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1. Extending Chirality in Group XIV Metallatranes

Author: Britta Glowacki-Pallach, Michael Lutter, Dieter Schollmeyer, Wolf Hiller, Viatcheslav Jouikov, Klaus Jurkschat, Technische Universität Dortmund [Dortmund] (TU), Johannes Gutenberg - Universität Mainz = Johannes Gutenberg University (JGU), 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), and We are grateful to TU Dortmund for financial support. We thank the Deutsche Forschungsgemeinschaft (DFG, German Research Foundation, Project number 452669688) and the state of North Rhine Westphalia for funding the 600 MHz NMR spectrometer Avance NEO.
Subjects: Inorganic Chemistry, [CHIM.INOR]Chemical Sciences/Inorganic chemistry, Physical and Theoretical Chemistry
Abstract: International audience; The syntheses of the racemic amino alcohol racN(CH2CMe2OH)(CMe2CH2OH)(CH2CHMeOH) (L22'1*H3, 2) and its representative N(CH2CMe2OH)(CMe2CH2OH)(CH2C-(R)HMeOH) (L22'1RH3, 3) with the stereogenic carbon center being R-configured are reported. Also reported are the stannatranes L22'1*SnOt-Bu (4) L22'1RSnOt-Bu (6) and germatranes L22'1*GeOEt (5) and L22'1RGeOEt (7) as well as the trinuclear tin oxocluster [(mu 3-O)(mu 3-O-t-Bu){SnL22'1R}3] (8). NMR and IR spectroscopy, electrospray ionization mass spectrometry (ESI MS), and single crystal X-ray diffraction analysis characterize these compounds. Computational studies accompany the experimental work and help understand the diastereoselectivity observed in the course of the metallatrane syntheses.
Published: 2023

2. Cs2Ln3CuS8 (Ln = La–Nd, Sm–Tb): Synthesis, Crystal Structure, and Magnetic and Optical Properties

Author: Tatiana A. Pomelova, Charlène Delacotte, Natalia V. Kuratieva, Pierric Lemoine, Stéphane Cordier, SangJun Park, Thierry Guizouarn, Vincent Pelletier, Regis Gautier, Nikolay G. Naumov, Nikolaev Institute of Inorganic Chemistry [Novosibirsk] (NIC), Siberian Branch of the Russian Academy of Sciences (SB RAS), 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), Novosibirsk State Technical University, Russian Academy of Sciences [Moscow] (RAS), and International Research Project CLUSPOM 2019-2023 bewteen France and Russia. Innovative Molecules, Materials & Nanomaterials: From Primitive Bricks to the Design of Functional Devices
Subjects: Inorganic Chemistry, crystal structure, magnetocaloric, [CHIM.CRIS]Chemical Sciences/Cristallography, magnetic properties, [CHIM.INOR]Chemical Sciences/Inorganic chemistry, Physical and Theoretical Chemistry, DFT calculations, lanthanide sulfide
Abstract: International audience; This work reports the preparation of new quaternary sulfides Cs(2)Ln(3)CuS(8) (Ln = La-Nd, Sm-Tb), their original crystal and electronic structures, and their magnetic properties. The sulfides were prepared using a reactive flux method from mixtures of Ln(2)S(3) (EuS), Cs(2)S(6), Cu(2)S, and S. They crystallize in a new type of structure (C2/m space group) and exhibit a layer-like crystal structure, which is a hybrid of those of the ACe(2)CuS(6) series (A = Cs, K) and that of K(2)CeCu(2)S(4). The values of the optical band gap calculated by the Kubelka-Munk equation are in the range of 1.2-2.62 eV depending on the nature of the Ln ion. The Cs(2)Gd(3)CuS(8) compound displays relatively great magnetic refrigerating properties at cryogenic temperature with the mass entropy change (-ΔS(M)) reaching 19.5 J kg(-1) K(-1) at 3.5 K for ΔH = 5 T.
Published: 2023

3. Mixed-Valence Conductors from Ni Bis(diselenolene) Complexes with a Thiazoline Backbone

Author: Hadi Hachem, HengBo Cui, Reizo Kato, Pere Alemany, Enric Canadell, Olivier Jeannin, Marc Fourmigué, Dominique Lorcy, 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), RIKEN - Institute of Physical and Chemical Research [Japon] (RIKEN), University of Barcelona, Institut de Ciència de Materials de Barcelona (ICMAB), Consejo Superior de Investigaciones Científicas [Madrid] (CSIC), This work was supported in part by Université de Rennes 1 (Ph.D. grant to H.H.) and by the JSPS KAKENHI (grant JP16H06346). The stay of H.H. to RIKEN was supported in part by the RIKEN International Program Associate and by Rennes Métropole. We thank Takaaki Minamidate (RIKEN) and Thierry Guizouarn (Rennes) for the magnetic susceptibility (SQUID) measurements. Work in Spain was supported by MINECO through Grants PGC2018-096955-B-C44 and PID2021-128217NB-I00, Generalitat de Catalunya (2017SGR1506 and 2017SGR1289). E.C. acknowledges the support of the Spanish MINECO through the Severo Ochoa FUNFUTURE (CEX2019-000917-S) Excellence Centre distinction and P.A. acknowledges the support from the Maria de Maeztu Units of Excellence Program (MDM-2017-0767). Their support is gratefully acknowledged., Université de Rennes 1, Japan Society for the Promotion of Science, Ministerio de Ciencia, Innovación y Universidades (España), Ministerio de Ciencia e Innovación (España), Generalitat de Catalunya, Kato, Reizo, Alemany, Pere, Canadell, Enric, Jeannin, Olivier, Fourmigué, Marc, and Lorcy, Dominique
Subjects: Inorganic Chemistry, Molecular conductors, Crystal-structure, Metal dithiolene complexes, [CHIM]Chemical Sciences, Single-component conductors, Physical and Theoretical Chemistry
Abstract: Highly conducting, mixed-valence, multi-component nickel bis(diselenolene) salts were obtained by electrocrystallization of the monoanionic species [Ni(Me-thiazds)2]-1 (Me-thiazds: N-methyl-1,3-thiazoline-2-thione-4,5-diselenolate), with 1:2 and 1:3 stoichiometries depending of the counter ion used (Et4N+ and nBu4N+ vs Ph4P+, respectively). This behavior strongly differs from that of the corresponding monoanionic dithiolene complexes whose oxidation afforded the single component neutral species. This provides additional rare examples of mixed-valence conducting salts of nickel diselenolene complexes, only known in two examples with the dsit (1,3-dithiole-2-thione-4,5-diselenolate) and dsise (1,3-dithiole-2-selone-4,5-diselenolate) ligands. The mixed-valence salts form highly dimerized or trimerized bi- and trimetallic units, rarely seen with such nickel complexes. Transport measurements under a high pressure (up to 10 GPa) and band structure calculations confirm the semiconducting character of [Ph4P][Ni(Me-thiazds)2]3 and the quasi metallic character of [Et4N][Ni(Me-thiazds)2]2 and [NBu4]x[Ni(Me-thiazds)2]2 salts (0 < x < 1)., This work was supported in part by Université de Rennes 1 (Ph.D. grant to H.H.) and by the JSPS KAKENHI (grant JP16H06346). The stay of H.H. to RIKEN was supported in part by the RIKEN International Program Associate and by Rennes Métropole. We thank Takaaki Minamidate (RIKEN) and Thierry Guizouarn (Rennes) for the magnetic susceptibility (SQUID) measurements. Work in Spain was supported by MINECO through Grants PGC2018-096955-B-C44 and PID2021-128217NB-I00, Generalitat de Catalunya (2017SGR1506 and 2017SGR1289). E.C. acknowledges the support of the Spanish MINECO through the Severo Ochoa FUNFUTURE (CEX2019-000917-S) Excellence Centre distinction and P.A. acknowledges the support from the Maria de Maeztu Units of Excellence Program (MDM-2017-0767). Their support is gratefully acknowledged., With funding from the Spanish government through the ‘Severo Ochoa Centre of Excellence’ accreditation (CEX2019-000917-S).
Published: 2023

4. Ytterbium(III) Complex with Photochromic Ruthenium(II) Acetylide Ligand: All Visible Light Photoswitching of NIR Luminescence

Author: Pramila Selvanathan, Elsa Tufenkjian, Olivier Galangau, Thierry Roisnel, François Riobé, Olivier Maury, Lucie Norel, Stéphane Rigaut, 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), The authors thank the Université de Rennes 1, the CNRS, the ANR (RuOxLux─ANR-12-BS07-0010-01), and MESR for support. This work was performed using HPC/AI resources from GENCI-[CINES/TGCC] (Grant 2020-AP010811752 and 2021-AP0090811914)., and ANR-12-BS07-0010,RuOxLux,Modulation redox de la luminescence à l'aide de complexes organométalliques du ruthénium associés à une unité luminescente(2012)
Subjects: Inorganic Chemistry, [CHIM.INOR]Chemical Sciences/Inorganic chemistry, Physical and Theoretical Chemistry
Abstract: International audience; We report a ruthenium(II) bisacetylide complex bearing a photochromic dithienylethene (DTE) acetylide arm and a coordinating bipyridyl on the trans acetylide unit. Its coordination with Yb(TTA)(3) centers (TTA = 2-thenoyltrifluoroacetonate) produces a bimetallic complex in which the dithienylethene isomerization is triggered by both ultraviolet (UV) light absorbed by the DTE unit and 450 nm excitation in a transition of the organometallic moiety. The redox behavior arising from the ruthenium(II) bisacetylide system is fully investigated by cyclic voltammetry and spectroelectrochemistry, revealing a lack of stability of the DTE-closed oxidized state preventing effective redox luminescence switching. On the other hand, the photoswitching of ytterbium(III) near-infrared (NIR) emission triggered by the photochromic reaction is fully operational. The electronic structure of this complex in its different states characterized by strong electronic coupling between the DTE and the ruthenium(II)-based moieties leading to metal-assisted photochromic behavior were rationalized with the help of time-dependent density functional theory (TD-DFT) calculations.
Published: 2023

5. Thorium- and Uranium-Mediated C–H Activation of a Silyl-Substituted Cyclobutadienyl Ligand

Author: Nikolaos Tsoureas, Thayalan Rajeshkumar, Oliver P. E. Townrow, Laurent Maron, Richard A. Layfield, University of Sussex, Laboratoire de physique et chimie des nano-objets (LPCNO), Institut National des Sciences Appliquées - Toulouse (INSA Toulouse), Institut National des Sciences Appliquées (INSA)-Université de Toulouse (UT)-Institut National des Sciences Appliquées (INSA)-Université de Toulouse (UT)-Institut de Chimie de Toulouse (ICT), Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Université de Toulouse (UT)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université de Toulouse (UT)-Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université de Toulouse (UT)-Fédération de recherche « Matière et interactions » (FeRMI), Institut National des Sciences Appliquées (INSA)-Université de Toulouse (UT)-Institut National des Sciences Appliquées (INSA)-Université de Toulouse (UT)-Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS), Chemistry Research Laboratory [Oxford, UK], and University of Oxford
Subjects: Inorganic Chemistry, OXIDATION-STATE, [CHIM]Chemical Sciences, COMPLEXES, Physical and Theoretical Chemistry
Abstract: Cyclobutadienyl complexes of the f-elements are a relatively new yet poorly understood class of sandwich and half-sandwich organometallic compounds. We now describe cyclobutadienyl transfer reactions of the magnesium reagent [(η4-Cb'''')Mg(THF)3] (1), where Cb'''' is tetrakis(trimethylsilyl)cyclobutadienyl, toward thorium(IV) and uranium(IV) tetrachlorides. The 1:1 stoichiometric reactions between 1 and AnCl4 proceed with intact transfer of Cb'''' to give the half-sandwich complexes [(η4-Cb'''')AnCl(μ-Cl)3Mg(THF)3] (An = Th, 2; An = U, 3). Using a 2:1 reaction stoichiometry produces [Mg2Cl3(THF)6][(η4-Cb'''')An(η3-C4H(SiMe3)3-κ-(CH2SiMe2)(Cl)] (An = Th, [Mg2Cl3(THF)6][4]; An = U [Mg2Cl3(THF)6][5]), in which one Cb'''' ligand has undergone cyclometalation of a trimethylsilyl group, resulting in the formation of an An–C σ-bond, protonation of the four-membered ring, and an η3-allylic interaction with the actinide. Complex solution-phase dynamics are observed with multinuclear nuclear magnetic resonance spectroscopy for both sandwich complexes. A computational analysis of the reaction mechanism leading to the formation of 4 and 5 indicates that the cyclobutadienyl ligands undergo C–H activation across the actinide center.
Published: 2022

6. Not All 3MC States Are the Same: The Role of 3MCcis States in the Photochemical N∧N Ligand Release from [Ru(bpy)2(N∧N)]2+ Complexes

Author: Katie Eastham, Paul A. Scattergood, Danny Chu, Rayhaan Z. Boota, Adrien Soupart, Fabienne Alary, Isabelle M. Dixon, Craig R. Rice, Samantha J. O. Hardman, Paul I. P. Elliott, University of Huddersfield, Photochimie théorique et computationnelle (LCPQ) (PTC), Laboratoire de Chimie et Physique Quantiques Laboratoire (LCPQ), Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Université de Toulouse (UT)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Fédération de recherche « Matière et interactions » (FeRMI), Institut National des Sciences Appliquées - Toulouse (INSA Toulouse), Institut National des Sciences Appliquées (INSA)-Université de Toulouse (UT)-Institut National des Sciences Appliquées (INSA)-Université de Toulouse (UT)-Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Centre National de la Recherche Scientifique (CNRS)-Institut National des Sciences Appliquées - Toulouse (INSA Toulouse), Institut National des Sciences Appliquées (INSA)-Université de Toulouse (UT)-Institut National des Sciences Appliquées (INSA)-Centre National de la Recherche Scientifique (CNRS)-Université Toulouse III - Paul Sabatier (UT3), Institut National des Sciences Appliquées (INSA)-Université de Toulouse (UT)-Institut National des Sciences Appliquées (INSA)-Centre National de la Recherche Scientifique (CNRS), and University of Manchester [Manchester]
Subjects: Inorganic Chemistry, [CHIM]Chemical Sciences, Physical and Theoretical Chemistry
Abstract: International audience; Ruthenium(II) complexes feature prominently in the development of agents for photoactivated chemotherapy, however, the excited state mechanisms by which photochemical ligand release operate remain unclear. We report here a systematic experimental and computational study of a series of complexes [Ru(bpy)2(N^N)]2+ (bpy = 2,2'-bipyridyl; N^N = bpy (1), 6-methyl-2,2'-bipyridyl (2), 6,6'-dimethyl-2,2'-bipyridyl (3), 1-benzyl-4-(pyrid-2-yl)-1,2,3-triazole (4), 1-benzyl-4-(6-methylpyrid-2-yl)-1,2,3-triazole (5), 1,1'-dibenzyl-4,4'-bi-1,2,3-triazolyl (6)) in which we probe the contribution to the promotion of photochemical N^N ligand release of the introduction of sterically encumbering methyl substituents and the electronic effect of replacement of pyridine by 1,2,3-triazole donors in the N^N ligand. Complexes 2 to 6 all release the ligand N^N on irradiation in acetonitrile solution to yield cis-[Ru(bpy)2(NCMe)2]2+ with resultant photorelease quantum yields that at first seem counter-intuitive and span a broad range. The data show that incorporation of a single sterically encumbering methyl substituent on the N∧N ligand (2 and 5) leads to a significantly enhanced rate of triplet metal-to-ligand charge-transfer (3MLCT) state deactivation but with little promotion of photoreactivity, whereas replacement of pyridine by triazole donors (4 and 6) leads to a similar rate of 3MLCT deactivation but with much greater photochemical reactivity. The data reported here, discussed in conjunction with previously reported data on related complexes, suggest that monomethylation in 2 and 5 sterically inhibits the formation of a 3MCcis state but promotes the population of 3MCtrans states which rapidly deactivate 3MLCT states and are prone to mediating ground-state recovery. On the other hand, increased photochemical reactivity in 4 and 6 seems to stem from the accessibility of 3MCcis states. The data provide important insights into the excited-state mechanism of photochemical ligand release by Ru(II) tris-bidentate complexes.
Published: 2022

7. LiMo8O10: Polar Crystal Structure with Infinite Edge-Sharing Molybdenum Octahedra

Author: Zachary T. Messegee, Philippe Gall, Hari Bhandari, Peter E. Siegfried, Chang-Jong Kang, Benjamin Chen, Carl R. Conti, Banghao Chen, Mark Croft, Qiang Zhang, Syed N. Qadri, Joseph Prestigiacomo, Nirmal J. Ghimire, Patrick Gougeon, Xiaoyan Tan, Institut des Sciences Chimiques de Rennes (ISCR), Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), and Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)
Subjects: Inorganic Chemistry, [CHIM]Chemical Sciences, Physical and Theoretical Chemistry
Abstract: International audience
Published: 2022

8. Pourbaix Diagram of Astatine Revisited: Experimental Investigations

Author: Lu Liu, Rémi Maurice, Nicolas Galland, Philippe Moisy, Julie Champion, Gilles Montavon, Laboratoire de physique subatomique et des technologies associées (SUBATECH), Institut National de Physique Nucléaire et de Physique des Particules du CNRS (IN2P3)-Centre National de la Recherche Scientifique (CNRS)-IMT Atlantique (IMT Atlantique), Institut Mines-Télécom [Paris] (IMT)-Institut Mines-Télécom [Paris] (IMT)-Nantes université - UFR des Sciences et des Techniques (Nantes univ - UFR ST), Nantes Université - pôle Sciences et technologie, Nantes Université (Nantes Univ)-Nantes Université (Nantes Univ)-Nantes Université - pôle Sciences et technologie, Nantes Université (Nantes Univ)-Nantes Université (Nantes Univ), 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), Chimie Et Interdisciplinarité : Synthèse, Analyse, Modélisation (CEISAM), Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Nantes université - UFR des Sciences et des Techniques (Nantes univ - UFR ST), Institut des Sciences et technologies pour une Economie Circulaire des énergies bas carbone (ISEC), CEA-Direction des Energies (ex-Direction de l'Energie Nucléaire) (CEA-DES (ex-DEN)), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA), the GIP ARRONAX for the production of At-211., and ANR-11-LABX-0018,IRON,Radiopharmaceutiques Innovants en Oncologie et Neurologie(2011)
Subjects: Inorganic Chemistry, [CHIM]Chemical Sciences, Physical and Theoretical Chemistry
Abstract: International audience; The Pourbaix diagram of an element displays its stable chemical forms with respect to the redox potential and pH of the solution, whose knowledge is fundamental for understanding and anticipating the chemistry of the element in a specified solution. Unlike most halogens, the Pourbaix diagram in the aqueous phase for astatine (At, Z = 85) is still under construction. In particular, the predominant domains of two astatine species assumed to exist under alkaline conditions, At$^-$ and AtO(OH)$_2$$^-$, need to be refined. Through high-performance ion-exchange chromatography, electromobility measurements, and competition experiments, the existence of At$^-$ and AtO(OH)$_2$$^-$ has been confirmed and the associated standard potential has been determined for the first time (0.86 ± 0.05 V vs the standard hydrogen electrode). On the basis of these results, a revised version of astatine’s Pourbaix diagram is proposed, covering the three oxidation states of astatine that exist in the thermodynamic stability range of water: At(-I), At(I), and At(III) (as $_2$$^-$, $_2$$^+$, AtO(+), AtO(OH), and AtO(OH)$_2$$^-$
Published: 2022

9. Un complexe de cuivre(I)-phénanthroline encombré mais stable : impact de la contrainte stérique et de la symétrie sur les propriétés de l'état excité

Author: Lea Gimeno, Brian T. Phelan, Emily A. Sprague-Klein, Thierry Roisnel, Errol Blart, Christophe Gourlaouen, Lin X. Chen, Yann Pellegrin, Chimie Et Interdisciplinarité : Synthèse, Analyse, Modélisation (CEISAM), Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Nantes université - UFR des Sciences et des Techniques (Nantes univ - UFR ST), Nantes Université - pôle Sciences et technologie, Nantes Université (Nantes Univ)-Nantes Université (Nantes Univ)-Nantes Université - pôle Sciences et technologie, Nantes Université (Nantes Univ)-Nantes Université (Nantes Univ), Chemical Sciences and Engineering Division [Argonne], Argonne National Laboratory [Lemont] (ANL), 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 Chimie de Strasbourg, Université de Strasbourg (UNISTRA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), and ANR-16-CE07-0012,PERCO,photogénération de forts pouvoirs réducteurs avec des photosensibilisateurs à base de complexes de cuivre(I)(2016)
Subjects: Inorganic Chemistry, [CHIM.THEO]Chemical Sciences/Theoretical and/or physical chemistry, [CHIM]Chemical Sciences, [CHIM.COOR]Chemical Sciences/Coordination chemistry, Physical and Theoretical Chemistry
Abstract: International audience; The steric strain around copper(I) in typical [Cu(NNR)2] + complexes, where NNR is a diimine ligand substituted in α of the nitrogen atoms by R, is known to strongly impact the excited-state properties. Generally speaking, the larger R, the longer the emission lifetime and higher quantum yield. However, the stability of the coordination scaffold can be at stake if the steric strain imposed by R is too large. In this work, we explore a way of fine-tuning the steric strain around Cu(I) to reach a balance between high emission quantum yield and stability in a highly bulky copper(I) complex. Taking stable [Cu(dipp)2] + and unstable [Cu(dtbp)2] + (where dipp and dtbp are respectively 2,9-diisopropyl-1,10-phenanthroline and 2,9-ditert-butyl-1,10phenanthroline) as boundary of two least and most sterically strained structures, we designed and characterized non-symmetrical ligand 2-isopropyl-9-tert-butyl-1,10-phenanthroline (L1) and corresponding complex [Cu(L1)2] + (Cu1). The key experimental findings are that Cu1 exhibits a rigid tetrahedral geometry in the ground state, close to that of [Cu(dtbp)2] + and with an intermediate stability between that of [Cu(dipp)2] + and [Cu(dtbp)2] +. Conversely, the non-symmetrical nature of ligand L1 leads to a shorter emission lifetime and smaller quantum yield than either [Cu(dipp)2] + or [Cu(dtbp)2] +. This peculiar behavior is rationalized through the in depth analysis of the ultrafast dynamics of the excited state measured with optical transient absorption spectroscopy and theoretical calculations performed on the ground and excited state of Cu1. Our main findings are that the obtained complex is significantly more stable than [Cu(dtbp)2] + despite the sterically strained coordination sphere. The non-symmetrical nature of the ligand translates into a strongly distorted structure in the excited state. The distortion can be described as a rocking motion of one ligand, entailing the premature extinction of the excited state via several deactivation channels.; La contrainte stérique autour du cuivre (I) dans les complexes typiques [Cu(NNR)2] +, où NNR est un ligand diimine substitué en α des atomes d'azote par R, est connue pour avoir un fort impact sur les propriétés des états excités. De manière générale, plus R est grand, plus la durée de vie de l'émission est longue et le rendement quantique élevé. Cependant, la stabilité de l'échafaudage de coordination peut être mise en jeu si la contrainte stérique imposée par R est trop importante. Dans ce travail, nous explorons un moyen de régler finement la contrainte stérique autour de Cu(I) pour atteindre un équilibre entre un rendement quantique d'émission élevé et la stabilité dans un complexe de cuivre(I) très volumineux. En prenant [Cu(dipp)2] + stable et [Cu(dtbp)2] + instable (où dipp et dtbp sont respectivement 2,9-diisopropyl-1,10-phenanthroline et 2,9-ditert-butyl-1, 10-phénanthroline) comme limite des deux structures les moins et les plus stériquement tendues, nous avons conçu et caractérisé le ligand non symétrique 2-isopropyl-9-tert-butyl-1,10-phénanthroline (L1) et le complexe correspondant [Cu(L1)2] + (Cu1). Les principaux résultats expérimentaux sont que Cu1 présente une géométrie tétraédrique rigide dans l'état fondamental, proche de celle de [Cu(dtbp)2] + et avec une stabilité intermédiaire entre celle de [Cu(dipp)2] + et [Cu(dtbp)2] +. Inversement, la nature non symétrique du ligand L1 entraîne une durée de vie d'émission plus courte et un rendement quantique plus faible que ceux de [Cu(dipp)2] + ou [Cu(dtbp)2] +. Ce comportement particulier est rationalisé par l'analyse approfondie de la dynamique ultrarapide de l'état excité, mesurée par spectroscopie d'absorption optique transitoire, et par des calculs théoriques effectués sur l'état fondamental et excité de Cu1. Nos principales conclusions sont que le complexe obtenu est significativement plus stable que [Cu(dtbp)2] + malgré la sphère de coordination stériquement tendue. La nature non symétrique du ligand se traduit par une structure fortement déformée dans l'état excité. La distorsion peut être décrite comme un mouvement de bascule d'un ligand, entraînant l'extinction prématurée de l'état excité via plusieurs canaux de désactivation.
Published: 2023

10. Coordination of Ethylamine on Small Silver Clusters: Structural and Topological (ELF, QTAIM) Analyses

Author: Corinne Lacaze-Dufaure, Yann Bulteau, Nathalie Tarrat, David Loffreda, Pierre Fau, Katia Fajerwerg, Myrtil L. Kahn, Franck Rabilloud, Christine Lepetit, Centre interuniversitaire de recherche et d'ingenierie des matériaux (CIRIMAT), Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Université de Toulouse (UT)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université de Toulouse (UT), Centre d'élaboration de matériaux et d'études structurales (CEMES), Institut National des Sciences Appliquées - Toulouse (INSA Toulouse), Institut National des Sciences Appliquées (INSA)-Université de Toulouse (UT)-Institut National des Sciences Appliquées (INSA)-Université de Toulouse (UT)-Institut de Chimie de Toulouse (ICT), Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université de Toulouse (UT)-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), Laboratoire de chimie de coordination (LCC), Institut de Chimie de Toulouse (ICT), Physico-chimie théorique (THEOCHEM), Institut Lumière Matière [Villeurbanne] (ILM), Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-Centre National de la Recherche Scientifique (CNRS)-Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-Centre National de la Recherche Scientifique (CNRS), and Centre National de la Recherche Scientifique (CNRS)
Subjects: Silver, Energy, Ag clusters, Metal clusters, Ligands, DFT, Ag-N and Ag-Ag bond energies, ELF and QTAIM topological analyses, [SPI.MAT]Engineering Sciences [physics]/Materials, [CHIM.THEO]Chemical Sciences/Theoretical and/or physical chemistry, Inorganic Chemistry, geometrical 2D/3D transition, Mathematical methods, [CHIM.COOR]Chemical Sciences/Coordination chemistry, [SPI.GPROC]Engineering Sciences [physics]/Chemical and Process Engineering, Ethylamine, Physical and Theoretical Chemistry
Abstract: International audience; Amine ligands are expected to drive the organization of metallic centers as well as the chemical reactivity of silver clusters early growing during the very first steps of the synthesis of silver nanoparticles via an organometallic route. Density functional theory (DFT) computational studies have been performed to characterize the structure, the atomic charge distribution, and the planar two-dimensional (2D)/three-dimensional (3D) relative stability of small-size silver clusters (Agn, 2 ≤ n ≤ 7), with or without an ethylamine (EA) ligand coordinated to the Ag clusters. The transition from 2D to 3D structures is shifted from n = 7 to 6 in the presence of one EA coordinating ligand, and it is explained from the analysis of the Ag–N and Ag–Ag bond energies. For fully EA saturated silver clusters (Agn–EAn), the effect on the 2D/3D transition is even more pronounced with a shift between n = 4 and 5. Subsequent electron localization function (ELF) and quantum theory of atoms in molecules (QTAIM) topological analyses allow for the fine characterization of the dative Ag–N and metallic Ag–Ag bonds, both in nature and in strength. Electron transfer from ethylamine to the coordinated silver atoms induces an increase of the polarization of the metallic core.
Published: 2022

11. Synthesis, Crystal Structure, and Luminescence Properties of the Iso-Reticular Series of Lanthanide Coordination Polymers Synthesized from Hexa-Lanthanide Molecular Precursors

Author: Haiyun Yao, Guillaume Calvez, Carole Daiguebonne, Yan Suffren, Kevin Bernot, Thierry Roisnel, 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), and The China Scholarship Council Ph.D. Program, a cooperation program with the French UT and INSA, is acknowledged for financial support.
Subjects: Coordination polymers, Ions, Inorganic Chemistry, Crystal structure, Lanthanides, [CHIM]Chemical Sciences, Physical and Theoretical Chemistry, Ligands
Abstract: International audience; Microwave-assisted reactions in DMSO, between a hexa-lanthanide octahedral complex ([Ln(6)(μ(6)-O)(μ(3)-OH)(8)(NO(3))(6)(H(2)O)(12)·2NO(3)·2H(2)O] with Ln = Nd-Yb plus Y) and either 3-halogenobenzoic acid (hereafter symbolized by 3-xbH with x = f or c for fluoro or chloro, respectively) or 4-halogenobenzoic acid (hereafter symbolized by 4-xbH with x = f, c, or b for fluoro, chloro, or bromo, respectively), lead to 1D lanthanide coordination polymers. These coordination polymers are almost iso-reticular. The crystal structure is described on the basis of the coordination polymer with chemical formula [Tb(4-fb)(3)(DMSO)(H(2)O)(2)·DMSO](∞) obtained from 4-fluorobenzoic acid (4-fbH) and the Tb(3+)-based octahedral complex: It crystallizes in the triclinic system, space group P1̅ (n°2), with the following cell parameters: a = 9.8561(9) Å, b = 10.5636(9) Å, c = 15.1288(15) Å, α = 100.840(3)°, β = 95.552(3)°, γ = 110.482(3)°, V = 1426.4(3) Å(3), and Z = 2. It can be described on the basis of 1D molecular chains. Luminescence properties of the Tb and Eu derivatives have been measured and compared vs the halogeno-function and its position (meta or para). Some molecular alloys have also been prepared to estimate the strength of the intermetallic energy transfers. To confirm that the hexa-nuclear complexes (and not the halogenated ligand) have a structuring effect for the formation of the straight chain-like molecular motif, another coordination polymer with chemical formula [Tb(4-npa)(3)DMSO·DMSO·H(2)O](∞) where 4-npaH symbolizes 4-nitro-phenyl-acetic acid has been prepared. It crystallizes in the triclinic system, space group P1̅ (n°2) with the following cell parameters: a = 7.8784(8) Å, b = 14.8719(16) Å, c = 15.2753(17) Å, α = 73.612(4)°, β = 86.406(4)°, γ = 83.104(4)°, V = 1703.8(3) Å(3), and Z = 2. Its crystal structure can be described on the basis of a molecular motif that is similar to the one observed in the five previous crystal structures which confirms the structuring effect of the hexa-nuclear complexes.
Published: 2022

12. Facile Melting-Crystallization Synthesis of Cs2NaxAg1–xInCl6: Bi Double Perovskites for White Light-Emitting Diodes

Author: Xiaoxi Li, Weiwei Li, Mengling Xia, Chao Liu, Neng Li, Zuhao Shi, Yinsheng Xu, Xianghua Zhang, Wuhan University of Science and Technology, Huazhong University of Science and Technology [Wuhan] (HUST), 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), and This work is financially supported by the National Natural Science Foundation of China (61975156, 61905082), the Hubei Natural Science Foundation (2020CFB641), the State Key Laboratory of Silicate Materials for Architectures (Wuhan University of Technology, SYSJJ2021-01), and the Fundamental Research Funds for the Central Universities (203134001).
Subjects: Inorganic Chemistry, [CHIM.MATE]Chemical Sciences/Material chemistry, [CHIM.INOR]Chemical Sciences/Inorganic chemistry, Physical and Theoretical Chemistry
Abstract: International audience; Lead-free double perovskites (DPs) have outstanding luminescent properties, which make them excellent candidates for wide use in optoelectronics. Herein, a solvent-free melting-crystallization technique, which can produce kilogram-scale DP microcrystals (DP-MCs) in one batch, is invented to synthesize the Cs(2)Na(x)Ag(1-x)InCl(6): Bi (x = 0, 0.2, 0.4, 0.6, 0.8, and 1) DP-MCs. The structure and composition analysis confirmed the products are pure Cs(2)Na(x)Ag(1-x)InCl(6) DP-MCs. Affected by Jahn-Teller distortion of AgCl(6) octahedra, self-trapped excitons appear in the excited state, resulting in the broadband emission (400-850 nm) of Cs(2)Ag(1-x)Na(x)InCl(6): Bi DP-MCs. The enhancement of the photoluminescence quantum yield can be realized by introducing Na(+) to break the parity-forbidden transition in the Cs(2)AgInCl(6) DP. Optimized Cs(2)Na(0.4)Ag(0.6)InCl(6): Bi DP-MC phosphors combined with commercial blue and green phosphors were coated on ultraviolet chips (365 nm) to fabricate white light-emitting diodes (WLEDs) from warm white (2930 K) to cold white (6957 K). An ultrahigh color rendering index of 97.1 and a CCT of 5548 K as well as Commission Internationale de l’Eclairage color coordinates of (0.331, 0.339) have been demonstrated. This kilogram-scale synthesis technique could stimulate the industrial development of WLEDs for general lighting based on DP-MC phosphors.
Published: 2022

13. Luminance and Brightness: Application to Lanthanide-Based Coordination Polymers

Author: Chloé Blais, Guillaume Calvez, Yan Suffren, Carole Daiguebonne, Cyril Paranthoen, Eric Bazin, Stéphane Freslon, Kevin Bernot, 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), Institut des Fonctions Optiques pour les Technologies de l'informatiON (Institut FOTON), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-École Nationale Supérieure des Sciences Appliquées et de Technologie (ENSSAT)-Centre National de la Recherche Scientifique (CNRS), Institut d'Électronique et des Technologies du numéRique (IETR), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-CentraleSupélec-Centre National de la Recherche Scientifique (CNRS)-Nantes Université - pôle Sciences et technologie, Nantes Université (Nantes Univ)-Nantes Université (Nantes Univ), Institut Universitaire de France (IUF), and Ministère de l'Education nationale, de l’Enseignement supérieur et de la Recherche (M.E.N.E.S.R.)
Subjects: Inorganic Chemistry, [CHIM]Chemical Sciences, Physical and Theoretical Chemistry
Abstract: International audience; Measuring the luminance of lanthanide-based coordination polymers under UV excitation is of prime importance for many technological applications. This study highlights that the quantum yield gives no information about the luminescence intensity of a solid-state compound. Indeed, compounds with high quantum yield can actually be poorly luminescent. Therefore, a brightness calculation or a luminance measurement are mandatory for a quantitative estimation of the luminescence intensity. The calculated brightness appears to be a convenient quantitative parameter for the estimation of the luminescence intensity in the infrared domain, in which luminance is senseless. It is also a useful parameter in the visible domain, but one must keep in mind that only compounds with similar colorimetric coordinates can be compared. For comparing the luminescence intensities of compounds that exhibit different emission colors, the luminance measurement seems to be the most efficient method. A home-made setup that allows this measurement with high reproducibility is described in detail. The luminance of several lanthanide-based coordination polymers with benzene-poly-carboxylate ligands is measured, and the results are compared with brightness and quantum yield measurements. A standard is suggested for calibration.
Published: 2022

14. Enantioenriched Ruthenium-Tris-Bipyridine Complexes Bearing One Helical Bipyridine Ligand: Access to Fused Multihelicenic Systems and Chiroptical Redox Switches

Author: Jan Storch, Jeanne Crassous, J. A. Gareth Williams, Jan Sýkora, Jaroslav Žádný, Ivana Císařová, Elsa Caytan, Marie Cordier, Nicolas Vanthuyne, Martin Kos, Vladimír Církva, Rafael Rodríguez, Institute of Chemical Process Fundamentals of the ASCR, Czech Republic, Synthèse Caractérisation Analyse de la Matière (ScanMAT), Université de Rennes (UR)-Institut de Chimie du CNRS (INC)-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), Charles University [Prague] (CU), Institut des Sciences Moléculaires de Marseille (ISM2), Aix Marseille Université (AMU)-École Centrale de Marseille (ECM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Durham University, We thank the Centre National de la Recherche Scientifique (CNRS) and the University of Rennes. This work was supported by the Czech Science Foundation (grant no. 20-19353S). M.K. is grateful to the Ministry of Education, Youth and Sports of the Czech Republic and EU–European Structural and Investment Funds—Operational Programme Research, Development, and Education for the project ÚCHP Mobilita II (CZ.02.2.69/0.0/0.0/18_053/0016920)., Centre National de la Recherche Scientifique (CNRS)-Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Institut de Chimie du CNRS (INC), 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: Tris, 010405 organic chemistry, Stereochemistry, Ligand, chemistry.chemical_element, 010402 general chemistry, 01 natural sciences, Redox, 0104 chemical sciences, Ruthenium, Inorganic Chemistry, Metal, Bipyridine, chemistry.chemical_compound, chemistry, visual_art, visual_art.visual_art_medium, [CHIM]Chemical Sciences, Physical and Theoretical Chemistry
Abstract: International audience; The synthesis and photophysical and chiroptical properties of novel aza[n]helicenes (6a-d, 10a,b, n = 4-7) substituted with one or two 2-pyridyl groups are described. The preparation was performed via an adapted Mallory reaction using aromatic imines as precursors. The obtained novel class of helical 2,2’-bipyridine ligands was then coordinated to Ru(bipy)(2)(2+) units, thus affording the first diastereomerically and enantiomerically pure [RuL(bipy)(2)](2+) (11a,c, L = 6a,c) or [Ru(2)L’(bipy)(4)](4+) (12, L’ = 10b) complexes. The topology and stereochemistry of these novel metal-based helical architectures were studied in detail, notably using X-ray crystallography. Interestingly, the coordination to ruthenium(II) enabled the preparation of fused multihelical systems incorporating aza- and ruthena-helicenes within the same scaffold. The photophysical, chiroptical, and redox properties of these complexes were examined in detail, and efficient redox-triggered chiroptical switching activity was evidenced.
Published: 2021

15. C–N and C–H Activation of an N-Heterocyclic Carbene by Magnesium(II) Hydride and Magnesium(I) Complexes

Author: Cameron Jones, Laurent Maron, Ambre Carpentier, K. Yuvaraj, Cory D. Smith, School of Chemistry, Monash University [Clayton], Laboratoire de physique et chimie des nano-objets (LPCNO), Institut National des Sciences Appliquées - Toulouse (INSA Toulouse), Institut National des Sciences Appliquées (INSA)-Université de Toulouse (UT)-Institut National des Sciences Appliquées (INSA)-Université de Toulouse (UT)-Institut de Chimie de Toulouse (ICT), Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Université de Toulouse (UT)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université de Toulouse (UT)-Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université de Toulouse (UT)-Fédération de recherche « Matière et interactions » (FeRMI), Institut National des Sciences Appliquées (INSA)-Université de Toulouse (UT)-Institut National des Sciences Appliquées (INSA)-Université de Toulouse (UT)-Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS), and Australian Research Council
Subjects: Steric effects, 010405 organic chemistry, Hydride, Magnesium, chemistry.chemical_element, 010402 general chemistry, 01 natural sciences, Medicinal chemistry, 0104 chemical sciences, Adduct, Inorganic Chemistry, IMes, chemistry.chemical_compound, chemistry, [PHYS.PHYS.PHYS-CHEM-PH]Physics [physics]/Physics [physics]/Chemical Physics [physics.chem-ph], Physical and Theoretical Chemistry, Isostructural, Carbene, Mesitylene
Abstract: International audience; Reactions of the hindered N-heterocyclic carbene, :C{(MesNCH)(2)} (IMes; Mes = mesityl), with a series of beta-diketiminatomagnesium(II) hydride and dimagnesium(I) complexes were carried out at 80 degrees C. The reactions involving the magnesium hydrides, [{((Ar)Nacnac)Mg(mu-H)}(2)] [(Ar)Nacnac = [(ArNCMe)(2)CH](-), where Ar = 2,6-diethylphenyl (Dep) or 2,6-diisopropylphenyl (Dip)], proceeded via activation of an exocyclic C-N bond of IMes, giving magnesium imidazolyl compounds [((Ar)Nacnac)Mg(mu-H)(mu-Imid)Mg((Ar)Nacnac)] (Imid = [NC2H2N-(Mes)C](-)) and mesitylene. A low-yield IMes methyl C-H activation product, [((Dep)Nacnac)Mg(IMes(-H))], was also obtained, via H-2 elimination, from the reaction between IMes and [{((Dep)Nacnac)Mg(mu-H)}(2)]. Reactions between IMes and dimagnesium(I) compounds [{((Ar)Nacnac)Mg}(2)] [Ar = 2,6-dimethylphenyl (Xyl) or Mes] afforded isostructural C-H activation products [((Ar)Nacnac)Mg(IMes(-H))] but in higher yields. Density functional theory calculations suggest that the reactions do not progress via stable adduct complex intermediates, which are sterically inaccessible.
Published: 2021

16. Ligand-Induced Cuboctahedral versus Icosahedral Core Isomerism within Eight-Electron Heterocyclic-Carbene-Protected Gold Nanoclusters

Author: Jianyu Wei, Samia Kahlal, Jean-François Halet, Alvaro Muñoz-Castro, Jean-Yves Saillard, 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), Laboratory for Innovative Key Materials and Structures (LINK), Saint-Gobain-National Institute of Materials Science-Centre National de la Recherche Scientifique (CNRS), National Institute for Materials Science (NIMS), Universidad Autonoma de Chile, and The authors are grateful to the Chilean–French ECOS-CONYCYT Program (Project C18E04) and the French–Chilean International Associated Laboratory for 'Multifunctional Molecules and Materials' (LIA-CNRS 1027). The Grand Equipment National de Calcul Intensif is acknowledged for HCP support (Project a0010807367). J.W. thanks the China Scholarship Council for a Ph.D. scholarship. A.M.-C. acknowledges support from FONDECYT (Funds 1180683 and 1221676).
Subjects: Superatoms, Inorganic Chemistry, Core Isomerism, N-heterocyclic Carbene, [CHIM.COOR]Chemical Sciences/Coordination chemistry, Physical and Theoretical Chemistry, Gold Nanoclusters
Abstract: International audience; The controlled structural modification of ligand-protected gold clusters is evaluated by a proper variation of the size and shape of N-heterocyclic carbene (NHC) ligands. Density functional theory calculations show that the Au(13) core of [Au(13)(NHC)(8)Br(4)](+) can be shaped into an icosahedron and/or a so far unexpected cuboctahedron depending on the sterical effect inferred by the NHC ligand side arms. As a result, the cluster properties can be modified, encouraging further exploration on controlled core isomerization in ligated gold cluster chemistry.
Published: 2022

17. Synthesis and Reactivity of Triangular Heterometallic Complexes Containing Zn-Zn Bond

Author: Shengjie Jiang, Yanping Cai, Ambre Carpentier, Iker del Rosal, Laurent Maron, Xin Xu, Laboratoire de physique et chimie des nano-objets (LPCNO), Institut National des Sciences Appliquées - Toulouse (INSA Toulouse), Institut National des Sciences Appliquées (INSA)-Université de Toulouse (UT)-Institut National des Sciences Appliquées (INSA)-Université de Toulouse (UT)-Institut de Chimie de Toulouse (ICT), Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Université de Toulouse (UT)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université de Toulouse (UT)-Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université de Toulouse (UT)-Fédération de recherche « Matière et interactions » (FeRMI), Institut National des Sciences Appliquées (INSA)-Université de Toulouse (UT)-Institut National des Sciences Appliquées (INSA)-Université de Toulouse (UT)-Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS), National Natural Science Foundation of China [21871204], and HPCs CALcul en Midi-Pyrenees (CALMIP-EOS grant) [1415]
Subjects: Inorganic Chemistry, [PHYS.PHYS.PHYS-CHEM-PH]Physics [physics]/Physics [physics]/Chemical Physics [physics.chem-ph], Physical and Theoretical Chemistry
Abstract: International audience; This work provides a facile access to a series oftriangular [Zn2M] (M = group 10 and 11 metals) clusters.Treatment of Zn-Zn-bonded compounds [LZn-ZnL](L=CH3C(2,6-iPr2C6H3N)CHC(CH3)(NCH2CH2PR2); R = Ph,iPr)with zero-valent transition-metal reagents selectively afforded thecorresponding triangular clusters [Zn2M], where M = Ni(0),Pd(0), and Pt(0). Notably, the isoelectronic triangular clusters[Zn2M]+, where M = Ag(I) and Cu(I), could also be obtained byreactions of [LZn-ZnL] with AgOTf and CuOTf, respectively.The [Zn2Ag]+complex containing elusive Zn-Ag bonds wasinvestigated by density functional theory analysis, showing a 3c-2ebonding feature in the metallic ring. The electrochemical behaviorsof [Zn2M] complexes were examined and revealed the donation ofelectron density from the Zn-Zn Sigma-bond to the metal centers. Reaction of the [Zn2Ni] complex with isocyanide gave heterometallicspecies by coordination of isocyanide to the nickel center, keeping the trimetallic ring core structure intact. In contrast, the Zn-Znbond was rapidly cleaved upon treatment of the [Zn2Ni] complex with dihydrogen or phenyl acetylene, generating the hydride- oracetylide-bridged heterotrimetallic complex
Published: 2022

18. Expanding the Toolbox of Octahedral Molybdenum Clusters and Nanocomposites Made Thereof: Evidence of Two-Photon Absorption Induced NIR Emission and Singlet Oxygen Production

Author: Noée Dumait, Stéphane Freslon, Maria Amela-Cortes, Yann Molard, Stéphane Cordier, Gregory Taupier, Soumaya Khlifi, Synthèse Caractérisation Analyse de la Matière (ScanMAT), Centre National de la Recherche Scientifique (CNRS)-Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Institut de Chimie du CNRS (INC), Institut des Sciences Chimiques de Rennes (ISCR), Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA), ANR-16-CE08-0013-02, Agence Nationale de la Recherche, ANR-16-CE08-0013,RENOIR,Sources 1D intégrées à large bande à base de nanocomposite émettant dans le rouge profond(2016), Université de Rennes (UR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), and Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)
Subjects: Nanocomposite, Cluster chemistry, Absorption spectroscopy, 010405 organic chemistry, Singlet oxygen, Silicones, Metal clusters, [CHIM.INOR]Chemical Sciences/Inorganic chemistry, 010402 general chemistry, Photochemistry, 01 natural sciences, Two-photon absorption, 0104 chemical sciences, Oxygen, Inorganic Chemistry, chemistry.chemical_compound, chemistry, [CHIM]Chemical Sciences, Physical and Theoretical Chemistry, Absorption (electromagnetic radiation), Phosphorescence, Excitation
Abstract: International audience; Bright NIR phosphorescence from octahedral molybdenum clusters has been known since the 1980s. However, their behavior toward NIR excitation has never been investigated. Here we report their abilities to emit NIR light and produce singlet oxygen upon two-photon absorption. This behavior is observed in solution, in the solid state, and when clusters are embedded homogeneously in a poly(dimethylsiloxane) matrix. Such discoveries open new perspectives in several fields like optoelectronics, photodynamic therapy, or bioimaging.
Published: 2021

19. Triple-Decker Sandwich Complexes of Tungsten with Planar and Puckered Middle Decks

Author: Ranjit Bag, Suvam Saha, Sundargopal Ghosh, Thierry Roisnel, Rini Prakash, Indian Institute of Technology Madras (IIT Madras), 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), CRG/2019/001280, Science and Engineering Research Board, 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: Cluster chemistry, Hydrogen, 010405 organic chemistry, Chemistry, Thermal decomposition, chemistry.chemical_element, [CHIM.INOR]Chemical Sciences/Inorganic chemistry, Tungsten, Ligands, 010402 general chemistry, Ring (chemistry), 01 natural sciences, 0104 chemical sciences, Inorganic Chemistry, Crystallography, Planar, Metals, [CHIM]Chemical Sciences, Physical and Theoretical Chemistry, Molecular structure, Boron
Abstract: A triple-decker complex of tungsten, [(Cp*W)2{μ-η6:η6-B4H4Co2(CO)5}(H)2] (1; Cp* = η5-C5Me5), with a planar middle deck has been isolated by thermolysis of an in situ formed intermediate from the reaction of Cp*WCl4 and LiBH4 with Co2(CO)8. In addition, we have also isolated another triple-decker complex, [(Cp*W)2{μ-η6:η6-B5H5Fe(CO)3}(H)2] (4), having a puckered central ring, from a similar reaction with Fe2(CO)9. Clusters 1 and 4 are unprecedented examples of a triple-decker complex having a 24-valence electron with bridging hydrogen atoms.
Published: 2021

20. A Combined Experimental and Theoretical Investigation of Arene-Supported Actinide and Ytterbium Tetraphenolate Complexes

Author: Francis Y. T. Lam, Jordann A. L. Wells, Tatsumi Ochiai, Connor J. V. Halliday, Karl N. McCabe, Laurent Maron, Polly L. Arnold, Edinburgh Napier University, Laboratoire de physique et chimie des nano-objets (LPCNO), Institut National des Sciences Appliquées - Toulouse (INSA Toulouse), Institut National des Sciences Appliquées (INSA)-Université de Toulouse (UT)-Institut National des Sciences Appliquées (INSA)-Université de Toulouse (UT)-Institut de Chimie de Toulouse (ICT), Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Université de Toulouse (UT)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université de Toulouse (UT)-Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université de Toulouse (UT)-Fédération de recherche « Matière et interactions » (FeRMI), Institut National des Sciences Appliquées (INSA)-Université de Toulouse (UT)-Institut National des Sciences Appliquées (INSA)-Université de Toulouse (UT)-Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS), U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences, and Biosciences at the Lawrence Berkeley National Laboratory under the Basic Energy Sciences' Quantum Information Science initiative [DE-AC02-05CH11231], Heavy Element Chemistry programs, EPSRC through the Centre for Doctoral Training in Critical Resource Catalysis (CRITICAT) [EP/L016419/1], UK Catalysis Hub [EP/K014714/1, EP/J018139/1], European Research Council (ERC) under the European Union [740311], and University of Edinburgh
Subjects: Inorganic Chemistry, [PHYS.PHYS.PHYS-CHEM-PH]Physics [physics]/Physics [physics]/Chemical Physics [physics.chem-ph], Physical and Theoretical Chemistry
Abstract: International audience; Modular tetraphenolate ligands tethered with a protective arene platform (para-phenyl or para-terphenyl) are used to support mononuclear An(IV) (An = Th, U) complexes with an exceptionally large and open axial coordination site at the metal. The base-free complexes and a series of neutral donor adducts were synthesized and characterized by spectroscopies and single-crystal X-ray diffraction. Anionic Th(IV) -ate complexes with an additional axial aryloxide ligand were also synthesized and characterized. The para-phenyl-tethered mononuclear complexes exhibit rare An(IV)-arene interactions, and the An(IV)-arene distance broadly increases with axial donor strength. The para-terphenyl-tethered complexes have almost no interaction with the arene base, isolating the central metal cation. Computational analysis of the mononuclear complexes and their reduced analogues, and Yb(III) congeners, as well as the effect of additional donor ligand binding, seek to elucidate the electronic structure of the metal-arene interactions and establish whether they, or their reduced or oxidized counterparts, could function as molecular qubits.
Published: 2022

21. Rational Preparation of Well-Defined Multinuclear Iridium-Aluminum Polyhydride Clusters and Comparative Reactivity

Author: Léon Escomel, Naïme Soulé, Emmanuel Robin, Iker Del Rosal, Laurent Maron, Erwann Jeanneau, Chloé Thieuleux, Clément Camp, Catalyse, Polymérisation, Procédés et Matériaux (CP2M), Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-École Supérieure de Chimie Physique Électronique de Lyon (CPE)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Laboratoire de physique et chimie des nano-objets (LPCNO), Institut National des Sciences Appliquées - Toulouse (INSA Toulouse), Institut National des Sciences Appliquées (INSA)-Université de Toulouse (UT)-Institut National des Sciences Appliquées (INSA)-Université de Toulouse (UT)-Institut de Chimie de Toulouse (ICT), Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Université de Toulouse (UT)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université de Toulouse (UT)-Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université de Toulouse (UT)-Fédération de recherche « Matière et interactions » (FeRMI), Institut National des Sciences Appliquées (INSA)-Université de Toulouse (UT)-Institut National des Sciences Appliquées (INSA)-Université de Toulouse (UT)-Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS), Université de Lyon, and 833
Subjects: Inorganic Chemistry, [PHYS.PHYS.PHYS-CHEM-PH]Physics [physics]/Physics [physics]/Chemical Physics [physics.chem-ph], Physical and Theoretical Chemistry
Abstract: International audience; We report an original alkane elimination approach, entailing the protonolysis of triisobutylaluminum by the acidic hydrides from Cp*IrH4. This strategy allows access to a series of well-defined tri- and tetranuclear iridium aluminum polyhydride clusters, depending on the stoichiometry: [Cp*IrH3Al(iBu) (2)](2) (1), [Cp*IrH2Al(iBu)](2) (2), [(Cp* IrH3)(2)Al(iBu)] (3), and [(Cp*IrH3)(3)Al] (4). Contrary to most transition-metal aluminohydride complexes, which can be considered as [AlHx+3](x-) aluminates and LnM(+) moieties, the situation here is reversed: These complexes have original structures that are best described as [Cp*IrHx](n-) iridate units surrounding cationic Al(III) fragments. This is corroborated by reactivity studies, which show that the hydrides are always retained at the iridium sites and that the [Cp*IrH3](-) moieties are labile and can be transmetalated to yield potassium ([KIrCp*H-3], 8) or silver (([AgIrCp*H-3](n), 10) derivatives of potential synthetic interest. DFT calculations show that the bonding situation can vary in these systems, from 3-center 2-electron hydride-bridged Lewis adducts of the form Ir-H -> Al to direct polarized metal-metal interaction from donation of d-electrons of Ir to the Al metal, and both types of interactions take place to some extent in each of these clusters.
Published: 2022

22. 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

23. Deaggregation of Zinc Dihydride by Lewis Acids Including Carbon Dioxide in the Presence of Nitrogen Donors

Author: Thomas P. Spaniol, Jun Okuda, Karl N. McCabe, Laurent Maron, Louis J. Morris, Florian Ritter, Institute of Inorganic Chemistry [Aachen] (IAC RWTH), Rheinisch-Westfälische Technische Hochschule Aachen University (RWTH), Laboratoire de physique et chimie des nano-objets (LPCNO), Institut National des Sciences Appliquées - Toulouse (INSA Toulouse), Institut National des Sciences Appliquées (INSA)-Université de Toulouse (UT)-Institut National des Sciences Appliquées (INSA)-Université de Toulouse (UT)-Institut de Chimie de Toulouse (ICT), Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Université de Toulouse (UT)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université de Toulouse (UT)-Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université de Toulouse (UT)-Fédération de recherche « Matière et interactions » (FeRMI), Institut National des Sciences Appliquées (INSA)-Université de Toulouse (UT)-Institut National des Sciences Appliquées (INSA)-Université de Toulouse (UT)-Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS), Deutsche Forschungsgemeinschaft, and Alexander von Humboldt foundation
Subjects: Denticity, PMDTA, Chemistry, Hydrosilylation, chemistry.chemical_element, Zinc hydride, Zinc, Tetramethylethylenediamine, Medicinal chemistry, Catalysis, Inorganic Chemistry, chemistry.chemical_compound, [PHYS.PHYS.PHYS-CHEM-PH]Physics [physics]/Physics [physics]/Chemical Physics [physics.chem-ph], Lewis acids and bases, Physical and Theoretical Chemistry
Abstract: International audience; Thermally sensitive polymeric zinc dihydride [ZnH2] (n) can conveniently be prepared by the reaction of ZnEt2 with [AlH3(NEt3)]. When reacted with CO2 (1 bar) in the presence of chelating N-donor ligands L-n = N,N,N',N'tetramethylethylenediamine (TMEDA), N,N,N',N'-tetramethyl-1,3-propanediamine (TMPDA), N,N,N',N.,N''-pentamethyldiethylenetriamine (PMDTA), and 1,4,7,10tetramethyl-1,4,7,10-tetraazacyclododecane (Me(4)TACD), insertion into the Zn-H bond readily occurred. Depending on the denticity n, formates [(L-n)Zn(OCHO)(2)] were isolated and structurally characterized, either as a molecule (L-n = TMEDA, TMPDA, PMDTA) or a charge-separated ion pair [(L-n)Zn(OCHO)][OCHO] (L-n = Me(4)TACD). The reaction of [ZnH2] n with the mild Lewis acid BPh3 in the presence of chelating N-donor ligands L-n gave a series of hydridotriphenylborates, either as a contact ion pair [(L-2)Zn(H)(HBPh3)] (L-2 = TMEDA, TMPDA) or a separated ion pair [(L-n)Zn(H)][HBPh3] (L-n = PMDTA, Me(4)TACD). In the crystal, the contact ion pair [(TMEDA)Zn(H)(HBPh3)] showed a bent Zn-H-B bridge indicative of a delocalized Zn-H-B interaction. In contrast, a linear Zn-H-B bridge for [(TMPDA)Zn(H)(HBPh3)] was observed, suggesting a contact ion pair. In THF solution, both complexes show an exchange with free BPh3 as well as [HBPh3](-). DFT calculations suggest the presence of [HBPh3](-) anion with a highly polarized B-H bond that interacts with the Lewis acidic zinc hydride cation [(L-2)Zn(H)](+). The hydridotriphenylborates [(L-n)Zn(H)(HBPh3)] underwent CO2 insertion to give (formato)zinc (formoxy)triphenylborate complexes [(L-n)Zn(OCHO)][(OCHO)BPh3] (L-n = TMPDA, PMDTA, Me(4)TACD). For L-n = TMEDA, a dinuclear complex [(L-n)(2)Zn-2(mu-OCHO)(3)][(OCHO)BPh3] was isolated. Hydridotriphenylborates [(L-n)Zn(H)(HBPh3)] catalyzed the hydrosilylation of CO2 (1 bar) by (BuMe2SiH)-Bu-n in THF at 70 degrees C to give formoxysilane and (methoxy)silane.
Published: 2021

24. Size-Exclusion Mechanism Driving Host–Guest Interactions between Octahedral Rhenium Clusters and Cyclodextrins

Author: Yann Molard, Clément Falaise, Stéphane Cordier, Anton A. Ivanov, Michael A. Shestopalov, Yuri V. Mironov, Kevin Laouer, Emmanuel Cadot, François Hache, Mohamed Haouas, David Landy, Pascale Changenet, 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), Nikolaev Institute of Inorganic Chemistry [Novosibirsk] (NIC), Siberian Branch of the Russian Academy of Sciences (SB RAS), Laboratoire d'Optique et Biosciences (LOB), École polytechnique (X)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS), Novosibirsk State University (NSU), Unité de Chimie Environnementale et Interactions sur le Vivant (UCEIV), Université du Littoral Côte d'Opale (ULCO), Institut des Sciences Chimiques de Rennes (ISCR), Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA), ANR-11-LBX0039-grant, Agence Nationale de la Recherche, 15-15-10006, Russian Science Foundation, Centre National de la Recherche Scientifique, Ministry of Science and Higher Education of the Russian Federation, R?gion Ile de France, 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 Jonchère, Laurent
Subjects: Circular dichroism, 010405 organic chemistry, Supramolecular chemistry, chemistry.chemical_element, Isothermal titration calorimetry, Crystal structure, Rhenium, 010402 general chemistry, 01 natural sciences, 0104 chemical sciences, Inorganic Chemistry, Crystallography, chemistry, [CHIM] Chemical Sciences, Cluster (physics), [CHIM]Chemical Sciences, Molecule, Physical and Theoretical Chemistry, Solvent effects
Abstract: International audience; In aqueous solution, cyclodextrins (CDs) are able to bind strongly either hydrophobic species or also hydrophilic molecules such as octahedral hexametallic cluster. Systematic investigation of the reactivity between native CDs (α- or β-CD) and water-soluble rhenium clusters [ReQ(CN)] with Q = S, Se, and Te were performed, leading to six new crystal structures revealing different types of supramolecular arrangements. Encapsulation of [ReQ(CN)] (Q = S, Se, or Te) within two β-CDs is observed regardless of the cluster size. Interestingly, different assembling scenarios are pointed out depending on the host-guest matching featured by no, partial, or deep inclusion complexes that involved either primary or secondary rim of the CD tori. In the specific case of α-CD, only the smaller cluster [ReS(CN)] is able to form inclusion complex with the tori host. Solution investigations, using a set of complementary techniques including isothermal titration calorimetry, multinuclear NMR methods, cyclic voltammetry, and electrospray ionization mass spectrometry, corroborate nicely conclusions of the solid-state studies. It appears clearly that size-matching supported by solvent effects play key roles in the stability of the host-guest complexes. At last, circular dichroism studies underline that the chirality induction from cyclodextrins to the rhenium cluster depends strongly on the strength of host-guest interactions.
Published: 2019

25. Understanding the Multiconfigurational Ground and Excited States in Lanthanide Tetrakis Bipyridine Complexes from Experimental and CASSCF Computational Studies

Author: Laurent Maron, Richard A. Andersen, Grégory Nocton, Corwin H. Booth, J. I. Amaro-Estrada, Robert L. Halbach, Department of Chemistry [Berkeley], University of California [Berkeley] (UC Berkeley), University of California (UC)-University of California (UC), Laboratoire de chimie moléculaire (LCM), École polytechnique (X)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Laboratoire de physique et chimie des nano-objets (LPCNO), Institut National des Sciences Appliquées - Toulouse (INSA Toulouse), Institut National des Sciences Appliquées (INSA)-Université de Toulouse (UT)-Institut National des Sciences Appliquées (INSA)-Université de Toulouse (UT)-Institut de Chimie de Toulouse (ICT), Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Université de Toulouse (UT)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université de Toulouse (UT)-Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université de Toulouse (UT)-Institut de Recherche sur les Systèmes Atomiques et Moléculaires Complexes (IRSAMC), Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Université de Toulouse (UT)-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS), Chemical Sciences Division [LBNL Berkeley] (CSD), Lawrence Berkeley National Laboratory [Berkeley] (LBNL), University of California [Berkeley], University of California-University of California, Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-École polytechnique (X), Institut de Recherche sur les Systèmes Atomiques et Moléculaires Complexes (IRSAMC), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Centre National de la Recherche Scientifique (CNRS)-Institut National des Sciences Appliquées - Toulouse (INSA Toulouse), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie de Toulouse (ICT-FR 2599), Institut National Polytechnique (Toulouse) (Toulouse INP), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Institut de Chimie du CNRS (INC)-Institut National Polytechnique (Toulouse) (Toulouse INP), and Université Fédérale Toulouse Midi-Pyrénées-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD)-Institut de Chimie du CNRS (INC)
Subjects: Lanthanide, 010405 organic chemistry, Electronic structure, [CHIM.INOR]Chemical Sciences/Inorganic chemistry, 010402 general chemistry, 01 natural sciences, Magnetic susceptibility, 0104 chemical sciences, Square antiprism, Inorganic Chemistry, Bipyridine, chemistry.chemical_compound, Crystallography, chemistry, Excited state, Molecular orbital, Physical and Theoretical Chemistry, Isostructural
Abstract: International audience; An alternative synthesis for M(κ2-bipy)4 (M = La, Ce) and [Li(thf)4][M(κ2-bipy)4] (M = Tb, Dy) and the crystal structures for M = La, Ce, and Tb are described. The isomorphous and isostructural neutral molecules, M = La and Ce, are polymeric in the solid-state, as are those of M = Sm and Eu, which were reported in earlier work. The polymeric network is built from eight coordinate units whose geometry in all four cases is that of a square prism. The known molecules, M = Yb and Lu, are also polymeric, but the eight coordinate units have dodecahedral geometries. The structure of the anions in the separated ion pair, [Li(thf)4][M(κ2-bipy)4], in which Tb is reported in this work and Lu is known, are monomeric with geometries that are between that of a square antiprism and a dodecahdron. The electronic structure, from CASSCF multireference quantum mechanical calculations, shows that the electronic ground states for M = La and Lu are multiconfigurational spin doublets and those for the M = Ce and Yb are multiconfigurational spin triplets. This is confirmed by magnetic susceptibility studies as a function of temperature that are consistent with the metals (La, Ce, Sm, Tb, Dy, Yb, and Lu) being trivalent, as are the LIII-edge XANES spectra (Ce, Yb), and divalent for Eu. The multiconfigurational nature of the ground states, developed from CASSCF molecular orbital calculations, renders a single Lewis structure and a single reference molecular orbital representation misleading. The results from the multireference calculations are extended to the other lanthanide molecules and are the genesis of a new model for understanding the magnetic properties of these molecules.
Published: 2019

26. Thermally Stable Ln(II) and Ca(II) Bis(benzhydryl) Complexes: Excellent Precatalysts for Intermolecular Hydrophosphination of C–C Multiple Bonds

Author: Alexander A. Trifonov, Elisa Louyriac, Gleb S. Plankin, Andrey S. Shavyrin, Alexander N. Selikhov, Laurent Maron, Anton V. Cherkasov, G. A. Razuvaev Institute of Organometallic Chemistry, Russian Academy of Sciences [Moscow] (RAS), Laboratoire de physique et chimie des nano-objets (LPCNO), Institut National des Sciences Appliquées - Toulouse (INSA Toulouse), Institut National des Sciences Appliquées (INSA)-Université de Toulouse (UT)-Institut National des Sciences Appliquées (INSA)-Université de Toulouse (UT)-Institut de Chimie de Toulouse (ICT), Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Université de Toulouse (UT)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université de Toulouse (UT)-Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université de Toulouse (UT)-Institut de Recherche sur les Systèmes Atomiques et Moléculaires Complexes (IRSAMC), Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Université de Toulouse (UT)-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS), Russian Foundation for Basic Research [17-73-20262], and Russian Science Foundation [17-73-20262] Funding Source: Russian Science Foundation
Subjects: chemistry.chemical_classification, Degree of unsaturation, 010405 organic chemistry, Ligand, Intermolecular force, Thermal decomposition, 010402 general chemistry, 01 natural sciences, Decomposition, 0104 chemical sciences, Inorganic Chemistry, Metal, Crystallography, chemistry, visual_art, visual_art.visual_art_medium, Thermal stability, [PHYS.PHYS.PHYS-CHEM-PH]Physics [physics]/Physics [physics]/Chemical Physics [physics.chem-ph], Physical and Theoretical Chemistry, Alkyl
Abstract: International audience; A series of Ln(II) and Ca(II) bis(alkyl) complexes with bulky benzhydryl ligands, [(p-tBu-C6H4)(2)-CH](2)M(L-n) (M = Sm, L = DME, n = 2 (1); M = Sm, Yb, Ca, L = TMEDA, n = 1 (2, 3, 4), were synthesized by the salt-metathesis reaction of MI2(THF)(n) (n = 0-2) and [(p-tBu-C6H4)(2)CH]Na--(+). In complex 1, the benzhydryl ligands are bound to the metal center in eta(2)-coordination mode. Unlike complex 1, in isomorphous complexes 3 and 4, due to the coordination unsaturation of the metal center, the both benzhydryl ligands coordinate to the metal in eta(3)-fashion. In complex 2, one ligand is eta(3)-coordinated while the second one is eta(4)-coordinated to the Sm(II) ion. Complexes 2-4 demonstrated unprecedented thermal stability: no evidence of decomposition was observed after heating their solutions in C6D6 at 100 degrees C during 72 h. Complex 1 behaves differently: thermolysis in C6D6 solution at 75 degrees C results in total decomposition in 8 h. Addition of DME promotes decomposition of 2-4 and makes it feasible at 40 degrees C. Complexes 1-4 demonstrated high catalytic activity and excellent regio- and chemoselectivities in intermolecular hydrophosphination of double and triple C-C bonds with both primary and secondary phosphines. Complexes 2 and 3 enable addition of PhPH2 toward the internal C=C bond of Z- and E-stilbenes with 100% conversion under mild conditions. Double sequential hydrophosphination of phenylacetylene with Ph2PH and PhPH2 was realized due to the application of Yb(II) complex as a catalyst.
Published: 2019

27. 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

28. In Situ Synchrotron Powder Diffraction Study of Cd Intercalation into Chevrel Phases: Crystal Structure and Kinetic Effect

Author: Clotilde Boulanger, Olivier Hernandez, José Barbosa, Carmelo Prestipino, Maryline Guilloux-Viry, Serge Paofai, Catherine Dejoie, Institut Jean Lamour (IJL), Institut de Chimie du CNRS (INC)-Université de Lorraine (UL)-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), European Synchrotron Radiation Facility (ESRF), Université de Lorraine (UL)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), and Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA)
Subjects: In situ, 010405 organic chemistry, Intercalation (chemistry), Chevrel phases, powder diffraction, chemistry.chemical_element, Crystal structure, [CHIM.INOR]Chemical Sciences/Inorganic chemistry, 010402 general chemistry, Kinetic energy, Electrochemistry, 01 natural sciences, 0104 chemical sciences, Inorganic Chemistry, Chalcogen, Crystallography, electrochemistry, chemistry, Molybdenum, [CHIM]Chemical Sciences, Physical and Theoretical Chemistry, Powder diffraction, Cd removal
Abstract: International audience; Chevrel phases are molybdenum chalcogenides of formula M MoX (where M is a cation and X is a chalcogen) that present a complex and captivating intercalation chemistry that has drawn the interest of the solid-state chemistry community since their discovery. This property has a huge potential for applied science and device development for energy storage and pollutant removal and detection, but a deeper knowledge of the intercalation processes and chemistry is still necessary. In the present work, the intercalation of Cd in aqueous solution has been studied, taking advantage of the complementarity of electrochemical characterization and synchrotron powder diffraction acquired during an in situ combined experiment. During the experiment, industrially adequate electrochemical conditions (room temperature and reduced process time) were applied, allowing a better understanding of the intercalation processes. The intercalated phases obtained by electrochemistry have been characterized ex situ, and for the first time the structures of CdMoX (X = S, Se) have been determined. Unexpectedly, CdMoSe presents a trigonal crystal structure with only cavity 2 occupied, which has not been encountered before for Chevrel phases.
Published: 2019

29. 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

30. 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

31. Synthesis, Crystal Structure, and Liquid Exfoliation of Layered Lanthanide Sulfides KLn2CuS6 (Ln = La, Ce, Pr, Nd, Sm)

Author: Nikolay G. Naumov, Tatiana A Pomelova, Nadezhda A Nebogatikova, Maxim R. Ryzhikov, Alexander G. Cherkov, Natalia V. Kuratieva, Arthur Huguenot, Régis Gautier, Tatiana Yu Podlipskaya, Russian Academy of Sciences [Moscow] (RAS), Novosibirsk State Tech. Univ., 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), Novosibirsk State University (NSU), Federal Agency for Scientific Organizations / MASSCOTE (ANR-15-CE05-0027), ANR-15-CE05-0027,MASSCOTE,Matériaux Sulfures à Structures Complexes: application à la Thermoélectricité(2015), 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, Flux method, Chalcogenide, Nanoparticle, Crystal structure, Exfoliation joint, Inorganic Chemistry, chemistry.chemical_compound, Crystallography, chemistry, [CHIM]Chemical Sciences, Orthorhombic crystal system, Physical and Theoretical Chemistry, Monoclinic crystal system
Abstract: International audience; Among the great amount of known lanthanide nanoparticles, reports devoted to chalcogenide ones are deficient. The properties of such nanoparticles remain almost unknown due to the lack of simple and proper synthetic methods avoiding hydrolysis and allowing preparation of oxygen-free lanthanide nanoparticles. A liquid exfoliation method was used to select the optimum strategy for the preparation of quaternary lanthanide sulfide nanoparticles. Bulk KLn(2)CuS(6) (Ln = La-Sm) materials were obtained via a reactive flux method. The crystal structures of three new members of the KLn(2)CuS(6) series were determined for Pr, Nd, and Sm as well as for known KLa2CuS6. KLn(2)CuS(6) (Ln = La, Pr, Nd) compounds crystallize in the monoclinic C2/c space group, whereas KSm2CuS6 crystallizes in the orthorhombic Fddd space group. The analysis of their electronic structures confirms that the main bonding interactions occur within the anionic {Ln(2)CuS(6)}(-) layers. Due to their layered structure, exfoliation of these compounds is possible using ultrasonic treatment in appropriate solvents with the formation of colloidal solutions. Colloidal particles show a plate-like morphology with a lateral size of 100-200 nm and a thickness of 2-10 nm. Highly negative or positive charges found in isopropanol and acetonitrile dispersions, respectively, are associated with high stability and concentration of the dispersions.
Published: 2018

32. Highly Luminescent Europium-Based Heteroleptic Coordination Polymers with Phenantroline and Glutarate Ligands

Author: Stéphane Freslon, Belkacem Benmerad, Sabrina Belaid, Carole Daiguebonne, Yan Suffren, Kevin Bernot, Roza Maouche, Olivier Guillou, Sofiane Bouacida, Université Abderrahmane Mira [Béjaïa], Université Mentouri Constantine [Algérie] (UMC), Université Larbi-Ben-Mhidi [Oum-El-Bouaghi] (OEB), 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), Ministère de l'Enseignement Supérieur et de la Recherche Scientifique, Université frères Mentouri Constantine I (UMC), 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, 010405 organic chemistry, Chemistry, Intermetallic, chemistry.chemical_element, Single-crystal, Crystal structure, 010402 general chemistry, 01 natural sciences, Lanthanides coordination polymers, 0104 chemical sciences, Inorganic Chemistry, chemistry.chemical_compound, Crystallography, phenantroline, Glutaric acid, [CHIM]Chemical Sciences, Physical and Theoretical Chemistry, Isostructural, Europium, Luminescence, Photoluminescence, Derivative (chemistry), Monoclinic crystal system
Abstract: Isostructural lanthanide-based coordination polymers with general chemical formula [Ln(phen)(glu)(NO3)]∞ with Ln = La-Tm (except Ce and Pm) have been synthesized by hydrothermal methods (H2glu stands for glutaric acid and phen stands for 1,10-phenantroline). They crystallize in the monoclinic system with the P21/c (no. 14) space group. The crystal structure has been solved on the basis of the La derivative. It can be described as the superimposition of molecular chains of dimeric La(phen)(NO3)-La(phen)(NO3) units bridged by glutarate ligands. Luminescent properties have been explored and show that the Eu derivative exhibits the highest luminance observed for Eu-based coordination polymers (85 to 105 cd·m-2). Effects of the dilution of the Eu3+ and Tb3+ luminescent ions by Gd3+ optically inactive ions are unexpected and to the best of our knowledge unprecedented. This could be related to the different intermetallic energy-transfer mechanisms in competition and to the nonisotropic distribution of the lanthanide ions in these molecular alloys. The investigation of molecular alloys with general chemical formula [Eu1-xTbx(phen)(glu)(NO3)]∞ with 0 ≤ x ≤ 1 highlights a very sizable and constant Eu3+ luminescence whatever the x value, which further confirms the existence of very strong intermetallic energy transfers in this family of compounds. It is also noticeable that some coordination polymers based on weakly emissive lanthanide ions exhibit very well defined emission spectra.
Published: 2021

33. Azide-Coordination in Homometallic Dinuclear Lanthanide(III) Complexes Containing Nonequivalent Lanthanide Metal Ions: Zero-Field SMM Behavior in the Dysprosium Analogue

Author: Sourav Biswas, Pankaj Kalita, Olivier Cador, Abinash Swain, Pawan Kumar, Vierandra Kumar, Gopalan Rajaraman, Jessica Flores Gonzalez, Vadapalli Chandrasekhar, Joydev Acharya, Fabrice Pointillart, Indian Institute of Technology Kanpur (IIT Kanpur), Indian Institute of Technology Bombay (IIT Bombay), Tata Institute of Fundamental Research, 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), We thank the Department of Science and Technology (DST), India, the CNRS, Université de Rennes 1, the European Commission through the ERC-CoG 725184 MULTIPROSMM (Project No. 725184) for financial support, and also support for the Single Crystal CCD X-ray Diffractometer facility at IIT-Kanpur. V.C. is grateful to the DST for a J. C. Bose fellowship. P.K. and A.S. thank the University Grants Commission (UGC), India for Senior Research Fellowships. G.R. acknowledges DST/SERB for funding (Nos. CRG/2018/000430, DST/SJF/CSA-03/2018-10, SB/SJF/2019-20/12). We sincerely thank Mr. Prakash Nayak, NISER, Bhubanswar, Odisha, India, for the PXRD measurements., European Project: 725184,H2020-EU.1.1. - EXCELLENT SCIENCE - European Research Council (ERC),MULTIPROSMM(2017), Tata Institute of Fundamental Research [Bangalore], 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: Ions, Lanthanide, Azides, Schiff base, 010405 organic chemistry, Chemistry, Ligand, Metal ions in aqueous solution, Ab initio, [CHIM.INOR]Chemical Sciences/Inorganic chemistry, Ligands, 010402 general chemistry, 01 natural sciences, 0104 chemical sciences, Inorganic Chemistry, chemistry.chemical_compound, Crystallography, Deprotonation, Magnetic properties, Lanthanides, [CHIM]Chemical Sciences, Density functional theory, Azide, Physical and Theoretical Chemistry
Abstract: International audience; A series of homometallic dinuclear lanthanide complexes containing nonequivalent lanthanide metal centers [Ln(2)(LH(2))(LH)(CH(3)OH)(N(3))]·xMeOH·yH(2)O [1, Ln = Dy(III), x = 0, y = 2; 2, Ln = Tb(III), x = 1, y = 1] have been synthesized [LH(4) = 6-((bis(2-hydroxyethyl)amino)-N’-(2-hydroxybenzylidene)picolinohydrazide] and characterized. The dinuclear assembly contains two different types of nine-coordinated lanthanide centers, because the nonequivalent binding of the azide co-ligand as well as the varying coordination of the deprotonated Schiff base ligand. Detailed magnetic studies have been performed on the complexes 1 and 2. Complex 1 and its diluted analogue (1(5%)) are zero-field SMMs with effective energy barriers (U(eff)) of magnetization reversal equal to 59(3) K and 66(3) K and relaxation times of τ(0) = 10(4) × 10(-6) s and 10(4) × 10(-8) s, respectively. On the other hand, complex 2 shows a field-induced SMM behavior. Combined ab initio and density functional theory calculations were performed to explain the experimental findings and to unravel the nature of the magnetic anisotropy, exchange-coupled spectra, and magnetic exchange interactions between the two lanthanide centers.
Published: 2021
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34. On the Spin-State Dependence of Redox Potentials of Spin Crossover Complexes

Author: Azzedine Bousseksou, Isabelle M. Dixon, Alix Sournia-Saquet, Sylvain Rat, Lionel Salmon, Gábor Molnár, Laboratoire de Chimie et Physique Quantiques (LCPQ), Institut de Recherche sur les Systèmes Atomiques et Moléculaires Complexes (IRSAMC), Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Centre National de la Recherche Scientifique (CNRS)-Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC), Laboratoire de chimie de coordination (LCC), Institut National Polytechnique (Toulouse) (Toulouse INP), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Institut de Chimie de Toulouse (ICT-FR 2599), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Université de Toulouse (UT)-Université de Toulouse (UT)-Centre National de la Recherche Scientifique (CNRS)-Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Université de Toulouse (UT)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC), Institut de Chimie de Toulouse (ICT), Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Université de Toulouse (UT)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université de Toulouse (UT)-Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Centre National de la Recherche Scientifique (CNRS), Institut National des Sciences Appliquées - Toulouse (INSA Toulouse), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Université Toulouse III - Paul Sabatier (UT3), and Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Centre National de la Recherche Scientifique (CNRS)-Institut National des Sciences Appliquées - Toulouse (INSA Toulouse)
Subjects: Electrochemical reduction, Spin states, 010405 organic chemistry, Chemistry, Spin transition, Charge (physics), 010402 general chemistry, 01 natural sciences, Quantum mechanics, 0104 chemical sciences, Inorganic Chemistry, Mathematical methods, Spin crossover, Chemical physics, Oxidation, Molecule, [CHIM]Chemical Sciences, Molecular orbital, Density functional theory, Physical and Theoretical Chemistry, Redox reactions, Spin-½
Abstract: International audience; Resistance switching properties of nanoscale junctions of spin crossover molecules have received recently much interest. In many cases, this property has been traced back to the variation of molecular orbital energies upon spin transition. However, one can also expect a substantial reorganization of the molecular structure due to charge localization, which calls for a better understanding of the relationship between the redox potential and the spin state of the molecule. To investigate this issue, we carried out a detailed density functional theory and variable temperature cyclic voltammetry investigation of the benchmark compound [Fe(HB(1,2,4-triazol-1-yl)3)2] in solution. We show that, for a correct thermodynamical picture, it is necessary to take into account the charge transfer-induced electronic and structural reorganization as well as spin equilibria in the oxidized and reduced species.
Published: 2020

35. Nickel(0)-Induced β-H Elimination of Magnesium Alkyls: Formation and Reactivity of Heterometallic Hydrides

Author: Xin Xu, Jiasu Huang, Iker del Rosal, Xizhou Zheng, Laurent Maron, Bei Zhao, Soochow University, Laboratoire de physique et chimie des nano-objets (LPCNO), Institut National des Sciences Appliquées - Toulouse (INSA Toulouse), Institut National des Sciences Appliquées (INSA)-Université de Toulouse (UT)-Institut National des Sciences Appliquées (INSA)-Université de Toulouse (UT)-Institut de Chimie de Toulouse (ICT), Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Université de Toulouse (UT)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université de Toulouse (UT)-Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université de Toulouse (UT)-Institut de Recherche sur les Systèmes Atomiques et Moléculaires Complexes (IRSAMC), Université Toulouse III - Paul Sabatier (UT3), and Université de Toulouse (UT)-Université de Toulouse (UT)-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS)
Subjects: Inorganic Chemistry, Nickel, chemistry, Magnesium, Polymer chemistry, chemistry.chemical_element, [PHYS.PHYS.PHYS-CHEM-PH]Physics [physics]/Physics [physics]/Chemical Physics [physics.chem-ph], Physical and Theoretical Chemistry
Abstract: We report the synthesis and reactivity of heterometallic Mg-Ni complexes with bridging hydrides. Treatment of magnesium monoalkyl complexes, which are supported by a tridentate β-diketiminato ligand bearing a pendent phosphine group, with nickel(0) reagent Ni(COD)
Published: 2020

36. Field-Induced Single Molecular Magnetism and Photoluminescence in Rare Cocrystals of Isomorphic Lanthanide(III) Coordination Compounds with Fully Substituted Pyridine-4-carboxamide Ligand

Author: Balkaran Singh Sran, Fabrice Pointillart, Sanyog Sharma, Olivier Cador, Geeta Hundal, Guru Nanak Dev University, Punjab, 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), BSS is thankful to UGC-BSR for a research fellowship and IFCPAR/CEFIPRA for Raman- Charpak fellowship, GH is thankful to CSIR (Research grant No. 01(2971)/19/EMR-II) for financial support. G.H. thanks the DST (Department of Science and Technology, India) for providing facilities under FIST and PURSE programs and the UGC (University Grants Commission) under CAS-II and UPE programs. SS is thankful to the CSIR for the fellowship of Research Associate. This work was supported by CNRS, Université de Rennes 1 and the European Commission through the ERC-CoG 725184 MULTIPROSMM (project n. 725184)., 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, Photoluminescence, 010405 organic chemistry, 010402 general chemistry, 01 natural sciences, 3. Good health, 0104 chemical sciences, Coordination complex, Inorganic Chemistry, Magnetization, Crystallography, chemistry.chemical_compound, chemistry, Pyridine, Molecule, Non-covalent interactions, [CHIM.COOR]Chemical Sciences/Coordination chemistry, Physical and Theoretical Chemistry, Luminescence
Abstract: A series of four isomorphous, 1:2 (complex/L) rare cocrystals of coordination compounds of Ln(III) ions as [Ln(L)(NO3)3(H2O)]2[L]2 (Ln(III) = Gd (1), Tb (2), Dy (3), and Ho (4)), were synthesized with N,N-diisobutylisonicotinamide (L) using a metal-to-ligand ratio of 1:1. All compounds are dimeric in nature with two cocrystallized L molecules centro-symmetrically interspersed between two dimeric units with H-bonded bridges between them to form interesting, self-assembled H-bonded tapes along the c-axis. Detailed Shape analysis and Hirshfeld analysis are done to demonstrate geometry around the metal centers and various noncovalent interactions present in the systems, respectively. Magnetic studies show that compound 3 is a field-induced single-molecule magnet (SMM) for which the magnetization relaxes through a combination of Orbach (Δ = 51 K and τ0 = 3.1 × 10-7 s) and Raman mechanisms. Solid-state luminescence studies reveal that compounds 1, 2, and 3 are photoluminescent in the visible range, while 4 exhibits luminescence in the NIR region. Compound 3 shows cold white-light emission with Commission Internationale de l'Eclairage (CIE) coordinates (0.31, 0.30) and correlated color temperature (CCT) value of 6942 K.
Published: 2020

37. Uranium Metallocene Azides, Isocyanates, and Their Borane-Capped Lewis Adducts

Author: John Arnold, Michael A. Boreen, Trevor D. Lohrey, Stephan Hohloch, Laurent Maron, Fabian A. Watt, Karl N. McCabe, Department of Chemistry [Berkeley], University of California [Berkeley] (UC Berkeley), University of California (UC)-University of California (UC), Laboratoire de physique et chimie des nano-objets (LPCNO), Institut National des Sciences Appliquées - Toulouse (INSA Toulouse), Institut National des Sciences Appliquées (INSA)-Université de Toulouse (UT)-Institut National des Sciences Appliquées (INSA)-Université de Toulouse (UT)-Institut de Chimie de Toulouse (ICT), Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Université de Toulouse (UT)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université de Toulouse (UT)-Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université de Toulouse (UT)-Institut de Recherche sur les Systèmes Atomiques et Moléculaires Complexes (IRSAMC), Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Université de Toulouse (UT)-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS), University of Paderborn, Freie Universität Berlin, and Universität Innsbruck [Innsbruck]
Subjects: 010405 organic chemistry, Ligand, Borane, 010402 general chemistry, Cyanate, 01 natural sciences, Medicinal chemistry, Isocyanate, 0104 chemical sciences, Inorganic Chemistry, chemistry.chemical_compound, chemistry, Cyclopentadienyl complex, [PHYS.PHYS.PHYS-CHEM-PH]Physics [physics]/Physics [physics]/Chemical Physics [physics.chem-ph], Azide, Physical and Theoretical Chemistry, Linkage isomerism, Metallocene
Abstract: Uranium(IV) metallocene complexes (CpiPr4)2U(N3)2 (1-N3), (CpiPr)2U(NCO)2 (1-NCO), and (CpiPr4)2U(OTf)2 (1-OTf) containing the bulky CpiPr4 ligand (CpiPr4 = tetra(isopropyl)cyclopentadienyl) were prepared directly from reactions between (CpiPr4)2UI2 or (CpiPr4)2UI and corresponding pseudohalide salts. The mixed-ligand complex (CpiPr4)2U(N3)(OTf) (1-N3-OTf) was isolated after heating a 1:1 mixture of 1-N3 and 1-OTf. The coordination of 1 equiv B(C6F5)3 to 1-N3 produced the borane-capped azide (CpiPr4)2U(N3)[(μ-η1:η1-N3)B(C6F5)3] (2-N3), while the reaction of 1 equiv B(C6F5)3 with 1-NCO yielded (CpiPr4)2U(NCO)[(μ-η1:η1-OCN)B(C6F5)3] (2-NCO) in which the borane-capped cyanate ligand had rearranged to become O-bound to uranium. The reaction of (CpiPr4)2UI and NaOCN led to the isolation of the uranium(III) cyanate-bridged "molecular square" [(CpiPr4)2U(μ-η1:η1-OCN)]4 (3-OCN). Cyclic voltammetry and UV-vis spectroscopy revealed small differences in the electronic properties between azide and isocyanate complexes, while X-ray crystallography showed nearly identical solid-state structures, with the most notable difference being the geometry of borane coordination to the azide in 2-N3 versus the cyanate in 2-NCO. Reactivity studies comparing 3-OCN to the azide analogue [(CpiPr4)2U(μ-η1:η1-N3)]4 (3-N3) demonstrated significant differences in the chemistry of cyanates and azides with trivalent uranium. A computational analysis of 1-NCO, 1-N3, 2-NCO, and 2-N3 has provided a basis for understanding the energetic preference for specific linkage isomers and the effect of the B(C6F5)3 coordination on the bonding between uranium, azide, and isocyanate ligands.
Published: 2020

38. Chemistry of Dimetallaoctaborane(12) with Chalcogen-Based Borate Ligands: Obedient versus Disobedient Clusters

Author: Chandan Nandi, Sundargopal Ghosh, Mohammad Zafar, Vincent Dorcet, Ketaki Kar, Sourav Kar, Thierry Roisnel, Indian Institute of Technology Madras (IIT Madras), 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), Indian Institute of Technology Madras, Department of Science and Technology, Ministry of Science and Technology, India, 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.chemical_element, Metal carbonyl, Cobalt, Growth, [CHIM.INOR]Chemical Sciences/Inorganic chemistry, 010402 general chemistry, 01 natural sciences, Chalcogen, 0104 chemical sciences, Inorganic Chemistry, Octaborane, Crystallography, chemistry, Cluster, Cluster (physics), [CHIM]Chemical Sciences, Reactivity (chemistry), Physical and Theoretical Chemistry, Boron
Abstract: The reactions of dimetallaoctaboranes(12) [(Cp*M)2B6H10] [M = Co (1) or Rh (2); Cp* = η5-C5Me5] with different chalcogen sources, such as Li[BH2E3] and Li[BH3EPh] (E = S, Se, or Te), led to two unique reaction outcomes. For example, the formation of 10-vertex nido-[(Cp*M)2B6E2H6] (3, M = Co, E = S; 4, M = Co, E = Se; 5, M = Co, E = Te; 6, M = Rh, E = Se) from compounds 1 and 2 is a typical representation of a cluster growth reaction, while the formation of arachno-[(Cp*Co)2B6H9(EPh)] [E = S (9), Se (10), or Te (11)] is a rare method that yielded arachno clusters, keeping the core geometry identical. The formation of arachno-9-11 is a unique method that converts disobedient cluster 1 to obedient clusters 9-11. Further, the reactivity of nido-4 with various metal carbonyls presented sequential cluster growth reactions, which afforded 11-vertex nido-[(Cp*Co)2B6Se2H6{Fe(CO)3}] (7) and 13-vertex fused closo-[(Cp*Co)2B6Se2H6{Ru3(CO)8}] (8). The core geometry of nido-7 is uncommon and very similar to that of [C2B9H11]2- with a unique open pentahapto-coordinating five-membered face.
Published: 2020

39. Supramolecular Anchoring of Octahedral Molybdenum Clusters onto Graphene and Their Synergies in Photocatalytic Water Reduction

Author: Maria Amela-Cortes, Pierric Lemoine, Yann Molard, Marta Feliz, Stéphane Cordier, Pedro Atienzar, Noée Dumait, Universitat Politècnica de València (UPV), Synthèse Caractérisation Analyse de la Matière (ScanMAT), Université de Rennes (UR)-Institut de Chimie du CNRS (INC)-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), I-Link1063, Consejo Superior de Investigaciones Científicas, PGC2018-099744, Ministerio de Ciencia, Innovación y Universidades, Université de Rennes 1, Centre National de la Recherche Scientifique (CNRS)-Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Institut de Chimie du CNRS (INC), 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: Aromatic compounds, Cluster chemistry, Supramolecular chemistry, [CHIM.INOR]Chemical Sciences/Inorganic chemistry, 010402 general chemistry, 7. Clean energy, 01 natural sciences, supramolecular chemistry, law.invention, Absorption, Inorganic Chemistry, Metal, chemistry.chemical_compound, QUIMICA ORGANICA, law, Cluster (physics), [CHIM]Chemical Sciences, Physical and Theoretical Chemistry, 010405 organic chemistry, Chemistry, Graphene, graphene, Two dimensional Materials, Metal cluster, Hydrocarbons, 0104 chemical sciences, Chemical engineering, visual_art, visual_art.visual_art_medium, Photocatalysis, Pyrene, Hybrid material, photocatalysis
Abstract: [EN] Dihydrogen (H-2) production from sunlight should become one of the most important energy production means in the future. To reach this goal, low-cost and efficient photocatalysts still need to be discovered. Here we show that red near-IR luminescent metal cluster anions, once combined with pyrene-containing cations, are able to photocatalytically produce molecular hydrogen from water. The pyrene moieties act simultaneously as energy transmitters and as supramolecular linkers between the cluster anions and graphene. This association results in a hybrid material combining the emission abilities of pyrene and cluster moieties with the electronic conduction efficiency of graphene. Hydrogen evolution reaction (HER) studies show that this association induces a significant increase of H 2 production compared to that produced separately by clusters or graphene. Considering the versatility of the strategy described to design this photocatalytic hybrid material, transition-metal clusters are promising candidates to develop new, environmentally friendly, and low-cost photocatalysts for HER., The Severo Ochoa Program (SEV-2016-0683), Ministerio de Ciencia, Innovation y Universidades (PGC2018-099744), Consejo Superior de Investigaciones Cientificas (I-Link1063), and University of Rennes are thanked for financial support. We thank Dr. Marta Puche for her technical assistance with the preparation of dispersed graphene solutions at the ITQ.
Published: 2019

40. Formation of Mono- and Polynuclear Luminescent Lanthanide Complexes based on the Coordination of Preorganized Phosphonated Pyridines

Author: Franck Camerel, Embarek Bentouhami, Olivier Jeannin, Loïc J. Charbonnière, Jérémy Salaam, Lilia Tabti, Sylvana Bahamyirou, Sarah Cianférani, Oscar Hernandez Alba, Alexandre Lecointre, Aline Nonat, Institut Pluridisciplinaire Hubert Curien ( IPHC ), Université de Strasbourg ( UNISTRA ) -Centre National de la Recherche Scientifique ( CNRS ), Institut des Sciences Chimiques de Rennes ( ISCR ), Université de Rennes 1 ( UR1 ), Université de Rennes ( UNIV-RENNES ) -Université de Rennes ( UNIV-RENNES ) -Ecole Nationale Supérieure de Chimie de Rennes-Institut National des Sciences Appliquées ( INSA ) -Centre National de la Recherche Scientifique ( CNRS ), Sciences Analytiques et Interactions Ioniques et Biomoléculaires ( DSA-IPHC ), Université de Strasbourg ( UNISTRA ) -Centre National de la Recherche Scientifique ( CNRS ) -Université de Strasbourg ( UNISTRA ) -Centre National de la Recherche Scientifique ( CNRS ), University of Ferhat Abbas Setif 1, CNRS, Centre National de la Recherche Scientifique, Université de Strasbourg, GIS, Genome Institute of Singapore, Institut Pluridisciplinaire Hubert Curien (IPHC), Institut National de Physique Nucléaire et de Physique des Particules du CNRS (IN2P3)-Université de Strasbourg (UNISTRA)-Centre National de la Recherche Scientifique (CNRS), Institut des Sciences Chimiques de Rennes (ISCR), Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA), Département Sciences Analytiques et Interactions Ioniques et Biomoléculaires (DSA-IPHC), Institut National de Physique Nucléaire et de Physique des Particules du CNRS (IN2P3)-Université de Strasbourg (UNISTRA)-Centre National de la Recherche Scientifique (CNRS)-Institut National de Physique Nucléaire et de Physique des Particules du CNRS (IN2P3)-Université de Strasbourg (UNISTRA)-Centre National de la Recherche Scientifique (CNRS), Université Ferhat-Abbas Sétif 1 [Sétif] (UFAS1), Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut National de Physique Nucléaire et de Physique des Particules du CNRS (IN2P3)-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 Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut National de Physique Nucléaire et de Physique des Particules du CNRS (IN2P3)-Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut National de Physique Nucléaire et de Physique des Particules du CNRS (IN2P3)-Centre National de la Recherche Scientifique (CNRS)
Subjects: pyridine, Lanthanide, lanthanide, Hydrogen, 010405 organic chemistry, Chemistry, Hydrogen bond, Ligand, Quantum yield, chemistry.chemical_element, 010402 general chemistry, [ CHIM ] Chemical Sciences, 01 natural sciences, Phosphonate, 0104 chemical sciences, Inorganic Chemistry, polynuclear assemblies, Crystallography, chemistry.chemical_compound, luminescence, phosphonate, [CHIM.COOR]Chemical Sciences/Coordination chemistry, Physical and Theoretical Chemistry, Luminescence, Stoichiometry
Abstract: International audience; A series of polynuclear assemblies based on ligand L (1,4,7-tris[hydrogen (6-methylpyridin-2-yl)phosphonate]-1,4,7-triazacyclononane) has been developed. The coordination properties of ligand L with LnIII (Ln = La, Eu, Tb, Yb, Lu) have been studied in water (pH = 7.0) and in D2O (pD = 7.0) by UV-absorption spectrometry, spectrofluorimetry, 1H and 31P NMR, DOSY, ESI-mass spectrometry, and X-ray diffraction. This nonadentate ligand forms highly stable mononuclear complexes in water and provides a very efficient shielding of the Ln cations, as emphasized by the very good luminescence properties of the Yb complex in D2O, especially regarding its lifetime (τD2O = 10.2 μs) and quantum yield (φD2O = 0.42%). In the presence of excess LnIII cation, polynuclar complexes of [(LnL)2Lnx] stoichiometry (x = 1 and x = 2) are observed in solution. In the solid state, a dinuclear complex of La could be isolated and structurally characterized by X-ray diffraction, unraveling the presence of strong hydrogen bonding interactions between a La(H2O)9 3+ cation and the [LaL]3- complex. © 2018 American Chemical Society.
Published: 2018

41. 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

42. Unexpected Magnetic Ordering on the Cr Substructure in UCr2Si2C and Structural Relationships in Quaternary U-Cr-Si-C Compounds

Author: A. Vernière, Bernard Malaman, Gérard Venturini, Mathieu Pasturel, Pierric Lemoine, 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 Jean Lamour (IJL), Institut de Chimie du CNRS (INC)-Université de Lorraine (UL)-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), and Université de Lorraine (UL)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)
Subjects: 010302 applied physics, Magnetic moment, Chemistry, chemistry.chemical_element, 02 engineering and technology, equipment and supplies, 021001 nanoscience & nanotechnology, 01 natural sciences, Inorganic Chemistry, Chromium, Crystallography, 0103 physical sciences, [CHIM]Chemical Sciences, Substructure, Physical and Theoretical Chemistry, 0210 nano-technology, Quaternary, human activities, Carbon
Abstract: International audience; Previous experimental and theoretical studies revealed that carbon insertion into the RCrSi compounds drastically affects the magnetic behavior, since chromium does not carry any magnetic moment in RCrSiC (R = Y, La-Sm, Gd-Er) compounds in contrast to RCrSi (R = Y, Sm, Gd-Lu, Th) compounds. In this study, we report on the unexpected magnetic ordering of chromium atoms in the isotype quaternary UCrSiC compound. While specific heat and magnetic measurements suggest a Pauli paramagnetic behavior, neutron powder diffraction reveals an antiferromagnetic ordering of the chromium substructure at high temperature ( T > 300 K), while that of uranium remains nonmagnetically ordered down to 2 K. Its magnetic behavior, inverse in comparison to the RCrSiC carbides involving a magnetic lanthanide, is discussed in relation with the singularity of its crystal structure among the series. Moreover, the crystallographic structures and the structural stability of UCrSiC and of two other quaternary U-Cr-Si-C compounds (i.e., UCrSiC and UCrSiC), based on the full occupancy of interstitial sites by carbon atoms, are discussed and compared to those of the related ternary intermetallics. Finally, the low-temperature form of UCrSi, corresponding to a displacive transformation around 210 K of the ThCrSi-type structure, is reinvestigated by considering a higher symmetry monoclinic unit cell ( C2/ m) instead of the previously reported triclinic cell ( P1̅). The antiferromagnetic ordering at low temperature ( T = 30(2) K) of the uranium substructure is confirmed, and its magnetic structure is reanalyzed and discussed considering the monoclinic crystal structure.
Published: 2018

43. Aqueous Solvation of SmI3: A Born–Oppenheimer Molecular Dynamics Density Functional Theory Cluster Approach

Author: J. I. Amaro-Estrada, Laurent Maron, Alejandro Ramírez-Solís, Jorge Hernández-Cobos, Universidad Autonoma del Estado de Morelos (UAEM), Universidad Nacional Autónoma de México = National Autonomous University of Mexico (UNAM), Laboratoire de physique et chimie des nano-objets (LPCNO), Institut National des Sciences Appliquées - Toulouse (INSA Toulouse), Institut National des Sciences Appliquées (INSA)-Université de Toulouse (UT)-Institut National des Sciences Appliquées (INSA)-Université de Toulouse (UT)-Institut de Chimie de Toulouse (ICT), Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Université de Toulouse (UT)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université de Toulouse (UT)-Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université de Toulouse (UT)-Institut de Recherche sur les Systèmes Atomiques et Moléculaires Complexes (IRSAMC), Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Université de Toulouse (UT)-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS), CONACYT Basic Science project [253679], DGAPA-UNAM, and DGAPA-UNAM [IG100416]
Subjects: Aqueous solution, 010405 organic chemistry, Chemistry, Born–Oppenheimer approximation, Solvation, 010402 general chemistry, 01 natural sciences, 0104 chemical sciences, Inorganic Chemistry, symbols.namesake, Molecular dynamics, Chemical physics, symbols, Cluster (physics), Molecule, Density functional theory, [PHYS.PHYS.PHYS-CHEM-PH]Physics [physics]/Physics [physics]/Chemical Physics [physics.chem-ph], Physical and Theoretical Chemistry
Abstract: International audience; We report the results of Born-Oppenheimer molecular dynamics (BOMD) simulations on the aqueous solvation of the SmI3 molecule and of the bare Sm3+ cation at room temperature using the cluster microsolvation approach including 37 and 29 water molecules, respectively. The electronic structure calculations were done using the M062X hybrid exchange-correlation functional in conjunction with the 6-31G** basis sets for oxygen and hydrogen. For the iodine and samarium atoms, the Stuttgart-Koln relativistic effective-core potentials were utilized with their associated valence basis sets. When SmI3 is embedded in the microsolvation environment, we find that substitution of the iodine ions by water molecules around Sm(III) cannot be achieved due to an insufficient number of explicit water molecules to fully solvate the four separate metal and halogen ions. Therefore, we studied the solvation dynamics of the bare Sm3+ cation with a 29-water molecule model cluster. Through the Sm-O radial distribution function and the evolution of the Sm-O distances, the present study yields a very tightly bound first rigid Sm(III) solvation shell from 2.3 to 2.9 angstrom whose integration leads to a coordination number of 9 water molecules and a second softer solvation sphere from 3.9 to 5 angstrom with 12 water molecules. No water exchange processes were found. The theoretical EXAFS spectrum is in excellent agreement with the experimental spectrum for Sm(III) in liquid water. The strong differences between the solvation patterns of Sm(III) vs Sm(II) are discussed in detail.
Published: 2018

44. 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

45. Designing a Thermoelectric Copper-Rich Sulfide from a Natural Mineral: Synthetic Germanite Cu22Fe8Ge4S32

Author: Laura Paradis-Fortin, Pierric Lemoine, Emmanuel Guilmeau, Gérard Le Caër, Ventrapati Pavan Kumar, Bernard Malaman, Stéphane Cordier, Vincent Caignaert, Bernard Raveau, Laboratoire de cristallographie et sciences des matériaux (CRISMAT), Université de Caen Normandie (UNICAEN), Normandie Université (NU)-Normandie Université (NU)-École Nationale Supérieure d'Ingénieurs de Caen (ENSICAEN), Normandie Université (NU)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche sur les Matériaux Avancés (IRMA), Normandie Université (NU)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université de Rouen Normandie (UNIROUEN), Normandie Université (NU)-Institut national des sciences appliquées Rouen Normandie (INSA Rouen Normandie), Institut National des Sciences Appliquées (INSA)-Normandie Université (NU)-Institut National des Sciences Appliquées (INSA)-Centre National de la Recherche Scientifique (CNRS)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université de Rouen Normandie (UNIROUEN), Institut National des Sciences Appliquées (INSA)-Normandie Université (NU)-Institut National des Sciences Appliquées (INSA)-Centre National de la Recherche Scientifique (CNRS), 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 Jean Lamour (IJL), Institut de Chimie du CNRS (INC)-Université de Lorraine (UL)-Centre National de la Recherche Scientifique (CNRS), Institut de Physique de Rennes (IPR), Université de Rennes (UR)-Centre National de la Recherche Scientifique (CNRS), ANR-15-CE05-0027, Agence Nationale de la Recherche, ANR-15-CE05-0027,MASSCOTE,Matériaux Sulfures à Structures Complexes: application à la Thermoélectricité(2015), École Nationale Supérieure d'Ingénieurs de Caen (ENSICAEN), Normandie Université (NU)-Normandie Université (NU)-Centre National de la Recherche Scientifique (CNRS)-Université de Caen Normandie (UNICAEN), Normandie Université (NU)-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 Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Centre National de la Recherche Scientifique (CNRS), and Université de Lorraine (UL)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)
Subjects: Sulfide, Physical and chemical processes, Analytical chemistry, chemistry.chemical_element, Mineralogy, 02 engineering and technology, 010402 general chemistry, 01 natural sciences, Inorganic Chemistry, Metal, Thermal conductivity, Electrical resistivity and conductivity, Cations, Seebeck coefficient, Thermoelectric effect, Mössbauer spectroscopy, [CHIM]Chemical Sciences, Physical and Theoretical Chemistry, Thermoelectrics, [PHYS]Physics [physics], chemistry.chemical_classification, Minerals, Chemistry, Crystal structure, 021001 nanoscience & nanotechnology, Copper, 0104 chemical sciences, visual_art, visual_art.visual_art_medium, 0210 nano-technology
Abstract: International audience; This study shows that the design of copper-rich sulfides by mimicking natural minerals allows a new germanite-type sulfide Cu22Fe8Ge4S32 with promising thermoelectric properties to be synthesized. The Mössbauer spectroscopy and X-ray diffraction analyses provide evidence that the structure of our synthetic compound differs from that of the natural germanite mineral Cu26Fe4Ge4S32 by its much higher Cu(+)/Cu(2+) ratio and different cationic occupancies. The coupled substitution Cu/Fe in the Cu26-xFe4+xGe4S32 series also appears as a promising approach to optimize the thermoelectric properties. The electrical resistivity, which decreases slightly as the temperature increases, shows that these materials exhibit a semiconducting behavior, but are at the border of a metallic state. The magnitudes of the electrical resistivity and Seebeck coefficient increase with x, which suggests that Fe for Cu substitution decreases the hole concentration. The thermal conductivity decreases as the temperature increases leading to a moderately low value of 1.2 W m(-1) K(-1) and a maximum ZT value of 0.17 at 575 K.
Published: 2017

46. Experimental and Theoretical Investigation of the Anti-Ferromagnetic Coupling of CrIII Ions through Diamagnetic −O–NbV–O– Bridges

Author: Marijana Jurić, Filip Torić, Vito Despoja, Lidija Androš Dubraja, Andrew Ozarowski, Damir Pajić, William Lafargue-Dit-Hauret, Andrej Zorko, Xavier Rocquefelte, Rudjer Boskovic Institute [Zagreb], Department of Physics [Zagreb], Faculty of Science [Zagreb], University of Zagreb-University of Zagreb, Jozef Stefan Institute [Ljubljana] (IJS), Florida State University [Tallahassee] (FSU), Institut des Sciences Chimiques de Rennes (ISCR), Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA), This work has been supported by the Croatian ScienceFoundation under Project Nos. IP-2014-09-4079 and UIP-2014-09-8276. A.Z. acknowledges the financial support of theSlovenian Research Agency through the Program No. P1-0125and the Project No. Bi-US/14-15-039. National High MagneticField Laboratory is supported by the NSF through theCooperative Agreement DMR-1157490, the State of Florida,and the Department of Energy. X.R. and W.L.D.H. thankCCIPL (Nantes) computing centre for computational facilities., Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), and Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)
Subjects: Chemistry, Physics, Triatomic molecule, 02 engineering and technology, Crystal structure, 010402 general chemistry, 021001 nanoscience & nanotechnology, 01 natural sciences, 0104 chemical sciences, law.invention, Inorganic Chemistry, Crystallography, Magnetization, Computational chemistry, law, Oxo-Bridged Complexes, Chromium, Niobium, Magnetic Properties, DFT Calculation, [CHIM]Chemical Sciences, Molecule, Density functional theory, Orthorhombic crystal system, Physical and Theoretical Chemistry, 0210 nano-technology, Ground state, Electron paramagnetic resonance
Abstract: The synthesis and properties of a novel hetero-tetranuclear compound [Cr2(bpy)4(μ-O)4Nb2(C2O4)4]·3H2O (1 ; bpy = 2, 2′-bipyridine), investigated by single-crystal X-ray diffraction, magnetization measurements, IR, UV/visible spectroscopy, electron paramagnetic resonance (EPR ; X- and Q-bands and high-field), and density functional theory (DFT) calculations, are reported. Crystal structure of 1 (orthorhombic Pcab space group) consists of a square-shaped macrocyclic {; ; ; ; ; Cr2(μ-O)4Nb2}; ; ; ; ; core in which CrIII and NbV ions are alternately bridged by oxo ions and three uncoordinated water molecules. The intramolecular CrIII···CrIII distances through the −O–NbV–O– bridges are 7.410(2) and 7.419(2) Å, while diagonal separation is 5.406(2) Å. The temperature dependence of magnetization M(T) evidences an anti-ferromagnetic ground state, which originates from a magnetic interaction between two CrIII ions of spin 3/2 through two triatomic −O–NbV–O– diamagnetic bridges. A spin Hamiltonian appropriate for polynuclear isolated magnetic units was used. The best-fitting curve for this model is obtained with the parameters gCr = 1.992(3), J = −12.77(5) cm–1, and |D| = 0.17(4) cm–1. The CrIII···CrIII dimer model is confirmed by EPR spectra, which exhibit a pronounced change of their shape around the temperature corresponding to the intradimer coupling J. The EPR spectra simulations and DFT calculations reveal the presence of a single-ion anisotropy that is close to being uniaxial, D = −0.31 cm–1 and E = 0.024 cm–1.
Published: 2017

47. Pressure-Stabilized Cubic Perovskite Oxyhydride BaScO2H

Author: Yasuto Noda, Olivier Hernandez, Noboru Taguchi, Chris J. Pickard, Hikari Sakaebe, Yoshihiro Goto, Cédric Tassel, Mark Green, Yoji Kobayashi, Yoshiharu Uchimoto, Hiroshi Kageyama, Kyoto University [Kyoto], 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), EP/G007489/2, Engineering and Physical Sciences Research Council, Royal Society, 25810040, Japan Society for the Promotion of Science, Wolfson Foundation, Kyoto University, 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: Hydride, Neutron diffraction, Ab initio, Oxide, chemistry.chemical_element, 02 engineering and technology, 010402 general chemistry, 021001 nanoscience & nanotechnology, 01 natural sciences, 3. Good health, 0104 chemical sciences, Inorganic Chemistry, Crystallography, chemistry.chemical_compound, chemistry, Octahedron, [CHIM]Chemical Sciences, Scandium, Physical and Theoretical Chemistry, 0210 nano-technology, Spectroscopy, Perovskite (structure)
Abstract: International audience; We report a scandium oxyhydride BaScO2H prepared by solid state reaction under high pressure. Rietveld refinements against powder synchrotron X-ray and neutron diffraction data revealed that BaScO2H adopts the ideal cubic perovskite structure (Pm3̅m), where oxide (O(2-)) and hydride (H(-)) anions are disordered. (1)H nuclear magnetic resonance (NMR) spectroscopy provides a positive chemical shift of about +4.4 ppm, which can be understood by the distance to the nearest (and possibly the next nearest) cation from the H nucleus. A further analysis of the NMR data and calculations based on ab initio random structure searches suggest a partial cis preference in ScO4H2 octahedra. The present oxyhydride, if compositionally or structurally tuned, may become a candidate for H(-) conductors.
Published: 2017

48. Efficient Photoswitch System Combining a Dimethyldihydropyrene Pyridinium Core and Ruthenium(II) Bis-Terpyridine Entities

Author: Guy Royal, Martial Boggio-Pasqua, Frédéric Lafolet, Saioa Cobo, Frédérique Loiseau, Eric Saint-Aman, Margot Jacquet, Assil Bakkar, Département de Chimie Moléculaire - Chimie Inorganique Redox Biomimétique (DCM - CIRE ), Département de Chimie Moléculaire (DCM), Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université Grenoble Alpes [2016-2019] (UGA [2016-2019])-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université Grenoble Alpes [2016-2019] (UGA [2016-2019]), Interfaces, Traitements, Organisation et Dynamique des Systèmes (ITODYS (UMR_7086)), Université Paris Diderot - Paris 7 (UPD7)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Photochimie théorique et computationnelle (LCPQ) (PTC), Laboratoire de Chimie et Physique Quantiques (LCPQ), Institut de Recherche sur les Systèmes Atomiques et Moléculaires Complexes (IRSAMC), Institut National des Sciences Appliquées - Toulouse (INSA Toulouse), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Centre National de la Recherche Scientifique (CNRS)-Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Institut National des Sciences Appliquées - Toulouse (INSA Toulouse), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Institut de Chimie du CNRS (INC)-Institut de Recherche sur les Systèmes Atomiques et Moléculaires Complexes (IRSAMC), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Institut de Chimie du CNRS (INC), Département de Chimie Moléculaire - Chimie Inorganique Redox Biomimétique (DCM - CIRE), Institut de Chimie Moléculaire de Grenoble (ICMG)-Université Joseph Fourier - Grenoble 1 (UJF)-Centre National de la Recherche Scientifique (CNRS)-Université Grenoble Alpes (UGA), Centre National de la Recherche Scientifique (CNRS)-Université Paris Diderot - Paris 7 (UPD7), Centre National de la Recherche Scientifique (CNRS)-Institut National des Sciences Appliquées - Toulouse (INSA Toulouse), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Centre National de la Recherche Scientifique (CNRS)-Institut National des Sciences Appliquées - Toulouse (INSA Toulouse), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Institut de Recherche sur les Systèmes Atomiques et Moléculaires Complexes (IRSAMC), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées, Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Centre National de la Recherche Scientifique (CNRS)-Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Institut de Recherche sur les Systèmes Atomiques et Moléculaires Complexes (IRSAMC), and Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)
Subjects: endocrine system, Photoisomerization, Photoswitch, 010405 organic chemistry, Chemistry, chemistry.chemical_element, 010402 general chemistry, Photochemistry, 01 natural sciences, 0104 chemical sciences, Ruthenium, [CHIM.THEO]Chemical Sciences/Theoretical and/or physical chemistry, Inorganic Chemistry, chemistry.chemical_compound, Photochromism, Chelation, Pyridinium, Physical and Theoretical Chemistry, Terpyridine, Cyclic voltammetry, ComputingMilieux_MISCELLANEOUS
Abstract: Terpyridine ruthenium complexes linked to the dimethyldihydropyrene (DHP) photochromic unit have been synthesized and fully characterized by cyclic voltammetry and absorption and emission spectroscopy. The study of the photoisomerization reaction undergone by the DHP motif under visible light irradiation is reported. In comparison to previous work, the introduction of an electron-withdrawing pyridinium spacer between the chelating terpyridine unit and the DHP skeleton has considerably tuned the photochromic properties of the free ligands and their corresponding complexes in term of time response and photoreversibility. A rapid, reversible, and complete conversion between the closed and the open forms has been clearly evidenced under visible light irradiation. Only slight perturbations have been induced by the presence of ruthenium centers. Experimental findings and their interpretation have been supported by theoretical calculations.
Published: 2017

49. Differences and Similarities between Lanthanum and Rare-Earth Iodate Anhydrous Polymorphs: Structures, Thermal Behaviors, and Luminescent Properties

Author: Yan Suffren, Olivier Leynaud, Isabelle Gautier-Luneau, Alain Brenier, Philippe Plaindoux, Optique et Matériaux (NEEL - OPTIMA), Institut Néel (NEEL), Institut polytechnique de Grenoble - Grenoble Institute of Technology (Grenoble INP )-Centre National de la Recherche Scientifique (CNRS)-Université Grenoble Alpes [2016-2019] (UGA [2016-2019])-Institut polytechnique de Grenoble - Grenoble Institute of Technology (Grenoble INP )-Centre National de la Recherche Scientifique (CNRS)-Université Grenoble Alpes [2016-2019] (UGA [2016-2019]), 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), X'Press : diffraction et hautes pressions (NEEL - X'Press), Automatisation & caractérisation (NEEL - AUTOCARAC), Institut Lumière Matière [Villeurbanne] (ILM), Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-Centre National de la Recherche Scientifique (CNRS), Optique et Matériaux (OPTIMA ), 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), X'Press (X'Press), Automatisation et Caractérisation (AUTOCARAC ), 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, metal iodates, infrared nonlinear optics, Inorganic chemistry, chemistry.chemical_element, 02 engineering and technology, Crystal structure, 010402 general chemistry, 01 natural sciences, Inorganic Chemistry, chemistry.chemical_compound, Differential scanning calorimetry, matrices, Lanthanum, [CHIM]Chemical Sciences, polar, Physical and Theoretical Chemistry, Isostructural, Iodate, transparency, crystal-structure, 021001 nanoscience & nanotechnology, laser, 0104 chemical sciences, 2nd-harmonic generation, Crystallography, chemistry, Acentric factor, sphere, nd, 0210 nano-technology, Solid solution
Abstract: International audience; The Ln(IO)(HIO) (y = 1 or 1.33) compounds are isostructural with the La(IO)(HIO) phases, but thermal studies reveal different behaviors. On the one hand, the partial thermal decompositions of these lanthanide compounds lead to the Ln(IO) formulation, with a room temperature structure different from the β-La(IO) obtained from La(IO)(HIO). On the other hand, the partial thermal decompositions of the LaLn(IO)(HIO) compounds prepared with lanthanides ions (Ce, Pr, Nd, Sm, Eu, Gd, and Yb) lead to acentric β-LaLn(IO). As for β-La(IO), reversible structural transitions from β-LaLn(IO) to centrosymmetric γ-LaLn(IO) are observed. Differential scanning calorimetry analyses of LaLn(IO) solid solutions show that the transition temperatures vary with the lanthanide concentration in the solid solution. A transition is observed only up to a certain fraction of lanthanide-ion substitution; this substitution limit decreases with the cationic radius of the lanthanide ion. Finally, the β-LaNd(IO) and β-LaYb(IO) phases are investigated by luminescence spectroscopy.
Published: 2016

50. Understanding the Scarcity of Thorium Peroxide Clusters

Author: Shane S. Galley, Thomas E. Albrecht-Schmitt, Cayla E. Van Alstine, Laurent Maron, Department of Chemistry and Biochemistry, Tallahassee (DCB), Florida State University [Tallahassee] (FSU), Laboratoire de physique et chimie des nano-objets (LPCNO), Institut de Recherche sur les Systèmes Atomiques et Moléculaires Complexes (IRSAMC), Institut National des Sciences Appliquées - Toulouse (INSA Toulouse), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Centre National de la Recherche Scientifique (CNRS)-Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Institut National des Sciences Appliquées - Toulouse (INSA Toulouse), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Institut de Chimie de Toulouse (ICT-FR 2599), Institut National Polytechnique (Toulouse) (Toulouse INP), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Institut de Chimie du CNRS (INC)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université Fédérale Toulouse Midi-Pyrénées-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD)-Institut de Chimie du CNRS (INC), Institut National des Sciences Appliquées (INSA)-Université de Toulouse (UT)-Institut National des Sciences Appliquées (INSA)-Université de Toulouse (UT)-Institut de Chimie de Toulouse (ICT), Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Université de Toulouse (UT)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université de Toulouse (UT)-Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université de Toulouse (UT)-Institut de Recherche sur les Systèmes Atomiques et Moléculaires Complexes (IRSAMC), Université Toulouse III - Paul Sabatier (UT3), and Université de Toulouse (UT)-Université de Toulouse (UT)-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS)
Subjects: [PHYS]Physics [physics], Zirconium, 010405 organic chemistry, Inorganic chemistry, Ionic bonding, chemistry.chemical_element, Thorium, 010402 general chemistry, 01 natural sciences, Peroxide, 0104 chemical sciences, Inorganic Chemistry, chemistry.chemical_compound, chemistry, Radiolysis, [CHIM]Chemical Sciences, Mother liquor, Methanol, Physical and Theoretical Chemistry, Acetonitrile
Abstract: bibtex: ISI:000414820100007 bibtex\location:'1155 16TH ST, NW, WASHINGTON, DC 20036 USA',publisher:'AMER CHEMICAL SOC',type:'Article',affiliation:'Albrecht-Schmitt, TE (Reprint Author), Florida State Univ, Dept Chem & Biochem, Tallahassee, FL 32306 USA. Galley, Shane S.; Van Alstine, Cayla E.; Albrecht-Schmitt, Thomas E., Florida State Univ, Dept Chem & Biochem, Tallahassee, FL 32306 USA. Maron, Laurent, Inst Natl Sci Appl, Lab Phys & Chim Nanoobjets, F-31077 Toulouse 4, France.','author-email':'albrecht-schmitt@chem.fsu.edu',da:'2018-12-05','doc-delivery-number':'FM2MY',eissn:'1520-510X','funding-acknowledgement':'Center for Actinide Science and Technology, an Energy Frontier Research Center - U.S. Department of Energy, Office of Science, Basic Energy Sciences [DE-SC0016568]','funding-text':'This work was supported as part of the Center for Actinide Science and Technology, an Energy Frontier Research Center funded by the U.S. Department of Energy, Office of Science, Basic Energy Sciences, under Award DE-SC0016568.','journal-iso':'Inorg. Chem.','keywords-plus':'MOLECULAR-ORBITAL METHODS; VALENCE BASIS-SETS; ENERGY; PSEUDOPOTENTIALS; ACTINIDES; EXCHANGE; ELEMENTS; IR','number-of-cited-references':'26','orcid-numbers':'Albrecht-Schmitt, Thomas/0000-0002-2989-3311','research-areas':'Chemistry','times-cited':'2','unique-id':'ISI:000414820100007','usage-count-last-180-days':'2','usage-count-since-2013':'14','web-of-science-categories':'Chemistry, Inorganic & Nuclear'\; International audience; The reaction of Th(NO3)(4)center dot 5H(2)O with 3 equiv of 2,2',6',2\''\-terpyridine (terpy) in a mixture of acetonitrile and methanol results in formation of the trinuclear thorium peroxide cluster \[\Th(O-2)(terpy)-(NO3)(2)](3). This cluster is assembled via bridging by mu eta(2):eta(2) peroxide anions between thorium centers. It decomposes upon removal from the mother liquor to yield Th(terpy)(NO3)(4) and Th(terpy)(NO3)(4)(EtOH). The peroxide formation appears to be radiolytic in origin and is, most likely, generated from radiolysis of water by short-lived daughters generated from Th-232 decay. This cluster does not form when freshly recrystallized Th(NO3)(4)center dot 5H(2)O is used as the starting material and requires an aged source of thorium. Analysis of the bonding in these clusters shows that, unlike uranium(VI) peroxide interactions, thorium(IV) complexation by peroxide is quite weak and largely ionic. This explains its much lower stability, which is more comparable to that observed in similar zirconium(IV) peroxide clusters.
Published: 2017

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