 50 °C lead to a third structural family with the general chemical formula [Ln(tma)(H(2)O)(3)·1.5H(2)O](∞) with Ln = Ho-Lu plus Y. Homo-lanthanide coordination polymers that belong to the latter two families do not exhibit luminescence in the visible region. Therefore, we used a phase induction strategy to obtain molecular alloys that belong to these structural families and show sizeable emission. The random distribution of the lanthanide ions over the metallic sites has been investigated using (89)Y and (139)La solid-state NMR spectroscopy experiments. Luminescent properties of homo- and hetero-nuclear coordination polymers based on Eu(3+) and Tb(3+) have been studied in detail and compared. As a result, this study strongly suggests that exchange-based intermetallic energy transfer mechanisms play an important role in these systems. It also suggests the presence of an intermetallic exchange pathway through π-stacking interactions.
Published: 2022
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8. Impact of intermolecular non-covalent interactions in a CuI8PdII1 discrete assembly: conformers’ geometries and stimuli-sensitive luminescence properties

Author: Florent Moutier, Jana Schiller, Constance Lecourt, Ali Moustafa Khalil, Vincent Delmas, Guillaume Calvez, Karine Costuas, Christophe Lescop, Institut des Sciences Chimiques de Rennes (ISCR), 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: polymetallic Cu(I) ion complexes, TD DFT calculations, Organic Chemistry, conformers, luminescence, [CHIM.CRIS]Chemical Sciences/Cristallography, Mechanochromism, [CHIM.COOR]Chemical Sciences/Coordination chemistry, General Chemistry, Catalysis
Abstract: International audience; A new highly solid-state luminescent phase of a previously reported weakly luminescent Cu I 8 Pd II 1 dicationic assembly is reported revealing the high geometrical versatility of this moiety that importantly alters its luminescent properties. This very minor new species B c is based on a different conformer scaffold than the one encountered in the previously reported B o form and, essentially differs from B o by displaying shorter Cu I -Cu I intermetallic distances. DFT calculations allow concluding that the predominance in the solid-state of the weakly luminescent and less stable B o phase is due to the extra stability induced by a larger number of intermolecular non-covalent π-CH interactions in its crystalline packing and not by the intrinsic stability of the Cu I 8 Pd II 1 dicationic moiety. Calculations also revealed that a more stable conformation B calc is expected in vacuum, which bears a different distribution of Cu I -Cu I intermetallic distances than the dications in B o and B c phases. Taking into account that the geometrical alterations are associated to drastic changes of luminescence properties, this confer to the Cu I 8 Pd II 1 assembly high potentiality as stimuli-sensitive luminescent materials. Indeed, by applying mechanical or thermal stress to samples of B o phase, new phases B g and B m , respectively, were obtained. Alterations of the solid-state photophysical properties of these new species compared to those recorded for B o are reported together with a combined experimental and computed study of the structures/properties relationships observed in these phases.
Published: 2022
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9. 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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10. Hexanuclear Molecular Precursors as Tools to Design Luminescent Coordination Polymers with Lanthanide Segregation

Author: Olivier Guillou, Haiyun Yao, Yan Suffren, Carole Daiguebonne, Kevin Bernot, 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), The China Scholarship Council Ph.D. Program, a cooperation program with the French UT and INSA, is acknowledged for financial support., 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, 02 engineering and technology, Crystal structure, [CHIM.INOR]Chemical Sciences/Inorganic chemistry, 010402 general chemistry, Ligands, 01 natural sciences, Inorganic Chemistry, Lanthanides, [CHIM]Chemical Sciences, Physical and Theoretical Chemistry, Isostructural, chemistry.chemical_classification, Ions, Chemistry, Polymer, 021001 nanoscience & nanotechnology, Chemical formula, 0104 chemical sciences, Coordination polymers, Crystallography, Orthorhombic crystal system, 0210 nano-technology, Luminescence, Europium
Abstract: International audience; Solvothermal reactions between hexanuclear complexes with the general chemical formula [Ln(6)(μ(6)-O)(μ(3)-OH)(8)(NO(3))(6)(H(2)O)(12)]·2NO(3)·2H(2)O and 2-bromobenzoic acid (2-bbH) lead to a series of isostructural one-dimensional coordination polymers with the general chemical formula [Ln(2)(2-bb)(6)](∞) with Ln = Sm, Eu, Tb, Dy, and Y. These coordination polymers crystallize in the orthorhombic space group Fdd2 (No. 43) with the following cell parameters: a = 29.810(3) Å, b = 51.185(6) Å, c = 11.7913(14) Å, V = 17992(4) Å(3), and Z = 16. The europium- and terbium-based derivatives show sizable luminescence intensities under UV excitation. Isostructural heterolanthanide coordination polymers have also been prepared. Their luminescent properties suggest that during the synthetic process the starting hexanuclear complexes are destroyed but strongly influence the distribution of the different lanthanide ions over the metallic sites of the crystal structure. Indeed, it is possible to prepare heterolanthanide coordination polymers in which lanthanide-ion segregation is controlled.
Published: 2021
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11. 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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12. 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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13. 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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14. 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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15. 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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16. 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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17. 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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18. 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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19. 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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20. 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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21. 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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22. Self-assembly of a terbium(III) 1D coordination polymer on mica

Author: Andrea Caneschi, Matteo Mannini, Quentin Evrard, Guillaume Calvez, Carole Daiguebonne, Yan Suffren, Olivier Guillou, Felix Houard, Giuseppe Cucinotta, 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), 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.), Rennes MetropoleRegion Bretagne, INSA Rennes, CNRSCentre National de la Recherche Scientifique (CNRS), Fondazione Ente Cassa Risparmio di Firenze (progetto SPIN-E)Fondazione Cassa Risparmio Firenze [2017.0730], MIUR-Italy ('Progetto Dipartimenti di Eccellenza 2018-2022) [B96C1700020008], 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, Coordination polymer, polymer, General Physics and Astronomy, chemistry.chemical_element, Terbium, 02 engineering and technology, engineering.material, 010402 general chemistry, Epitaxy, lcsh:Chemical technology, 01 natural sciences, lcsh:Technology, Full Research Paper, chemistry.chemical_compound, Adsorption, nanostructuration, luminescence, Nanotechnology, surface, [CHIM]Chemical Sciences, General Materials Science, lcsh:TP1-1185, atomic force microscopy (AFM), Electrical and Electronic Engineering, lcsh:Science, lcsh:T, Muscovite, self-assembly, 021001 nanoscience & nanotechnology, lcsh:QC1-999, 0104 chemical sciences, Crystallography, Nanoscience, chemistry, engineering, lcsh:Q, Self-assembly, Mica, terbium complexes, 0210 nano-technology, Luminescence, lcsh:Physics
Abstract: The terbium(III) ion is a particularly suitable candidate for the creation of surface-based magnetic and luminescent devices. In the present work, we report the epitaxial growth of needle-like objects composed of [Tb(hfac)3·2H2O]n (where hfac = hexafluoroacetylacetonate) polymeric units on muscovite mica, which is observed by atomic force microscopy. The needle-like shape mimics the structure observed in the crystalline bulk material. The growth of this molecular organization is assisted by water adsorption on the freshly air-cleaved muscovite mica. This deposition technique allows for the observation of a significant amount of nanochains grown along three preferential directions 60° apart from another. The magnetic properties and the luminescence of the nanochains can be detected without the need of surface-dedicated instrumentation. The intermediate value of the observed luminescence lifetime of the deposits (132 µs) compared to that of the bulk (375 µs) and the CHCl3 solution (13 µs) further reinforces the idea of water-induced growth.
Published: 2019
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23. 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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24. 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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25. 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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26. 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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27. 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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28. 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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29. A series of chiral metal–organic frameworks based on fluorene di- and tetra-carboxylates: syntheses, crystal structures and luminescence properties

Author: Pascal Roussel, Cyril Poriel, Thierry Roisnel, Vincent Dorcet, Nathalie Audebrand, Julien Robin, Guillaume Calvez, Jérôme Canivet, Institut Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier (ICGM), Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)-Centre National de la Recherche Scientifique (CNRS), 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), IRCELYON-Ingéniérie, du matériau au réacteur (ING), Institut de recherches sur la catalyse et l'environnement de Lyon (IRCELYON), 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)-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), Unité de Catalyse et Chimie du Solide - UMR 8181 (UCCS), Université d'Artois (UA)-Centrale Lille-Institut de Chimie du CNRS (INC)-Université de Lille-Centre National de la Recherche Scientifique (CNRS), Institut Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier (ICGM ICMMM), Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Centre National de la Recherche Scientifique (CNRS)-Université de Montpellier (UM)-Université Montpellier 1 (UM1)-Université Montpellier 2 - Sciences et Techniques (UM2)-Institut de Chimie du CNRS (INC), Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Université de Lyon-Université de Lyon-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC), Centrale Lille Institut (CLIL)-Université d'Artois (UA)-Centrale Lille-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Lille, 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, 02 engineering and technology, Crystal structure, Fluorene, [CHIM.INOR]Chemical Sciences/Inorganic chemistry, 010402 general chemistry, Photochemistry, 01 natural sciences, Methane, chemistry.chemical_compound, General Materials Science, Carboxylate, ComputingMilieux_MISCELLANEOUS, biology, Ligand, General Chemistry, 021001 nanoscience & nanotechnology, Condensed Matter Physics, biology.organism_classification, 0104 chemical sciences, Crystallography, chemistry, Tetra, Metal-organic framework, 0210 nano-technology, Luminescence
Abstract: A series of optically pure carboxylate ligands based on a fluorene backbone were synthesized and used for the elaboration of four chiral metal–organic frameworks (6, 7, 8, and 9) containing Cu-based paddle-wheels. The positions and numbers of coordinating carboxylate functions on the ligand core govern the resulting MOF topologies, leading to a 1D framework (8), 2D grids with (7) or without interpenetration (6), and a 3D (9) framework and showing calculated porosities ranging from 8 to 47% of the unit-cell volumes. Ligands as well as corresponding MOFs possess luminescence properties with blue emission. The most porous MOF (9), made of a tetracarboxylate ligand, exhibits a BET apparent surface area of 467 m2 g−1 and methane and carbon dioxide storage capacities of 26.5 cm3 g−1 and 129 cm3 g−1, respectively, at 303 K and 30 bar.
Published: 2017
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30. 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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31. 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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32. 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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33. Extending the lanthanide–terephthalate system: Isolation of an unprecedented Tb(III)-based coordination polymer with high potential porosity and luminescence properties

Author: Kevin Bernot, François Le Natur, Stéphane Freslon, Olivier Guillou, 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), 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, Coordination polymer, Organic Chemistry, Inorganic chemistry, Crystal structure, [CHIM.INOR]Chemical Sciences/Inorganic chemistry, Chemical formula, Evaporation (deposition), Analytical Chemistry, Inorganic Chemistry, chemistry.chemical_compound, Crystallography, chemistry, Luminescence, Ethylene glycol, Spectroscopy, Monoclinic crystal system
Abstract: International audience; A novel coordination polymer with chemical formula {[Tb(bdc)1.5(H2O)](DMF)(H2O)}1 (1) has been synthesizedby reaction between 1,4-benzene-dicarboxylic acid (H2bdc) and di-cationic hexanuclear entity[Tb6O(OH)8(NO3)6(H2O)12]2+ in an ethylene glycol (EG)/N,N-dimethylformamide (DMF) mixture. Thiscompound has been obtained as single crystals by slow evaporation in air at room temperature. If thehexanuclear entity is destroyed during the reaction, the coordination polymer that is obtained is originaland presents promising potential micro-porosity and luminescent properties. It crystallizes in the monoclinicsystem, space group C12/c1 (No. 15) with the cell parameters a = 23.7540(1) Å, b = 10.5390(4) Å,c = 19.7580(3) Å, b = 125.8100(1) and Z = 8.
Published: 2015
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34. Nanometrization of Lanthanide-Based Coordination Polymers

Author: Stéphane Cordier, Olivier Guillou, Guillaume Calvez, Chrystelle Neaime, Kevin Bernot, Carole Daiguebonne, Fabien Grasset, Stéphane Freslon, 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 Institute for Materials Science (NIMS), Laboratory for Innovative Key Materials and Structures (LINK), SAINT-GOBAIN-National Institute of Materials Science-Centre National de la Recherche Scientifique (CNRS), Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), and Saint-Gobain-National Institute of Materials Science-Centre National de la Recherche Scientifique (CNRS)
Subjects: Lanthanide, Polymers, Inorganic chemistry, Nanoparticle, 02 engineering and technology, 010402 general chemistry, 01 natural sciences, Lanthanoid Series Elements, Catalysis, chemistry.chemical_compound, Organometallic Compounds, luminescence, [CHIM]Chemical Sciences, lanthanides, Group 2 organometallic chemistry, chemistry.chemical_classification, Ions, Organic Chemistry, General Chemistry, Polymer, 021001 nanoscience & nanotechnology, 0104 chemical sciences, Solvent, Solutions, coordination polymers, chemistry, Heteronuclear molecule, post-synthesis processing, Physical chemistry, nanoparticles, 0210 nano-technology, Luminescence, Ethylene glycol
Abstract: International audience; Heteronuclear lanthanide-based coordination polymers are microcryst. powders, the luminescence properties of which can be precisely tuned by judicious choice of the rare-earth ions. In this study, we demonstrate that such materials can also be obtained as stable solns. of nanoparticles in non-toxic polyols. Bulk powders of the formula [Ln2-2xLn'2x(bdc)3[n.8901]4 H2O]∞ (where H2bdc denotes 1,4-benzene-dicarboxylic acid, 0≤x≤1, and Ln and Ln' denote lanthanide ions of the series La to Tm plus Y) afford nanoparticles that have been characterized by dynamic light-scattering (DLS) and transmission electron microscopy (TEM) measurements. Their luminescence properties are similar to those of the bulk materials. Stabilities vs. time and vs. diln. with another solvent have been studied. This study has revealed that it is possible to tune the size of the nanoparticles. This process offers a reliable means of synthesizing suspensions of nanoparticles with tunable luminescence properties and tunable size distributions in a green solvent (glycerol). The process is also extendable to other coordination polymers and other solvents (ethylene glycol, for example). It constitutes a new route for the facile solubilization of lanthanide-based coordination polymers.
Published: 2015
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35. 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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36. Influence of photoinduced electron transfer on lanthanide-based coordination polymer luminescence: a comparison between two pseudoisoreticular molecular networks

Author: Guillaume Calvez, Stéphane Freslon, Kevin Bernot, Vincent Michel, Olivier Guillou, Yun Luo, Carole Daiguebonne, Xiao Fan, 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), 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, Coordination polymer, Inorganic chemistry, 02 engineering and technology, Crystal structure, [CHIM.INOR]Chemical Sciences/Inorganic chemistry, 010402 general chemistry, 021001 nanoscience & nanotechnology, 01 natural sciences, Homonuclear molecule, Photoinduced electron transfer, 0104 chemical sciences, Inorganic Chemistry, Isophthalic acid, Crystallography, chemistry.chemical_compound, chemistry, Heteronuclear molecule, Physical and Theoretical Chemistry, Isostructural, 0210 nano-technology
Abstract: International audience; The luminescent properties of two families of heteronuclear lanthanide-containing coordination polymers are compared. These families have general chemical formulas [Ln2-2xLn'2x(ip)3(H2O)9*6H2O]∞ and [Ln2-2xLn'2x(aip)2(H2O)10*(aip)*4H2O]∞ where H2ip and H2aip stand for isophthalic acid and 5-amino-isophthalic acid, respectively, and where Ln and Ln' are one of the lanthanide ions between Sm(3+) and Dy(3+). Heteronuclear compounds that belong to each family are isostructural to the already reported homonuclear compounds [Gd2(ip)3(H2O)9*6H2O]∞ and [Eu2(aip)2(H2O)10*(aip)*4H2O]∞, respectively. These two crystal structures are very similar. However, despite similar chemical formulas, similar crystal structures, and similar hydration rates, these two families of compounds present very different luminescent properties that have thus been deeply investigated. This study demonstrates that these different optical behaviors can be attributed to the presence of a PET (photoinduced electron transfer) mechanism that is only present in the amino-isophthalate-containing coordination polymers.
Published: 2014
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37. 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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38. 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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39. Heteronuclear lanthanide-based coordination polymers exhibiting tunable multiple emission spectra

Author: Laurent Le Pollès, Stéphane Freslon, Xiao Fan, Kevin Bernot, Guillaume Calvez, Olivier Guillou, Carole Daiguebonne, 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, Intermetallic, Analytical chemistry, 02 engineering and technology, General Chemistry, [CHIM.INOR]Chemical Sciences/Inorganic chemistry, 010402 general chemistry, 021001 nanoscience & nanotechnology, 01 natural sciences, 7. Clean energy, 0104 chemical sciences, Electron transfer, Solid-state nuclear magnetic resonance, Heteronuclear molecule, Materials Chemistry, Physical chemistry, Emission spectrum, 0210 nano-technology, Luminescence, Spectroscopy
Abstract: International audience; Reactions in water at room temperature between lanthanide ions and 5-hydroxy-1,3-benzene-dicarboxylic acid hereafter referred to as H2(hip) lead to a new family of lanthanide-based hetero-nuclear compounds with the general chemical formula [Ln2 2xLn2x 0(hip)2(H2O)10,(hip),4H2O]N where Ln and Ln0 ¼ Pr-Lu or Y and where 0 # x # 1. The physico-chemical properties of this family have been characterized by PXRD, TDXD, TG/TD, EDS, SEM, 89Y solid state NMR spectroscopy and optical spectroscopy. The luminescent properties of these compounds are studied in detail. This study reveals that the competition between intermetallic energy transfer and photo-induced electron transfer gives rise to complex multiple emission spectra. It is therefore possible, for some Ln/Ln0 compositions, to obtain green, yellow or red emission by tuning the excitation wavelength over a 50 nm range. From a global point of view, this study shows that this series of compounds could be of great interest as far as luminescent coordination polymers usable as taggants for the fight against counterfeiting are aimed.
Published: 2014
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40. 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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41. Experimental and theoretical evidence that electrostatics governs easy-axis orientation in DyIII-based molecular chains

Author: Guillaume Calvez, Olivier Guillou, Olivier Cador, Thierry Guizouarn, Fabrice Pointillart, Julie Jung, Kevin Bernot, François Le Natur, Boris Le Guennic, 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), 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: Magnetometer, Chemistry, Relaxation (NMR), Metals and Alloys, General Chemistry, [CHIM.INOR]Chemical Sciences/Inorganic chemistry, Electrostatics, Catalysis, Symmetry (physics), Surfaces, Coatings and Films, Electronic, Optical and Magnetic Materials, law.invention, Crystallography, Magnetic anisotropy, Chain (algebraic topology), Ab initio quantum chemistry methods, Chemical physics, law, Orientation (geometry), Materials Chemistry, Ceramics and Composites
Abstract: International audience; Magnetic slow relaxation is observed in a DyIII-based molecular chain and the magnetic easy-axis is determined via single-crystal magnetometry. Ab initio calculations confirm its orientation and highlight that the latter is governed neither by coordination polyhedron symmetry nor by the chain direction but rather by the single-ion electrostatic environment, a feature that is confirmed by a similar theoretical analysis on other DyIII chains.
Published: 2014
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42. 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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43. 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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44. 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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45. Color and Brightness Tuning in Heteronuclear Lanthanide Terephthalate Coordination Polymers

Author: Olivier Guillou, Guillaume Calvez, Martin R. Mitchell, Carole Daiguebonne, Victor Haquin, Mael Etienne, Jean-Claude G. Bünzli, Svetlana V. Eliseeva, Laurent Le Pollès, Sharon E. Ashbrook, Stéphane Freslon, 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), Department of Chemistry 'Ugo Schiff', Università degli Studi di Firenze = University of Florence [Firenze] (UNIFI), Ecole Polytechnique Fédérale de Lausanne (EPFL), 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: chemistry.chemical_classification, Lanthanide, Brightness, Luminescence, Chemistry, Structure elucidation, Inorganic chemistry, Intermetallic, 02 engineering and technology, Polymer, Nuclear magnetic resonance spectroscopy, [CHIM.MATE]Chemical Sciences/Material chemistry, [CHIM.INOR]Chemical Sciences/Inorganic chemistry, 010402 general chemistry, 021001 nanoscience & nanotechnology, 01 natural sciences, Chemical formula, 0104 chemical sciences, Inorganic Chemistry, Coordination polymers, Heteronuclear molecule, Lanthanides, Physical chemistry, 0210 nano-technology
Abstract: International audience; Heteronuclear lanthanide terephthalate coordination polymers with the general chemical formula [Ln2-2xLn′2x(bdc)3(H2O)4]∞, for which bdc2- symbolizes benzene-1,4-dicarboxylate (or terephthalate) and Ln and Ln′ represent trivalent rare earth ions, were synthesized and structurally characterized. Analysis of the Y/Lu compounds by 89Y and 13C solid-state NMR spectroscopy was carried out, and the results support the hypothesis of randomly distributed lanthanide ions. The spectroscopic and colorimetric properties of this family of compounds were investigated in detail. The resulting data demonstrate that this series of compounds presents highly tunable luminescence properties and clearly indicate that intermetallic deactivation processes play an important role in the emission mechanism. Playing with intermetallic distances allows one to tune the color and the brightness of the lanthanide emission in these coordination polymers.
Published: 2013
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46. Synthesis, Crystal Structure and Luminescent Properties of New Lanthanide-Containing Coordination Polymers Involving 4,4'-oxy-bis-benzoate as Ligand

Author: Yun Luo, Guillaume Calvez, Carole Daiguebonne, Stéphane Freslon, Thierry Roisnel, Kevin Bernot, Yanjun Zheng, 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), China Scholarship Council, French UT 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, DECOMPOSITION, Coordination polymer, 02 engineering and technology, Crystal structure, [CHIM.INOR]Chemical Sciences/Inorganic chemistry, 010402 general chemistry, 01 natural sciences, HYDROTHERMAL SYNTHESIS, chemistry.chemical_compound, METAL-ORGANIC FRAMEWORKS, EXCITATION, PROGRAM, General Materials Science, Isostructural, HELICAL CHAINS, REFINEMENT, Ligand, POROSITY, General Chemistry, 021001 nanoscience & nanotechnology, Condensed Matter Physics, 0104 chemical sciences, Crystallography, Heteronuclear molecule, chemistry, ACID, Metal-organic framework, COMPLEXES, 0210 nano-technology, Monoclinic crystal system
Abstract: International audience; Reactions in water between the disodium salt of 4,4'-oxy-bis-benzoic acid (H(2)oba) and lanthanide chlorides lead to three families of coordination polymers with respective general chemical formulae [Ln(2)(oba)(3)(H2O)(5)center dot H2O](infinity) with Ln = La-Nd (Family 1), [Ln(2)(oba)(3)(H2O)(6)center dot 3H(2)O](infinity) with Ln = Sm-Ho or Y (Family 2) and [Ln(2)(oba)(3)(H2O)(5.5)center dot 0.5H(2)O](infinity) with Ln = Sm-Dy (Family 3). Compounds that belong to Family 1 are isostructural. The crystal structure has been solved on the basis of the La-containing compound. This compound crystallizes in the monoclinic system, space group P2/n (no. 13) with a = 23.622(4) angstrom, b = 6.066(1) angstrom, c = 29.414(6) angstrom, beta = 102.034(7)degrees, V = 4129.0(13) angstrom(3) and Z = 4. Compounds that belong to Family 2 are isostructural. The crystal structure has been solved on the Gd-containing compound. This compound crystallizes in the monoclinic system, space group P2/a (no. 14) with a = 9.9474(1) angstrom, b = 15.6416(2) angstrom, c = 28.7511(4) angstrom, beta = 95.117(1)degrees, V = 4455.65(10) angstrom(3) and Z = 4. Compounds that belong to Family 3 are isostructural. The crystal structure has been solved on the Gd-containing compound. This compound crystallizes in the monoclinic system, space group C2/c (no. 15) with a = 59.6523(11) angstrom, b = 8.2064(1) angstrom, c = 16.9558(2) angstrom, beta = 95.447(1)degrees, V = 8262.9(2) angstrom(3) and Z = 4. The three crystal structures are three-dimensional and rather compact. Their potential porosities are rather low. They have been estimated as 95 m(2) g(-1), 113 m(2) g(-1), and 36 m(2) g(-1) respectively. The luminescent properties under UV irradiation of these compounds have been explored. In particular, quantum yields, lifetimes and colorimetric coordinates of the Tb- and the Eu-containing coordination polymers have been determined. A heteronuclear coordination polymer with chemical formula [EuTb(oba)(3)(H2O)(5.5)center dot 0.5H(2)O](infinity) has been synthesized and characterized. It belongs to the structural family 3. Its luminescent properties have been explored in detail in order to better understand the energy transfer mechanisms and to evaluate the tunability of these families of compounds.
Published: 2013
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47. Structural and luminescence characterizations of lanthanide-based coordination polymers involving naphthalene-1,4,5,8-tetra-carboxylate as ligand

Author: Florence Le Dret, Yanjun Zheng, Magatte Camara, Guillaume Calvez, Kevin Bernot, Carole Daiguebonne, Olivier Guillou, Nicolas Kerbellec, 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 MatériauxInorganiques:Chimie Douce etCristallographie (LCPM), Université deZiguinchor, Chercheur indépendant, 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, Crystal growth, 02 engineering and technology, Crystal structure, [CHIM.INOR]Chemical Sciences/Inorganic chemistry, 010402 general chemistry, 01 natural sciences, Inorganic Chemistry, chemistry.chemical_compound, Materials Chemistry, Carboxylate, Thermal analysis, Physical and Theoretical Chemistry, biology, Chemistry, Ligand, Rare earth alloys and compounds, [CHIM.MATE]Chemical Sciences/Material chemistry, 021001 nanoscience & nanotechnology, biology.organism_classification, 0104 chemical sciences, Crystallography, Photo-luminescence properties, Tetra, 0210 nano-technology, Luminescence, Monoclinic crystal system
Abstract: Reactions in water between lanthanide ions and the sodium salt of naphthalene-1,4,5,8-tetra-carboxylic acid lead to three families of coordination polymers as microcrystalline powders and/or single crystals. Their respective chemical formulae are {[Ln(ntc)(H2O)5][Ln(H2O)10]1/3,3H2O}∞ with Ln = Ce, Gd or Eu (family 1), [NaYb(ntc)(H2O)6,4H2O]∞ (family 2), and [Ln2(ntc)1.5(H2O)11,9H2O]∞ with Ln = Dy–Er and Y (family 3). The crystal structure of family 1 has been solved on the basis of the Ce-containing compound. This compound crystallizes in the monoclinic system, space group C2/c (n°15) with a = 32.2307(6) A, b = 6.6168(1) A, c = 22.4244(4) A, β = 91.814(1)°, V = 4779.92(14) A3 and Z = 4. The only compound that constitutes family 2 crystallizes in the monoclinic system, space group C2/c (n°15) with a = 6.3396(1) A, b = 18.0440(2) A, c = 19.6225(2) A, β = 95.451(1)°, V = 2234.50(5)A3 and Z = 4. The crystal structure of family 3 has been solved on the basis of the Er-containing compound. This compounds crystallizes in the monoclinic system, space group P21/a (n°14) with a = 22.0121(2) A, b = 6.6973(1) A, c = 26.4380(4) A, β = 108.4469(4)°, V = 3697.27(9) A3 and Z = 4. Its crystal structure can be described as a co-crystallization of the two others. Surprisingly, all these compounds present low-dimensionality while lanthanide-containing coordination polymers involving similar ligands, such as benzene-1,2,4,5-tetracarboxylate, show most often high dimensionality. The thermal behavior and the photo-luminescence properties of the compounds that belong to the third family have been studied.
Published: 2013
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48. 3D Organization of Dysprosium Cubanes

Author: Guillaume Calvez, Xiaohui Yi, Carole Daiguebonne, Olivier Guillou, 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), 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, Inorganic chemistry, chemistry.chemical_element, 02 engineering and technology, Crystal structure, [CHIM.INOR]Chemical Sciences/Inorganic chemistry, 010402 general chemistry, 021001 nanoscience & nanotechnology, Isonicotinic acid, 01 natural sciences, 0104 chemical sciences, Inorganic Chemistry, chemistry.chemical_compound, Crystallography, chemistry, Cubane, Dysprosium, Molecule, Metal-organic framework, 0210 nano-technology, Porosity, ComputingMilieux_MISCELLANEOUS
Abstract: The reaction of isonicotinic acid N-oxide and Dy(NO)3·6H2O under aerobic conditions leads to the formation of a porous lanthanide, a cubane-based 3D edifice of the formula [Dy4(μ3-OH)3(μ3-O)(NOPyCOO)6(OH)(H2O)3·(DMF)3(H2O)12]∞ (NOPyCOO = pyridine-4-carboxylate N-oxide). Crystal structure investigations show that the [Dy4(μ3-OH)3(μ3-O)] cubane cores are interconnected by organic ligands to form an extended porous structure. Thermogravimetric analyses and temperature-dependent X-ray diffraction analyses evidence that the compound is stable upon dehydration/desolvatation up to 200 °C. Calculations for the N2 kinetic radius afford a void volume of 3603 A3 per unit cell (33.8 %) and a potential porosity of 1400 m2 g–1. The large pores can potentially host molecules with a projected surface area as large as 20 A2 into a large pore volume (600 A3). Moreover, the onset of a slow magnetic relaxation has been observed and rationalized by a comparison with closely related 0D and 2D compounds.
Published: 2013
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49. Glass reactive sintering as an alternative route for the synthesis of NZP glass-ceramics

Author: Abdessamad Kidari, Jean Rocherullé, Guillaume Calvez, Stuart Hampshire, Sébastien Chenu, Ronan Lebullenger, Mickael J. Pomeroy, Patricia Bénard-Rocherullé, 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), 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, Mechanical Engineering, chemistry.chemical_element, Sintering, 02 engineering and technology, Porous glass, Tungsten, [CHIM.INOR]Chemical Sciences/Inorganic chemistry, 010402 general chemistry, 021001 nanoscience & nanotechnology, 01 natural sciences, Thermal expansion, 0104 chemical sciences, Phosphate glass, chemistry, Mechanics of Materials, visual_art, visual_art.visual_art_medium, Ionic conductivity, General Materials Science, Ceramic, Composite material, 0210 nano-technology, Tin
Abstract: International audience; The NZP-type crystal structure allows a large number of ionic substitutions which leads to ceramics with adjustable thermal expansion properties or interesting ionic conductivity. However, NZP is difficult to fabricate into monoliths because it requires both high temperatures and long sintering times. An alternative low temperature route to obtain a tungsten (IV) and tin (IV) containingNZP crystalline phase uses a process of glass reactive sintering of a phosphate glass. Using a microwave oven, a glass with the appropriate composition in the NaPO3-Sn(II)O-W(VI)O3 ternary diagram is prepared by a conventional melting and casting technique. After crushing, the glass powder is pressed at room temperature. The green pellet is cured during various times at temperatures where glass reactive sintering takes place. From XRD and DTA experiments, we have shown that different parameters influence the achievement of NZP phase. Consequently, specific conditions, such as (i) initial glass composition,(ii) equimolar quantities of SnOandWO3, (iii) glass particle size lower than 100 lm, and (iv) curing conducted under air, are required to obtain a glass-ceramic with a single crystalline phase with the NZP-type crystal structure
Published: 2012
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50. Lanthanide Aminoisophthalate Coordination Polymers: A Promising System for Tunable Luminescent Properties

Author: Yun Luo, Kevin Bernot, Stéphane Freslon, Carole Daiguebonne, Guillaume Calvez, 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), 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, Luminescence, Stereochemistry, Polymers, 02 engineering and technology, Polymer, Crystal structure, [CHIM.INOR]Chemical Sciences/Inorganic chemistry, 010402 general chemistry, 021001 nanoscience & nanotechnology, 01 natural sciences, 0104 chemical sciences, Ion, Inorganic Chemistry, Coordination polymers, Crystallography, chemistry, Group (periodic table), Lanthanides, Isostructural, 0210 nano-technology, Monoclinic crystal system
Abstract: International audience; Reactions in water between the disodium salt of 5-amino-1,3-benzenedicarboxylic acid or 5-aminoisophthalate (Na2aip) and lanthanide chlorides lead to two families of coordination polymers with the respective general chemical formulae {[Ln6(aip)7(H2O)24]*2(aip)*6H2O}∞ in which Ln = Tm or Yb (Family 1) and {[Ln2(aip)2(H2O)10]*(aip)*4H2O}∞ in which Ln = La-Er (except Pm) or Y (Family 2). Compounds belonging to Family 1 are isostructural. The crystal structure has been solved for the Er-containing compound. This compound crystallizes in the monoclinic system, space group P21/n (n°14) with a = 13.3439(3) Å, b = 27.3332(8) Å, c = 15.7191(4) Å, β = 97.90(1)°, V = 5680.41(82) Å3 and Z = 4. The crystal structure can be described as the juxtaposition of double helicoidal chains. Additional aminoisophthalate ions insuring the electroneutrality of the network are lying in the interchain space. Compounds belonging to Family 2 are isostructural. The crystal structure has been solved for the Eu-containing compound. This compound crystallizes in the monoclinic system, space group Pn (n°7) with a = 11.3427(2) Å, b = 10.6663(1) Å, c = 15.1639(3) Å, β = 97.8998(9)°, V = 1817.19(5) Å3 and Z = 2. The crystal structure can be described as the juxtaposition of zigzag double chains. Additional aminoisophthalate ligands are lying in the interchain space insuring the electroneutrality of the network. The luminescent properties under UV irradiation of these compounds have been explored. In particular, quantum yields, lifetimes and colorimetric coordinates of the Tb-, the Sm-, and the Dy-containing coordination polymers have been determined.
Published: 2011
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