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

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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. Colloidal suspensions of highly luminescent lanthanide-based coordination polymer molecular alloys for ink-jet printing and tagging of technical liquids

Author: David Jacob, Stéphane Freslon, Yan Suffren, Francois Le Natur, Youenn Pointel, Olivier Guillou, Kevin Bernot, Carole Daiguebonne, Guillaume Calvez, Institut des Sciences Chimiques de Rennes (ISCR), Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA), Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES), Institut Universitaire de France (IUF), Ministère de l'Education nationale, de l’Enseignement supérieur et de la Recherche (M.E.N.E.S.R.), Cordouan Technologies, Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), and Institut National des Sciences Appliquées (INSA)
Subjects: Lanthanide, Materials science, 010405 organic chemistry, Coordination polymer, Alloy, technology, industry, and agriculture, engineering.material, equipment and supplies, 010402 general chemistry, complex mixtures, 01 natural sciences, 0104 chemical sciences, Inorganic Chemistry, Colloid, chemistry.chemical_compound, [CHIM.POLY]Chemical Sciences/Polymers, chemistry, Chemical engineering, engineering, [CHIM.COOR]Chemical Sciences/Coordination chemistry, Luminescence
Abstract: International audience; Highly luminescent and color-tunable stable colloidal suspensions of molecular alloys are reported. They are produced via a green synthetic route in ethanol medium. The mean hydrodynamic diameter of the colloids is about 140 nm and the colloidal suspensions are stable for more than a month. The optical properties of the molecular alloy suspensions and their bulk counterparts are extremely similar. To the best of our knowledge, this series of suspensions constitutes the first example of hetero-lanthanide coordination polymer molecular alloy (LnCPMA)-based colloidal suspensions with sizeable luminescence intensity and a wide range of accessible colors. This high color tunability paves the road toward tagging of technical liquids. We also demonstrate that they can be used in ink-jet printers for luminescent anti-counterfeiting tagging.
Published: 2021
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3. Self-assembled luminescent Cu(<scp>i</scp>) tetranuclear metallacycles based on 3,3′-bipyridine ligands

Author: Guillaume Calvez, Christophe Lescop, Florent Moutier, Jana Schiller, Institut des Sciences Chimiques de Rennes (ISCR), Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA), Université de Rennes (UR), ANR (ANR PRC SMAC and ANR PRCI SUPRALUM) French National Research Agency (ANR), CNRS Centre National de la Recherche Scientifique (CNRS) European Commission, French 'Ministere de lEnseignement superieur, de la Recherche et de lInnovation', French 'Ministere des Affaires Etrangeres', Alexander von Humboldt Foundation Alexander von Humboldt Foundation, ANR-20-CE92-0012,SUPRALUM,Assemblages supramoléculaires luminescents pilotés par la chimie de coordination basés sur des précurseurs de l'ion Cu(I) pré-organisés et stabilisés par des ligands portant des éléments du groupe principal(2020), ANR-19-CE07-0027,SMAC,Composés avancés multifonctionnels commutables(2019), Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), and Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA)
Subjects: 010405 organic chemistry, Chemistry, Ligand, Organic Chemistry, Supramolecular chemistry, Halide, 010402 general chemistry, 01 natural sciences, 0104 chemical sciences, Ion, Self assembled, Crystallography, Bipyridine, chemistry.chemical_compound, [CHIM]Chemical Sciences, Luminescence, Bimetallic strip
Abstract: International audience; 3,3'-Bipyridine ligand B was reacted with pre-assembled [Cu-2(mu(2)-dppm)(2)] Cu(I) bimetallic flexible precursor A according to coordination-driven supramolecular chemistry synthetic principles. Outcomes obtained revealed the necessity to formally introduce bridging halide X ions (X = Cl, Br or I) in order to conduct selectively and successfully coordination-driven supramolecular syntheses. Therefore, [Cu-2(mu(2)-dppm)(2)(mu(2)-X)] bimetallic connecting nodes presenting a potential coordination angle of ca. 120 degrees are generated, which lead upon reaction with connecting ligand B to the selective formation of new tetranuclear metallacycles C-X. These derivatives are luminescent in the solid-state at room temperature with high emission quantum yields and a study of the temperature dependence of their photophysical properties was conducted, suggesting a ligand B centered triplet origin for their luminescence.
Published: 2021
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4. Rational Design of Dual IR and Visible Highly Luminescent Light-Lanthanides-Based Coordination Polymers

Author: Guillaume Calvez, Stéphane Freslon, Carole Daiguebonne, Kevin Bernot, Francois Le Natur, Yan Suffren, Olivier Guillou, Youenn Pointel, Institut des Sciences Chimiques de Rennes (ISCR), Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA), Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), and Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)
Subjects: chemistry.chemical_classification, Lanthanide, 010405 organic chemistry, Chemistry, Salt (chemistry), chemistry.chemical_element, Polymer, [CHIM.INOR]Chemical Sciences/Inorganic chemistry, 010402 general chemistry, 01 natural sciences, 0104 chemical sciences, Coordination complex, Inorganic Chemistry, Lanthanum, Physical chemistry, Thermal stability, Physical and Theoretical Chemistry, Isostructural, Luminescence
Abstract: A series of isostructural homo- and heterolanthanide coordination polymers of formula [Ln2(dcpa)3(H2O)]∞ with Ln = La-Gd have been obtained by reactions in water between the lightest lanthanide chlorides and the disodium salt of 4,5-dichlorophthalic acid (H2dcpa). They present particularly high thermal stability for coordination compounds (up to 400 °C). Their luminescent properties have been studied in detail. Interestingly an insensitivity to water coordination as well as a very strong effect of optical dilution is observed. Therefore, molecular alloys with very high lanthanum concentration have been prepared. Some of them present highly tunable and very intense luminescence. For example, to the best of our knowledge, [Sm0.04La1.96(dcpa)3(H2O)]∞ presents one of the highest overall quantum yields measured so far for a Sm3+-based coordination compound (QSmLigand = 9.2%), and [Nd0.03Sm0.14Eu0.03La1.8(dcpa)3(H2O)]∞ is one of the brightest (12 Cd·m-2 under 0.75 mW·cm-2 UV flux) multiemissive visible and near-infrared lanthanide-coordination polymers reported to date.
Published: 2020
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5. 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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6. 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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7. Intramolecular rearrangements guided by adaptive coordination-driven reactions toward highly luminescent polynuclear Cu(<scp>i</scp>) assemblies

Author: Karine Costuas, Sloane Evariste, Vivian Wing-Wah Yam, Ali Moustafa Khalil, Mehdi Elsayed Moussa, Guillaume Calvez, Christophe Lescop, Vincent Delmas, Boris Le Guennic, Hok-Lai Wong, Institut des Sciences Chimiques de Rennes (ISCR), Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA), City University of Hong Kong [Hong Kong] (CUHK), Agence Nationale de la Recherche, ANR Alexander von Humboldt-Stiftung University of Hong Kong, HKUHKU 17334216AoE/P-03/ 08 Centre National de la Recherche Scientifique, CNRS, Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), and Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)
Subjects: Materials science, Intrinsic luminescence, Adaptive coordination, Supramolecular chemistry, 010402 general chemistry, 01 natural sciences, Fluorescence, Inorganic Chemistry, Metal, Copper alloys, Platinum alloys, [CHIM]Chemical Sciences, Redistribution (chemistry), Scaffolds, Spin orbit coupling, 010405 organic chemistry, Copper compounds, Building blockes, Binary alloys, Metallacycle, Coordination-driven, Combinatorial chemistry, Photophysical properties, 0104 chemical sciences, Thermally activated delayed fluorescences, Heavy metals, visual_art, Intramolecular force, Intramolecular rearrangement, visual_art.visual_art_medium, Science, technology and society, Luminescence, Gold alloys, Coordination reactions, Supramolecular scaffolds
Abstract: International audience; Adaptive coordination-driven supramolecular chemistry based on conformationally flexible pre-organized luminescent Cu(I) precursors paves the way to the ready formation of intricate supramolecular scaffold possessing intrinsic luminescence properties. A formal ring extension of a tetrametallic Cu(I) metallacycle bearing Thermally Activated Delayed Fluorescence (TADF) properties can thus be carried out, affording a new hexametallic Cu(I) metallacycle 1 bearing modulated solid-state TADF properties. Attempts to adapt this ring extension process to the formation of targeted heterometallic Au2Cu4 and Pt2Cu8 assemblies led to the unexpected and ready formation of the Au2Cu10 and Pt4Cu11 derivatives 2 and 3, respectively. These outcomes strengthen the scope and perspectives of adaptive coordination-driven supramolecular chemistry compared to those of conventional coordination-driven supramolecular chemistry. Indeed, it guides concerted intramolecular fragmentation and redistribution of the particular building blocks used, affording selectively supramolecular scaffolds of higher nuclearity and complexity. The study of the solid-state photophysical properties of the assemblies 2 and 3 highlights enhanced and original behaviors, in which the heavy metal spin-orbit coupling values significantly influence the relaxation processes centered on the Cu(I) metal centers.
Published: 2020
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8. A Journey in Lanthanide Coordination Chemistry: From Evaporable Dimers to Magnetic Materials and Luminescent Devices

Author: Yan Suffren, Kevin Bernot, Guillaume Calvez, Olivier Guillou, Carole Daiguebonne, Institut des Sciences Chimiques de Rennes (ISCR), Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), We thank INSA Rennes, CNRS (EMERGENCE@INC program), the Region Bretagne, the Chinese Scholarship Council (CSC), the ERC Advanced Grant MolNanoMaS (project no. 267746), Italian MIUR through PRIN 'Record' (20097X44S7), and the FIRB 'Nano-PlasMag' (RBFR10OAI0) project for funding., European Project: 267746,EC:FP7:ERC,ERC-2010-AdG_20100224,MOLNANOMAS(2011), Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), and Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA)
Subjects: chemistry.chemical_classification, Lanthanide, Materials science, 010405 organic chemistry, Relaxation (NMR), General Medicine, General Chemistry, 010402 general chemistry, 01 natural sciences, 0104 chemical sciences, Coordination complex, Characterization (materials science), chemistry, X-ray photoelectron spectroscopy, Chemical physics, Molecular film, Molecule, [CHIM]Chemical Sciences, Luminescence
Abstract: International audience; Conspectus. Lanthanide ions are prime ingredients for the design of compounds, materials, and devices with unique magnetic and optical properties. Accordingly, coordination chemistry is one of the best tools for building molecular edifices from these ions because it allows careful control of the ions’ environment and of the dimensionality of the final compound.In this Account, we review our results on lanthanide-based dimers. We show how a pure fundamental study on lanthanide coordination chemistry allows the investigation of a full continuum of results from the compound to materials and then to devices. The conversion of molecules into materials is a tricky task because it requires strong molecular robustness toward the surface deposition processes as well as the preservation and detectability of the molecular properties in the material. Additionally, the passage of a material toward a device implies a material with a given function, for example, a tailored response to an external stimulus.To do so, we targeted neutral and isolated molecules whose transfer on surfaces by chemi- or physisorption is much easier than that of charged molecules or extended coordination networks. Then, we focused on molecules with very strong evaporability to avoid wet chemistry deposition processes that are more likely to damage the molecules and/or distort their geometries.We thus designed lanthanide dimers based on fluorinated β-diketonates and pyridine-N-oxide ligands. As expected, they show remarkable evaporability but also strong luminescence and interesting magnetic behavior because they behave as single-molecule magnets (SMMs). Ligand substitutions and stoichiometric modifications allow the optimization of the geometric organization of the dimers in the crystal packing as well as their evaporability, SMM behavior, luminescent properties, or their ability to be anchored on surfaces. Most of all, this family of molecules shows a strong ability to form thick films on various substrates. This allows converting these molecules to magnetic materials and luminescent devices.Magnetic materials can be designed by creating thick films of the dimers deposited on gold. These films have been designed and investigated with the most advanced techniques of on-surface imaging (atomic force microscopy, AFM), on-surface physicochemical characterization (X-ray photoelectron spectroscopy (XPS), time of flight-secondary ion mass spectroscopy (Tof-SIMS)), and on-surface magnetic investigation (low-energy muon spin relaxation (LE-μSR)). Contrary to what was previously observed on other SMM films, no depth dependence of the SMM behavior was observed. This means that the dimers do not suffer from the vacuum or substrate interface and behave similarly, whatever their localization. This exceptional magnetic robustness is a key ingredient in the creation of materials for molecular magnetic data storage.Luminescent devices can be obtained by layering molecular films of the dimers with a copper-rich solid-state electrolyte between ITO/Pt electrodes. The electromigration of Cu(2+) ions into films of Eu(3+), Tb(3+), and Dy(3+) dimers quenches their luminescence. This luminescence tuning by electromigration is reversible, and this setup can be considered to be a proof of concept of full solid-state luminescent device where reversible coding can be tailored by an electric field. It is envisioned for optical data storage purposes. In the future, it could also benefit from the SMM properties of the molecules to pave the way toward multifunctional molecular data storage devices.
Published: 2021
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9. 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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10. 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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11. Multi-Emissive Lanthanide-Based Coordination Polymers for Potential Application as Luminescent Bar-Codes

Author: Guillaume Calvez, Stéphane Freslon, Yan Suffren, Kevin Bernot, Laurent Le Pollès, Claire Roiland, Carole Daiguebonne, Jinzeng Wang, Olivier Guillou, Institut des Sciences Chimiques de Rennes (ISCR), Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA), Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES), The China Scholarship Council Ph.D. Program and the cooperation program with the French UT & INSA are acknowledged for financial support., Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), and Institut National des Sciences Appliquées (INSA)
Subjects: Lanthanide, chemistry.chemical_classification, 010405 organic chemistry, Chemistry, Intermetallic, Polymer, 010402 general chemistry, 01 natural sciences, Chemical formula, 0104 chemical sciences, Ion, Inorganic Chemistry, Physical chemistry, [CHIM.COOR]Chemical Sciences/Coordination chemistry, Emission spectrum, Physical and Theoretical Chemistry, Isostructural, Luminescence, ComputingMilieux_MISCELLANEOUS
Abstract: Isostructural lanthanide-based coordination polymers that are obtained by reactions in water of a lanthanide chloride and the sodium salt of 5-methoxyisophthalate (mip2-) have the general chemical formula [Ln2(mip)3(H2O)8·4H2O]∞ with Ln = Nd-Er except Pm plus Y (symbolized by [Ln2(mip)3]∞). Some of these homo-lanthanide compounds present very high luminescence brightness. The weak intermetallic energy transfer between lanthanide ions observed in these compounds allows the design of hetero-lanthanide coordination polymers with tunable luminescence properties. A molecular alloy that involved six different lanthanide ions (Nd3+, Sm3+, Eu3+, Gd3+, Tb3+, Dy3+) has been prepared and its luminescent properties have been studied. This compound, under a unique irradiation wavelength (λexc = 325 nm), exhibits almost 20 emission peaks in both the visible and the NIR regions at room temperature. This unprecedented richness of the emission spectrum could be of great interest as far as luminescent bar-codes are targeted.
Published: 2019
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12. Microcrystalline Core–Shell Lanthanide-Based Coordination Polymers for Unprecedented Luminescent Properties

Author: Guillaume Calvez, Kevin Bernot, Olivier Guillou, Valérie Demange, Carole Daiguebonne, Ahmad Abdallah, Amandine Rojo, Yan Suffren, Institut des Sciences Chimiques de Rennes (ISCR), Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA), Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES), Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), and Institut National des Sciences Appliquées (INSA)
Subjects: chemistry.chemical_classification, Lanthanide, 010405 organic chemistry, Intermetallic, Polymer, Crystal structure, 010402 general chemistry, 01 natural sciences, Chemical formula, 0104 chemical sciences, Coordination complex, Inorganic Chemistry, Crystallography, Microcrystalline, chemistry, [CHIM.COOR]Chemical Sciences/Coordination chemistry, Physical and Theoretical Chemistry, Luminescence
Abstract: International audience; Microcrystalline core-shell powders of lanthanide-based coordination polymers with general chemical formula ([Ln(cpbOH)])@([Ln'(cpbOH)]) with Hcpb = 1,4-carboxyphenylboronic acid have been synthesized and structurally characterized. Their luminescent properties have been studied. They are drastically different from those of heterolanthanide coordination polymers, also called "molecular alloys", that present the same crystal structure and chemical composition. Study of the photophysical properties of core-shell lanthanide-based coordination polymers reveals that it is possible to control efficiently the intermetallic energy transfers between lanthanide ions. Furthermore, multiemissive compounds, under unique irradiation, in both visible and infrared regions are easily feasible. Core-shell microstructured lanthanide-based coordination polymers have also been prepared with terephthalic (Hbdc) and trimesic (Htma) acids as ligands for evidencing that lanthanide-ion-based coordination compounds are excellent candidates for 3D molecular epitaxial growth.
Published: 2018
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13. Structural and Luminescence Properties of Anthracene- and Biphenyl-Based Lanthanide Bisphosphonate Ester Coordination Polymers

Author: Guillaume Calvez, Christophe Lescop, Kristijan Krekić, Rudolf Pietschnig, Dieter Klintuch, Institut des Sciences Chimiques de Rennes (ISCR), Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA), MASH Program, TESLA Program, Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), and Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)
Subjects: Biphenyl, Lanthanide, Anthracene, 010405 organic chemistry, Ligand, Biphenylene, 010402 general chemistry, 01 natural sciences, Phosphonate, 3. Good health, 0104 chemical sciences, Inorganic Chemistry, chemistry.chemical_compound, Crystallography, chemistry, [CHIM.COOR]Chemical Sciences/Coordination chemistry, Physical and Theoretical Chemistry, Luminescence, ComputingMilieux_MISCELLANEOUS, Derivative (chemistry)
Abstract: Coordinative networks containing lanthanide ions attached via phosphonate ester functionalities provide remarkable luminescence properties. On the basis of ditopic phosphonic ester ligands with biphenylene and 9,10-anthracenylene bridges, a series of compounds with formal composition {[M(NO3)3]L}n or {[M(NO3)3]2(L1)3}n (L = C28H40O6P2; L1 = C26H40O6P2) with M = La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, and Y have been synthesized, structurally characterized, and the luminescence behavior was explored in the visible and NIR spectral regions, where applicable. In contrast to closely related networks based on biphenyl bisphosphonate esters from previous work, no evidence for ligand-to-metal energy transfer could be observed, despite strong near-infrared emission in some cases. Unique behavior is found for the Eu derivative with the 9,10-anthracenylene bridge, which is nonemissive, showing neither ligand- nor metal-based emission.
Published: 2018
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14. Lanthanide-Based Coordination Polymers with a 4,5-Dichlorophthalate Ligand Exhibiting Highly Tunable Luminescence: Toward Luminescent Bar Codes

Author: Carole Daiguebonne, Albert-Manga Badiane, Yan Suffren, Karine Costuas, Stéphane Freslon, Olivier Guillou, Guillaume Calvez, Kevin Bernot, Magatte Camara, Université Assane SECK de Ziguinchor (UASZ), 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), French Cooperation Agency in Senegal, 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, Infrared, Ligand, 02 engineering and technology, Crystal structure, 010402 general chemistry, 021001 nanoscience & nanotechnology, 01 natural sciences, Homonuclear molecule, 0104 chemical sciences, Inorganic Chemistry, Crystallography, [CHIM.POLY]Chemical Sciences/Polymers, Heteronuclear molecule, [CHIM.COOR]Chemical Sciences/Coordination chemistry, Physical and Theoretical Chemistry, Isostructural, 0210 nano-technology, Luminescence
Abstract: International audience; Reactions in water of 4,5-dichlorophthalate (dcpa) with the heaviest lanthanide ions lead to a family of compounds with the general chemical formula [Ln(dcpa)(HO)·3HO], where Ln = Tb-Lu, Y. The synthesis, crystal structure, thermal behavior, and luminescent properties of this series of homonuclear compounds are described. Additionally, this family can be extended to isostructural heteronuclear compounds that can contain some light lanthanide ions and therefore present some original photophysical properties. These compounds show potential interest as multiemissive materials (visible and infrared light between 450 and 1600 nm) and could find application as luminescent bar codes.
Published: 2018
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15. Hexalanthanide Complexes as Molecular Precursors: Synthesis, Crystal Structure, and Luminescent and Magnetic Properties

Author: Olivier Guillou, Marin Puget, Carole Daiguebonne, Kevin Bernot, Yan Suffren, Haiyun Yao, Guillaume Calvez, Christophe Lescop, Institut des Sciences Chimiques de Rennes (ISCR), Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), China Scholarship Council, Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), and Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)
Subjects: 010405 organic chemistry, Chemistry, Ligand, Inorganic chemistry, Crystal structure, [CHIM.INOR]Chemical Sciences/Inorganic chemistry, 010402 general chemistry, 01 natural sciences, Chemical formula, 0104 chemical sciences, Inorganic Chemistry, Crystallography, chemistry.chemical_compound, Octahedron, [CHIM.COOR]Chemical Sciences/Coordination chemistry, Physical and Theoretical Chemistry, Isostructural, Solubility, Luminescence, Acetonitrile
Abstract: International audience; Reaction of hexanuclear octahedral molecular precursors with a 3-chlorobenzoate ligand affords an unprecedented family of isostructural polylanthanide complexes via solvothermal and microwave-assisted syntheses in an acetonitrile medium. The general chemical formula of the compounds that constitute this series is {[Ln(μ-OH)(HO)(NO)(3-cb)]·(CHCN)}, where 3-cb stands for 3-chlorobenzoate and Ln = Eu, Tb, Dy, Ho, Er, or Y. The crystal structure, solubility, and magnetic and luminescent properties of these complexes have been studied. The luminescent properties evidence that the composition of the hexalanthanide precursor is preserved during the synthetic process that is of particular interest for cases in which heterolanthanide complexes are targeted.
Published: 2017
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16. Lanthanide coordination polymers with 1,2-phenylenediacetate

Author: Guillaume Calvez, Yan Suffren, Stéphane Freslon, Olivier Guillou, Insa Badiane, Carole Daiguebonne, Magatte Camara, Kevin Bernot, Groupe Matériaux Inorganiques:Chimie Douce et Cristallographie (LCPM), Université deZiguinchor, Institut des Sciences Chimiques de Rennes (ISCR), Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), The French Cooperation Agency in Senegal is acknowledged for financial support., Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), and Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)
Subjects: Lanthanide, Luminescence, Coordination polymer, Inorganic chemistry, Crystal structure, [CHIM.INOR]Chemical Sciences/Inorganic chemistry, 010402 general chemistry, 01 natural sciences, Inorganic Chemistry, chemistry.chemical_compound, Group (periodic table), Materials Chemistry, [CHIM.COOR]Chemical Sciences/Coordination chemistry, Physical and Theoretical Chemistry, Isostructural, chemistry.chemical_classification, 010405 organic chemistry, Chemistry, Polymer, 0104 chemical sciences, Crystallography, [CHIM.POLY]Chemical Sciences/Polymers, Energy transfer, Monoclinic crystal system
Abstract: The CDIFX of Rennes is acknowledged for single crystal X-ray diffraction data collection.; International audience; Reactions in water between lanthanide chlorides and the di-sodium salt of 1,2-phenylenediacetic acid, Na2(o-pda), lead to two families of coordination polymers with respective chemical formulae [La2(o-pda)3(H2O)4,4H2O]∞ (1) and [Ln2(o-pda)3(H2O)2,2H2O]∞ (2) for Ln = Ce-Nd, Sm-Lu and Y. Compound 1 crystallises in the monoclinic system, space group C2/c (n°15), with a = 28.195(5) Å, b = 12.2305(3) Å, c = 8.7607(1) Å, β = 98.835(1)° and Z = 4. Its crystal structure and thermal properties are described. Compounds of family 2 are isostructural to a previously reported crystal structure. Luminescence properties of Eu- and Tb-based compounds have been studied.
Published: 2017
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17. 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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18. 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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19. 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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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. 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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25. Adaptive Coordination-Driven Supramolecular Syntheses toward New Polymetallic Cu(I) Luminescent Assemblies

Author: Ali Moustafa Khalil, Eugene Yau-Hin Hong, Sloane Evariste, Mehdi Elsayed Moussa, Vivian Wing-Wah Yam, Hok-Lai Wong, Boris Le Guennic, Guillaume Calvez, Christophe Lescop, Karine Costuas, Alan Kwun-Wa Chan, Institut des Sciences Chimiques de Rennes (ISCR), Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA), The University of Hong Kong (HKU), Agence Nationale de la Recherche, HKU 17334216, Research Grants Council, University Grants Committee, University of Hong Kong, University Research Committee, University of Hong Kong, Ministère de l'Enseignement Supérieur et de la Recherche, AoE/P-03/08, University Grants Committee, Centre National de la Recherche Scientifique, Alexander von Humboldt-Stiftung, ANR-12-IS07-0002,P-OPTOELECTR-MOLMAT,Matériaux pi-conjugués à base de phosphore : conception, synthèse et assemblages supramoléculaires pour l'émission et la collecte de lumière, la communication électronique et le transport de charge.(2012), Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), and Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)
Subjects: 010405 organic chemistry, Chemistry, Coordination polymer, Supramolecular chemistry, General Chemistry, Metallacycle, 010402 general chemistry, 01 natural sciences, Biochemistry, Fluorescence, Catalysis, 0104 chemical sciences, Metal, chemistry.chemical_compound, Crystallography, Colloid and Surface Chemistry, visual_art, visual_art.visual_art_medium, [CHIM]Chemical Sciences, Luminescence
Abstract: International audience; A thermally activated delayed fluorescence (TADF) tetrametallic Cu(I) metallacycle A behaves as a conformationally adaptive preorganized precursor to afford, through straightforward and rational coordination-driven supramolecular processes, a variety of room-temperature solid-state luminescent polymetallic assemblies. Reacting various cyano-based building blocks with A, a homometallic Cu(I) 1D-helical coordination polymer C and CuM discrete circular heterobimetallic assemblies D (M = Ni, Pd, Pt) are obtained. Their luminescence behaviors are studied, revealing notably the crucial impact of the spin-orbit coupling offered by the central M metal center on the photophysical properties of the heterobimetallic D derivatives.
Published: 2018
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26. 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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27. 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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28. Magnetic Anisotropy and Spin-Parity Effect Along the Series of Lanthanide Complexes with DOTA

Author: Olivier Cador, Javier Luzon, Guillaume Calvez, Marie-Emmanuelle Boulon, Roberta Sessoli, Alessio Milanesi, MAURO PERFETTI, GIUSEPPE CUCINOTTA, Kevin Bernot, Andrea Caneschi, Department of Chemistry 'Ugo Schiff', Università degli Studi di Firenze = University of Florence [Firenze] (UNIFI), Institut des Sciences Chimiques de Rennes (ISCR), Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA), Italian MIUR, Spanish research project, Région Bretagne, Rennes Métropole [MAT2011-27233-C02-02], Italian CINECA [HP10AI85MB], European Project, Università degli Studi di Firenze = University of Florence (UniFI), Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), European Commission, Ministero dell'Istruzione, dell'Università e della Ricerca, European Research Council, and Région Bretagne
Subjects: Lanthanide, Luminescence, [CHIM.INOR]Chemical Sciences/Inorganic chemistry, 010402 general chemistry, 01 natural sciences, Catalysis, Ion, Magnetization, chemistry.chemical_compound, Nuclear magnetic resonance, Lanthanides, luminescence, Molecule, DOTA, lanthanides, Spin (physics), Crystal field, crystal field, 010405 organic chemistry, Chemistry, Relaxation (NMR), General Medicine, General Chemistry, ab initio calculations, 0104 chemical sciences, 3. Good health, Crystallography, Magnetic anisotropy, Magnetic properti, magnetic properties
Abstract: Spotting trends: Upon going from TbIII to YbIII centers in the complexes of the DOTA4- ligand, a reorientation of the easy axis of magnetization from perpendicular to parallel to the Ln-O bond of the apical water molecule is experimentally observed and theoretically predicted (see picture; SMM = single-molecule magnet). Only ions with an odd number of electrons show slow relaxation of the magnetization. © 2013 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim., This work was supported by the European Research Council through the AdG “NoINanoMaS” (grant number 267746), by the Italian MIUR (PRIN 2008), Spanish research project MAT2011-27233-C02-02, Région Bretagne, Rennes Métropole, and by the Italian CINECA through the award number HP10AI85MB, 2011.
Published: 2012
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29. New Family of Porous Lanthanide-Containing Coordination Polymers: [Ln2(C2O4)3(H2O)6,12H2O]∞ with Ln = La−Yb or Y

Author: Stéphane Freslon, Olivier Guillou, Guillaume Calvez, Nicolas Kerbellec, Carole Daiguebonne, Doddy Kustaryono, Sciences Chimiques de Rennes / Matériaux Inorganiques: Chimie Douce et Réactivité (MICDR), Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Centre National de la Recherche Scientifique (CNRS), Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), and Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Centre National de la Recherche Scientifique (CNRS)
Subjects: Lanthanide, chemistry.chemical_classification, 010405 organic chemistry, Inorganic chemistry, General Chemistry, Polymer, Crystal structure, [CHIM.INOR]Chemical Sciences/Inorganic chemistry, 010402 general chemistry, Condensed Matter Physics, 01 natural sciences, Chemical formula, 0104 chemical sciences, law.invention, Crystallography, chemistry, law, Molecule, [CHIM.COOR]Chemical Sciences/Coordination chemistry, General Materials Science, Crystallization, Isostructural, Luminescence
Abstract: International audience; Reactions at low temperature in a mixture benzene/water between dimethyloxalate and a lanthanide chloride lead to a family of 3D-coordination polymers with general chemical formula [Ln2(C2O4)3(H2O)6 3 12H2O]¥, where Ln=La-Yb (except Pm) or Y. All these compounds are isostructural to the already described [Er2(C2O4)3(H2O)6 3 12H2O]¥. Their crystal structure can be described as the juxtaposition of channels with hexagonal cross-section. The channels are filled with crystallization water molecules. Their thermal dehydration produces a collapse of the molecular skeleton leading to amorphous compounds.On the opposite, their dehydration by freeze-drying is possible and the twelve crystallization water molecules can be removed without destruction of the molecular skeleton. The porosity of the dehydrated compounds has been estimated by computational methods to 483 m2 g-1. The luminescence properties of the Eu-containing and Tb-containing compounds are also briefly described.
Published: 2009
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30. 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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31. A family of lanthanide-based coordination polymers with boronic Acid as ligand

Author: Stéphane Freslon, Xiaohui Yi, Olivier Guillou, Carole Daiguebonne, Laurent Le Pollès, Xiao Fan, Kevin Bernot, Gang Huang, Guillaume Calvez, Institut des Sciences Chimiques de Rennes (ISCR), Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Software Engineering Institute [Peking], Peking University [Beijing], China Scholarship Council, Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), and Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA)
Subjects: chemistry.chemical_classification, Lanthanide, 010405 organic chemistry, Ligand, Nuclear magnetic resonance spectroscopy, Polymer, 010402 general chemistry, Photochemistry, 01 natural sciences, Chemical formula, 0104 chemical sciences, Inorganic Chemistry, Crystallography, chemistry.chemical_compound, chemistry, [CHIM]Chemical Sciences, Physical and Theoretical Chemistry, Phosphorescence, Luminescence, Boronic acid
Abstract: International audience; Reactions in water between the sodium salt of 4-carboxyphenylboronic acid (Hcpb) and lanthanide ions (Pr-Nd, Sm-Lu, and Y) led to a family of lanthanide-based coordination polymers with general chemical formula \[Ln(cpbOH)(H2O)2](cpb)\∞. Structural characterizations were ensured by single-crystal X-ray diffraction and solid-state NMR spectroscopy ((11)B, (13)C, and (89)Y). This family of compounds constitutes the first example of lanthanide-based coordination polymers involving 4-carboxyphenylboronic acid as ligand. To evaluate their potential usefulness, luminescent and magnetic properties of some of the compounds that constitute this family were explored. From a magnetic point of view, the Yb(III) compound is the more promising. On the other hand, upon UV irradiation (λexc = 303 nm) ligand phosphorescence is quite intense and offers a sizable blue component to emission spectra. This is quite unusual and can constitute an asset as far as white emission is targeted. Moreover, luminescence properties of these compounds are highly temperature-dependent, and some of them seem promising as molecular thermometers.[on SciFinder (R)]
Published: 2015
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32. 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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33. 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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34. 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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35. 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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36. 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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37. Coordination polymers based on heterohexanuclear rare earth complexes: toward independent luminescence brightness and color tuning

Author: Laurent Le Pollès, Guillaume Calvez, James Ledoux, Kevin Bernot, François Le Natur, Olivier Guillou, Carole Daiguebonne, Claire Roiland, Institut des Sciences Chimiques de Rennes (ISCR), Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Institut de Recherche Mathématique de Rennes (IRMAR), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-École normale supérieure - Rennes (ENS Rennes)-Université de Rennes 2 (UR2)-Centre National de la Recherche Scientifique (CNRS)-INSTITUT AGRO Agrocampus Ouest, Institut national d'enseignement supérieur pour l'agriculture, l'alimentation et l'environnement (Institut Agro)-Institut national d'enseignement supérieur pour l'agriculture, l'alimentation et l'environnement (Institut Agro), Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), AGROCAMPUS OUEST, Institut national d'enseignement supérieur pour l'agriculture, l'alimentation et l'environnement (Institut Agro)-Institut national d'enseignement supérieur pour l'agriculture, l'alimentation et l'environnement (Institut Agro)-Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Université de Rennes 2 (UR2), Université de Rennes (UNIV-RENNES)-École normale supérieure - Rennes (ENS Rennes)-Centre National de la Recherche Scientifique (CNRS)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), and Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA)
Subjects: Lanthanide, Models, Molecular, Luminescence, Luminescent Measurements, Coordination polymer, Polymers, Inorganic chemistry, Color, [CHIM.INOR]Chemical Sciences/Inorganic chemistry, 010402 general chemistry, Crystallography, X-Ray, 01 natural sciences, Lanthanoid Series Elements, Inorganic Chemistry, Metal, chemistry.chemical_compound, Organometallic Compounds, Physical and Theoretical Chemistry, Terephthalic acid, 010405 organic chemistry, [CHIM.MATE]Chemical Sciences/Material chemistry, Chemical formula, 0104 chemical sciences, Crystallography, Solid-state nuclear magnetic resonance, chemistry, visual_art, visual_art.visual_art_medium
Abstract: International audience; Reactions in solvothermal conditions between hexanuclear rare earth complexes and H2bdc, where H2bdc symbolizes terephthalic acid, lead to a family of monodimensional coordination polymers in which hexanuclear complexes act as metallic nodes. The hexanuclear cores can be either homometallic with general chemical formula [Ln6O(OH)8(NO3)6](2+) (Ln = Pr-Lu plus Y) or heterometallic with general chemical formula [Ln6xLn'6-6xO(OH)8(NO3)6](2+) (Ln and Ln' = Pr-Lu plus Y). Whatever the hexanuclear entity is, the resulting coordination polymer is iso-structural to [Y6O(OH)8(NO3)2(bdc)(Hbdc)2.2NO3.H2bdc]infinity, a coordination polymer that we have previously reported. The random distribution of the lanthanide ions over the six metallic sites of the hexanuclear entities is demonstrated by (89)Y solid state NMR, X-ray diffraction (XRD), and luminescent measurements. The luminescent and colorimetric properties of selected compounds that belong to this family have been studied. These studies demonstrate that some of these compounds exhibit very promising optical properties and that there are two ways of modulating the luminescent properties: (i) playing with the composition of the heterohexanuclear entities or (ii) playing with the relative ratio between two different hexanuclear entities. This enables the independent tuning of luminescence intensity and color.
Published: 2013
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38. 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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39. 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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40. 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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41. A luminescent and sublimable Dy(III)-based single-molecule magnet

Author: Roberta Sessoli, Giordano Poneti, Guillaume Calvez, Olivier Guillou, Fabrice Pointillart, Kevin Bernot, Carole Daiguebonne, Xiaohui Yi, Institut des Sciences Chimiques de Rennes (ISCR), Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Department of Chemistry 'Ugo Schiff', Università degli Studi di Firenze = University of Florence [Firenze] (UNIFI), CNRS, FEDER, European Commission, Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), and Università degli Studi di Firenze = University of Florence (UniFI)
Subjects: Lanthanide, 010405 organic chemistry, Chemistry, Organic Chemistry, Relaxation (NMR), Quantum yield, General Chemistry, [CHIM.INOR]Chemical Sciences/Inorganic chemistry, 010402 general chemistry, 01 natural sciences, Catalysis, thermal stability, 3. Good health, 0104 chemical sciences, Crystallography, Magnetization, Nuclear magnetic resonance, luminescence, Antiferromagnetism, Single-molecule magnet, lanthanides, magnetic properties, Isostructural, single-molecule magnets, Luminescence
Abstract: International audience; The reaction of [Ln(hfac)(3)]*2H(2)O and pyridine-N-oxide (PyNO) leads to isostructural dimers of the formula [Ln(hfac)(3)(PyNO)](2) (Ln=Eu, Gd, Tb, Dy). The Dy derivative shows a remarkable single-molecule magnet behavior with complex hysteresis at 1.4 K. The dynamics of the magnetization features are two relaxation regimes: a thermally activated one at high temperature (τ(0)=(5.62±0.4)×10(-11) s and Δ=(167±1) K) and a quantum tunneling regime at low temperature with a tunneling frequency of 0.42 Hz. The analysis of the Gd derivative evidences intradimer antiferromagnetic interactions (J=(-0.034±0.001) cm(-1)). Moreover, the Eu, Tb, and Dy derivatives are luminescent with quantum yield of 51, 53, and 0.1%, respectively. The thermal investigation of [Dy(hfac)(3)(PyNO)](2) shows that the dimers can be sublimated intact, suggesting their possible exploit as active materials for surface-confined nanostructures to be investigated by fluorimetry methods.
Published: 2012
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42. Magnetic anisotropy in a dysprosium/DOTA single-molecule magnet: Beyond simple magneto-structural correlations

Author: Giuseppe Cucinotta, Andrea Caneschi, Roberta Sessoli, Javier Luzón, Mauro Perfetti, Mael Etienne, Pierre-Emmanuel Car, Kevin Bernot, Guillaume Calvez, Department of Chemistry 'Ugo Schiff', Università degli Studi di Firenze = University of Florence [Firenze] (UNIFI), Institut des Sciences Chimiques de Rennes (ISCR), Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA), Università degli Studi di Firenze = University of Florence (UniFI), Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), and Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)
Subjects: lanthanide, chemistry.chemical_element, [CHIM.INOR]Chemical Sciences/Inorganic chemistry, 010402 general chemistry, 01 natural sciences, Catalysis, Heterocyclic Compounds, 1-Ring, Magnetics, chemistry.chemical_compound, Nuclear magnetic resonance, Ab initio quantum chemistry methods, luminescence, DOTA, Molecule, dysprosium, Single-molecule magnet, Physics::Atomic Physics, Anisotropy, Magneto, ComputingMilieux_MISCELLANEOUS, Molecular Structure, Condensed matter physics, 010405 organic chemistry, General Medicine, General Chemistry, equipment and supplies, 3. Good health, 0104 chemical sciences, Magnetic anisotropy, chemistry, Dysprosium, Ab initio calculations, magnetic properties, human activities
Abstract: Magnetic moments: The orientation of the title single-molecule magnet was investigated by magnetic single crystal and luminescence characterization, supported by ab initio calculations, and was found to be governed by the position of the hydrogen atoms of the apical water molecules. This finding suggests that simple magneto-structural correlations can give misleading clues for research in molecular magnetism as well as in the design of MRI contrast agents., This work was supported by the European Research Council through ERC-AdG “MolNanoMaS”.
Published: 2012
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43. 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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