Author: "Jean-Yves Saillard" - Searchworks@Jio Institute Digital Library Search Results

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1. Assignment of individual structures from intermetalloid nickel gallium cluster ensembles

Author: Maximilian Muhr, Johannes Stephan, Lena Staiger, Karina Hemmer, Max Schütz, Patricia Heiß, Christian Jandl, Mirza Cokoja, Tim Kratky, Sebastian Günther, Dominik Huber, Samia Kahlal, Jean-Yves Saillard, Olivier Cador, Augusto C. H. Da Silva, Juarez L. F. Da Silva, Janos Mink, Christian Gemel, and Roland A. Fischer
Subjects: Chemistry, QD1-999
Abstract: Abstract Poorly selective mixed-metal cluster synthesis and separation yield reaction solutions of inseparable intermetalloid cluster mixtures, which are often discarded. High-resolution mass spectrometry, however, can provide precise compositional data of such product mixtures. Structure assignments can be achieved by advanced computational screening and consideration of the complete structural space. Here, we experimentally verify structure and composition of a whole cluster ensemble by combining a set of spectroscopic techniques. Our study case are the very similar nickel/gallium clusters of M12, M13 and M14 core composition Ni6+xGa6+y (x + y ≤ 2). The rationalization of structure, bonding and reactivity is built upon the organometallic superatom cluster [Ni6Ga6](Cp*)6 = [Ga6](NiCp*)6 (1; Cp* = C5Me5). The structural conclusions are validated by reactivity tests using carbon monoxide, which selectively binds to Ni sites, whereas (triisopropylsilyl)acetylene selectively binds to Ga sites.
Published: 2024
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2. Structural Transformation of Metastable Two-Electron Superatom Au-Doped Cu-Rich Alloy Nanocluster

Author: Rhone P. Brocha Silalahi, Samia Kahlal, Jean-Yves Saillard, and C. W. Liu
Subjects: copper, gold, hydride, superatom, structural transformation, Organic chemistry, QD241-441
Abstract: The ability to fabricate bimetallic clusters with atomic precision offers promising prospects for elucidating the correlations between their structures and properties. Nevertheless, achieving precise control at the atomic level in the production of clusters, including the quantity of dopant, characteristic of ligands, charge state of precursors, and structural transformation, have remained a challenge. Herein, we report the synthesis, purification, and characterization of a new bimetallic hydride cluster, [AuCu11(H){S2P(OiPr)2}6(C≡CPh)3] (AuCu11H). The hydride position in AuCu11H was determined using DFT calculations. AuCu11H comprises a ligand-stabilized defective fcc Au@Cu11 cuboctahedron. AuCu11H is metastable and undergoes a spontaneous transformation through ligand exchange into the isostructural [AuCu11(Cl){S2P(OiPr)2}6(C≡CPh)3] (AuCu11Cl) and into the complete cuboctahedral [AuCu12{S2P(OiPr)2}6(C≡CPh)4]+ (AuCu12) through an increase in nuclearity. These structural transformations were tracked by NMR and mass spectrometry.
Published: 2024
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3. Surface modifications of eight-electron palladium silver superatomic alloys

Author: Subrat Kumar Barik, Chih-Yuan Chen, Tzu-Hao Chiu, Yu-Rong Ni, Franck Gam, Isaac Chantrenne, Samia Kahlal, Jean-Yves Saillard, and C. W. Liu
Subjects: Chemistry, QD1-999
Abstract: Atomically and structurally precise silver nanoclusters hold great potential for catalytic and optoelectronic applications. Here, the authors synthesize and characterize a series of atomically defined dithio- and diselenophosphate-protected eight-electron superatomic palladium-doped silver nanoclusters, including an unprecedented pair of selenolate-protected isomers.
Published: 2022
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4. Atom-Precise Ligated Copper and Copper-Rich Nanoclusters with Mixed-Valent Cu(I)/Cu(0) Character: Structure–Electron Count Relationships

Author: Bachir Zouchoune and Jean-Yves Saillard
Subjects: nanoclusters, copper, nanoalloys, electron count, superatoms, supermolecules, Organic chemistry, QD241-441
Abstract: Copper homometallic and copper-rich heterometallic nanoclusters with some Cu(0) character are reviewed. Their structure and stability are discussed in terms of their number of “free” electrons. In many aspects, this structural chemistry differs from that of their silver or copper homologs. Whereas the two-electron species are by far the most numerous, only one eight-electron species is known, but more electron-rich nanoclusters have also been reported. Owing to the relatively recent development of this chemistry, it is likely that more electron-rich species will be reported in the future.
Published: 2024
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5. Nickel(II)-Based Building Blocks with Schiff Base Derivatives: Experimental Insights and DFT Calculations

Author: Néstor Novoa, Carolina Manzur, Thierry Roisnel, Samia Kahlal, Jean-Yves Saillard, David Carrillo, and Jean-René Hamon
Subjects: nickel, Schiff base complexes, Sonogashira cross coupling, X-ray crystal structure, DFT calculations, Organic chemistry, QD241-441
Abstract: We have recently reported a series of neutral square planar tridentate Schiff base (L) complexes of the general formula [(L)M(py)], showing relatively high first-order hyperpolarizabilities and NLO redox switching behavior. In the present study, new members of this family of compounds have been prepared with the objective to investigate their potential as building blocks in the on-demand construction of D-π-A push–pull systems. Namely, ternary nickel(II) building blocks of general formula [(LA/D)Ni(4-pyX)] (4–7), where LA/D stands for an electron accepting or donating dianionic O,N,O-tridentate Schiff base ligand resulting from the monocondensation of 2-aminophenol or its 4-substituted nitro derivative and β-diketones R-C(=O)CH2C(=O)CH3 (R = methyl, anisyl, ferrocenyl), and 4-pyX is 4-iodopyridine or 4-ethynylpyridine, were synthesized and isolated in 60–78% yields. Unexpectedly, the Sonogashira cross-coupling reaction between the 4-iodopyridine derivative 6 and 4-ethynylpyridine led to the formation of the bis(4-pyridyl) acetylene bridged centrosymmetric dimer [{(LD)Ni}2(µ2-py-C≡C-py)] (8). Complexes 4–8 were characterized by elemental analysis, FT-IR and NMR spectroscopy, single crystal X-ray diffraction and computational methods. In each compound, the four-coordinate Ni(II) metal ion adopts a square planar geometry with two nitrogen and two oxygen atoms as donors occupying trans positions. In 8, the Ni…Ni separation is of 13.62(14) Å. Experimental results were proved and explained theoretically exploiting Density Functional Theory calculations.
Published: 2021
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6. Galvanic replacement-induced introduction of a heteroligand into bimetallic and trimetallic nanoclusters

Author: Jian-Hong Liao, Tzu-Hao Chiu, Hao Liang, Samia Kahlal, Jean-Yves Saillard, C. W. Liu, National Dong Hwa University (NDHU), Institut des Sciences Chimiques de Rennes (ISCR), Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), National Science and Technology Council of Taiwan [111-2123-M-259-002], GENCI computing resource [A0090807367], Instrumentation Center of National Taiwan Normal University (NSTC), China Scholarship Council [NSTC 111-2731-M-003-001], and 202006030018
Subjects: [CHIM]Chemical Sciences, General Materials Science
Abstract: International audience; Heteroleptic 8-electron silver-rich alloy nanoclusters, [Au@Au4Ag12(dtp)(7)(PPh3)(4)](2+) (1) and [Pt@Au4Ag11(dtp)(7)(PPh3)(4)] (2), were successfully synthesized via a galvanic replacement reaction of 1,1-dithiolate-protected M@Ag-20 (M = Au and Pt) nanoclusters with Au(i)-phosphine salts, leading to the alteration of the cluster nuclearity and geometry of shell skeletons but retaining the same 8-electron count.
Published: 2023
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7. Monocarboxylate-protected two-electron superatomic silver nanoclusters with high photothermal conversion performance

Author: Hao-Hai Wang, Jianyu Wei, Fahime Bigdeli, Farzaneh Rouhani, Hai-Feng Su, Ling-Xiao Wang, Samia Kahlal, Jean-François Halet, Jean-Yves Saillard, Ali Morsali, Kuan-Guan Liu, Ningxia University, 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), Tarbiat Modares University [Tehran], Xiamen University, National Institute for Materials Science (NIMS), Laboratory for Innovative Key Materials and Structures (LINK), Saint-Gobain-National Institute of Materials Science-Centre National de la Recherche Scientifique (CNRS), and This experimental work was supported by the National Natural Science Foundation of China (Grant No. 92161106), the Natural Science Foundation of Ningxia (Grant No. 2022AAC05017), the Foundation of State Key Laboratory of Physical Chemistry of Solid Surfaces (Grant No. 202013) and Tarbiat Modares University. We are extremely grateful to Wenyan Dan of Tongji University for his help with the crystal structure determination. The French Grand Equipement National de Calcul Intensif is acknowledged for HCP support (Project a0010807367).
Subjects: [CHIM.CRIS]Chemical Sciences/Cristallography, General Materials Science
Abstract: International audience; The first series of monocarboxylate-protected superatomic silver nanoclusters was synthesized and fully characterized by X-ray diffraction, fourier-transform infrared spectroscopy (FT-IR), X-ray photoelectron spectroscopy (XPS), and electrospray ionization mass spectrometry (ESI-MS). Specifically, compounds [Ag(16)(L)(8)(9-AnCO(2))(12)](2+) (L = Ph(3)P (I), (4-ClPh)(3)P (II), (2-furyl)(3)P (III), and Ph(3)As (IV)) were prepared by a solvent-thermal method under alkaline conditions. These clusters exhibit a similar unprecedented structure containing a [Ag(8)@Ag(8)](6+) metal kernel, of which the 2-electron superatomic [Ag(8)](6+) inner core shows a flattened and puckered hexagonal bipyramid of S(6) symmetry. Density functional theory calculations provide a rationalization of the structure and stability of these 2-electron superatoms. Results indicate that the 2 superatomic electrons occupy a superatomic molecular orbital 1S that has a substantial localization on the top and bottom vertices of the bipyramid. The π systems of the anthracenyl groups, as well as the 1S HOMO, are significantly involved in the optical and photothermal behavior of the clusters. The four characterized nanoclusters show high photothermal conversion performance in sunlight. These results show that the unprecedented use of mono-carboxylates in the stabilization of Ag nanoclusters is possible, opening the door for the introduction of various functional groups on their cluster surface.
Published: 2023
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8. Looking at platinum carbonyl nanoclusters as superatoms

Author: Jianyu Wei, Rémi Marchal, Didier Astruc, Samia Kahlal, Jean-François Halet, 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), Institut des Sciences Moléculaires (ISM), Université Montesquieu - Bordeaux 4-Université Sciences et Technologies - Bordeaux 1 (UB)-École Nationale Supérieure de Chimie et de Physique de Bordeaux (ENSCPB)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), National Institute for Materials Science (NIMS), Laboratory for Innovative Key Materials and Structures (LINK), Saint-Gobain-National Institute of Materials Science-Centre National de la Recherche Scientifique (CNRS), GENCI (Grand Equipement National de Calcul Intensif) [A0050807367], French Research National Agency French National Research Agency (ANR) [ANR-08-BLAN-0079-01], China Scholarship Council China Scholarship Council, and ANR-08-BLAN-0079,NanoTheo,Clusters nanométriques comme intermédiaires entre molécules et état solide. Une approche théorique(2008)
Subjects: [CHIM.THEO]Chemical Sciences/Theoretical and/or physical chemistry, [CHIM.COOR]Chemical Sciences/Coordination chemistry, General Materials Science
Abstract: International audience; Although the chemistry of carbonyl-protected platinum nanoclusters is well established, their bonding mode remains poorly understood. In most of them, the average Pt oxidation state is zero or slightly negative, leading to the apparent average configuration 5d(10) 6s(epsilon) (epsilon = 0 or very small) and the apparent conclusion that metal-metal bonding cannot arise from the completely filled 5d shell nor from the empty (or almost empty) 6s orbitals. However, DFT calculations show in fact that in these species the actual average configuration is 5d(10-x) 6s(x), which provides to the whole cluster a significant total number of 6s electrons that ensures metal-metal bonding. This ("excited") average configuration is to be related to that of coinage metals in ligated group 11 nanoclusters (nd(10) (n + 1)s(x)). Calculations show that metal-metal bonding in most of these platinum nanoclusters can be rationalized within the concepts of superatoms and supermolecules, in a similar way as for group 11 nanoclusters. The "excited" 5d(10-x) 6s(x) configuration results from a level crossing between 5d combinations and 6s combinations, the former transferring their electrons to the latter. This level crossing, which does not exist in the bare Pt-n clusters, is induced by the ligand shell, the role of which being thus not innocent with respect to metal-metal bonding.
Published: 2022
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9. Alloying dichalcogenolate-protected Ag21 eight-electron nanoclusters: a DFT investigation

Author: Jean-Yves Saillard, Tzu-Hao Chiu, Samia Kahlal, Isaac Chantrenne, Jian-Hong Liao, Franck Gam, Chen-Wei Liu, Institut des Sciences Chimiques de Rennes (ISCR), Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), National Dong Hwa University (NDHU), France-Taiwan ANR-MOST 2018 program (project Nanoalloys), GENCI French National Computer Resource Center [A0030807367], Ministry of Science and Technology of TaiwanMinistry of Science and Technology, Taiwan [MOST 109-2113-M-259-008, 108-2923-M-259-001], ANR-18-CE09-0037,Nanoalloys,Alliages superatomiques et de structure précise riches en argent et en cuivre(2018), Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA), Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), and Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)
Subjects: Valence (chemistry), Materials science, Icosahedral symmetry, Heteroatom, Doping, 02 engineering and technology, 010402 general chemistry, 021001 nanoscience & nanotechnology, 01 natural sciences, 0104 chemical sciences, Nanoclusters, Electronegativity, Crystallography, Atomic radius, [CHIM]Chemical Sciences, General Materials Science, 0210 nano-technology, Luminescence
Abstract: International audience; The isoelectronic doping of dichalcogenolato nanoclusters of the type [Ag-21{E2P(OR)(2)}(12)](+) (E = S, Se) by any heteroatom belonging to groups 9-12 was systematically investigated using DFT calculations. Although they can differ in their global structure, all of these species have the same M@M-12-centered icosahedral core. In any case, the different structure types are all very close in energy. In all of them, three different alloying sites can be identified (central, icosahedral, peripheral) and calculations allowed the trends in heteroatom site occupation preference across the group 9-12 family to be revealed. These trends are supported by complementary experimental results. They were rationalized on the basis of electronegativity, potential involvement in the bonding of valence d-orbitals and atom size. TD-DFT calculations showed that the effect of doping on optical properties is sizable and this should stimulate research on the modulation of luminescence properties in the dithiolato and diseleno families of complexes.
Published: 2022
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10. Ferrocene functionalized enantiomerically pure Schiff bases and their Zn(<scp>ii</scp>) and Pd(<scp>ii</scp>) complexes: a spectroscopic, crystallographic, electrochemical and computational investigation

Author: Salvador Celedón, Paul Hamon, Vania Artigas, Mauricio Fuentealba, Samia Kahlal, David Carrillo, Jean-Yves Saillard, Jean-René Hamon, Carolina Manzur, Pontificia Universidad Católica de Valparaíso (PUCV), 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), Fondo Nacional de Desarrollo Cientifico y Tecnologico (FONDECYT), Chile Comision Nacional de Investigacion Cientifica y Tecnologica (CONICYT) CONICYT FONDECYT [1090310], FONDEQUIP [EQM130154, EQM120095], Vicerrectoria de Investigacion y Estudios Avanzados, Pontificia Universidad Catolica de Valparaiso, Chile (VRIEA-PUCV), Centre National de la Recherche Scientifique (CNRS) Centre National de la Recherche Scientifique (CNRS), Universite de Rennes 1, VRIEAPUCV, and FONDECYT Comision Nacional de Investigacion Cientifica y Tecnologica (CONICYT) CONICYT FONDECYT
Subjects: Materials Chemistry, [CHIM]Chemical Sciences, General Chemistry, Catalysis
Abstract: International audience; In this contribution, we describe the synthesis, spectroscopic and structural characterization, as well as the electrochemical behavior of a series of four chiral ferrocene-functionalized Schiff base compounds derived from enantiomerically pure (1R,2R)-(-)-1,2-diaminocyclohexane. The ferrocene enaminones 3 and 4 were obtained upon monocondensation of ferrocenoylacetone Fc-C(= O)CH2C(QO)R (R = CH3, 1; 4-C6H4OH, 2; Fc = (eta(5)-C5H5)Fe(eta(5)-C5H4)) with one amino group of the primary diamine. The two bimetallic complexes 5 and 6 were prepared via a one-pot three-components template procedure involving half-unit 3, 4-methoxysalicylaldehyde and tetrahydrated zinc(II) nitrate for 5, and half-unit 4, 4-formyl-3-hydroxybenzoic acid and palladium(II) acetate for 6. All the syntheses were carried out in refluxing ethanol and compounds 3-6 were isolated as thermally stable, air and moisture compatible colored solids in 71-83% yields. They were characterized by several analytical (EA, ESI-MS) and spectroscopic methods (H-1/C-13 NMR, FT-IR, UV-vis), including the molecular structures of 3 and 4 that were unequivocally established by single crystal X-ray diffraction analyses. Both crystallize in the orthorhombic non-centrosymmetric space group P2(1)2(1)2(1) with two (R,R)-(-)-chiral carbon atoms in the structures. Cyclic voltammetry showed that the greatest anodic shifts (270 mV) of the ferrocenyl Fe(II)/Fe(III) redox potentials are observed for the D-pi-A push-pull derivative 6. Beyond experimental characterization, DFT- and TDDFT-based theoretical analyses of the new chiral ferrocene-containing Schiff base complexes allow interpretation of their observed spectroscopic, structural and electronic features.
Published: 2022
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11. Hydride‐containing 2‐Electron Pd/Cu Superatoms as Catalysts for Efficient Electrochemical Hydrogen Evolution

Author: Rhone P. Brocha Silalahi, Yongsung Jo, Jian‐Hong Liao, Tzu‐Hao Chiu, Eunsaem Park, Woojun Choi, Hao Liang, Samia Kahlal, Jean‐Yves Saillard, Dongil Lee, C. W. Liu, National Dong Hwa University (NDHU), Yonsei University, 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 was supported by the National Science and Technology Council of Taiwan (111-2123-M-259-002), the GENCI computing resource (grant A0090807367), the National Research Foundation of Korea grants (NRF-2022R1A2C3003610 and Carbon-to-X Project No. 2020M3H7A1096388), and the Instrumentation Center of National Taiwan Normal University (NSTC 111-2731-M-003-001). HL thanks the China Scholarship Council for a PhDgrant.
Subjects: superatom, copper, [CHIM]Chemical Sciences, hydride, General Medicine, General Chemistry, Palladium, Catalysis, hydrogen evolution reaction
Abstract: International audience; The first hydride-containing 2-electron palladium/copper alloys, [PdHCu11{S2P(O i Pr)2}6(C≡CPh)4] (PdHCu11) and [PdHCu12{S2P(O i Pr)2}5{S2PO(O i Pr)} (C≡CPh)4] (PdHCu12), are synthesized from the reaction of [PdH2Cu14{S2P(O i Pr)2}6(C≡CPh)6] (PdH2Cu14) with trifluoroacetic acid (TFA). X-ray diffraction reveals that the PdHCu11 and PdHCu12 kernels consist of a central PdH unit encapsulated within a vertex-missing Cu11 cuboctahedron and complete Cu12 cuboctahedron, respectively. DFT calculations indicate that both PdHCu11 and PdHCu12can be considered as axially-distorted 2-electron superatoms. PdHCu11 shows excellent HER activity, unprecedented within metal nanoclusters, with an onset potential of -0.05 V (at 10 mA cm-2), a Tafel slope of 40 mV dec-1, and consistent HER activity during 1000 cycles. Our study suggests that the accessible central Pd site is the key to HER activity and may provide guidelines for correlating catalyst structures and HER activity.
Published: 2023
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12. Phosphorescent cyclometalated platinum( ii ) complexes with phenyldiazine N^C ligands

Author: Mariia Hruzd, Samia Kahlal, Nicolas le Poul, Laurianne Wojcik, Marie Cordier, Jean-Yves Saillard, Julián Rodríguez-López, Françoise Robin-le Guen, Sébastien Gauthier, Sylvain Achelle, 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, Electrochimie Moléculaires et Chimie Analytique (CEMCA), Université de Brest (UBO)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut Brestois Santé Agro Matière (IBSAM), Université de Brest (UBO), Universidad de Castilla-La Mancha = University of Castilla-La Mancha (UCLM), and M. H. acknowledges the Région Bretagne, France and Conseil Départemental des Côtes d'Armor, France for her PhD funding (MMLum project).
Subjects: Inorganic Chemistry, expert elicitation, Chemical risk assessment chemical risk matrix expert elicitation real work situation, real work situation, Chemical risk assessment, chemical risk matrix, [CHIM]Chemical Sciences
Abstract: International audience; A series of phosphorescent platinum(II) complexes containing various phenyldiazine-type bidentate N^C ligands have been successfully synthesized and characterized. Structural modifications have been made to bidentate cyclometalating ligands regarding the nature of the diazine ring (pyrimidine, pyrazine and quinazoline), the substituent groups at the C4 position of the pyrimidine ring (OCH3, CF3) and the EDGs at the para position of the Pt atom (OCH3, Ph, NPh2, carbazol). In addition, the electronic properties of the azaheterocyclic ancillary ligand have been modulated in this series of complexes (pyridine, 4-methoxy-pyridine or pyrimidine). X-ray diffraction studies have been performed on three complexes, revealing Pt(II) ions in a distorted square-planar geometrical environment with no Pt(II)⋯Pt(II) interactions but with moderate π–π interactions in the solid-state structure. Electrochemical and computational studies suggest a ligand-centered reduction on the diazine ligands with, in some cases, additional contribution from the azaheterocyclic ancillary ligand, whereas oxidation occurs on the Pt-phenyl ring substituent moieties. All complexes exhibit phosphorescence emission ranging from green to red/near-infrared, both in solution and in the solid state. Complexes bearing a 2-(3-methoxyphenyl)pyrimidine ligand show the best PLQY of the series, up to 52% in a CH2Cl2 solution and 20% in the solid state. Furthermore, the solid state PLQY of one of the near-infrared emitting phenylquinazoline complex has been found to be 6%.
Published: 2023
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13. Carbonylmetallates as versatile 2-, 4- or 6-Electron Donor Metalloligands in Transition-Metal Complexes and Clusters: A Global Approach

Author: Noura Naili, Samia Kahlal, Bachir Zouchoune, Jean‐Yves Saillard, Pierre Braunstein, Université de Constantine, 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 de coordination (LCC), 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), and We thank the CNRS and the MESR (Paris) for funding. N.N. and B.Z. are grateful to the Algerian DGRS-DT for financial support.
Subjects: metal-metal bonds, metal clusters, Organic Chemistry, Density functional theory, [CHIM]Chemical Sciences, metal carbonyl fragments, General Chemistry, electron counts, Catalysis
Abstract: International audience; Carbonylmetallates [m]-, such as [MoCp(CO)3]-, [Mn(CO)5]-, [Co(CO)4]-, have long been successfully used in the preparation of hundreds of metal carbonyl complexes and clusters, in particular of the heterometallic type. We focus here on situations where [m]- can be viewed as a terminal, doubly- or even triply-bridging metalloligand, developing metal-metal interactions with one, two or three metal centres M, respectively. With metals M from the groups 10-12, is not straightforward or even impossible to rationalize the structure of the resulting clusters by applying the well-known Wade-Mingos rules. A very simple but global approach is presented to rationalize structures not obeying usual electron-counting rules by considering the anionic building blocks [m]- as metalloligands behaving formally as potential 2, 4 or 6 electron donors, similarly to what is typically encountered with e.g. halido ligands. Qualitative and theoretical arguments using DFT calculations highlight similarities between seemingly unrelated metal complexes and clusters and also entails a predicting power with high synthetic potential.
Published: 2023
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14. Controlled Shell and Kernel Modifications of Atomically Precise Pd/Ag Superatomic Nanoclusters

Author: Yu‐Rong Ni, Michael N. Pillay, Tzu‐Hao Chiu, Ying‐Yann Wu, Samia Kahlal, Jean‐Yves Saillard, C. W. Liu, National Dong Hwa University (NDHU), 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 was supported by the National Science and Technology Council in Taiwan (111-2123-M-259-002) and the GENCI French National Computer Resource Center (grant A0030807367).
Subjects: [CHIM.THEO]Chemical Sciences/Theoretical and/or physical chemistry, dithiophosphate, Organic Chemistry, Superatom, General Chemistry, [CHIM.MATE]Chemical Sciences/Material chemistry, [CHIM.CATA]Chemical Sciences/Catalysis, Catalysis, palladium hydride, atomically precise nanoclusters
Abstract: International audience; The first 8-electron Pd/Ag superatomic alloys with an interstitial hydride [PdHAg19(dtp)12] (dtp = S2P(O i Pr)2-) 1 and [PdHAg20(dtp)12]+2 are reported. The targeted addition of a single Ag atom to 1 is achieved by the reaction of one equivalent of trifluoroacetic acid, resulting in the formation of 2 in 55% yield. Further modification of the shell results in the formation of [PdAg21(dtp)12]+3 via an internal redox reaction, with the system retaining an 8-electron superatomic configuration. The interstitial hydride in 1 and 2, contributes its 1s1 electron to the superatomic electron count, and occupies a PdAg3 tetrahedron. The distributions of isomers corresponding to different dispositions of the outer capping Ag atoms are investigated by multinuclear VT-NMR spectroscopy. The emissive state of 3 has a lifetime of 200 μs (λex =448; λem =842), while 1 and 2 are non-emissive. The catalytic reduction of 4-nitrophenol is demonstrated with 1-3 at room temperature.
Published: 2023
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15. From 8- to 18-Cluster Electrons Superatoms: Evaluation via DFT Calculations of the Ligand-Protected W@Au(12)(dppm)(6) Cluster Displaying Distinctive Electronic and Optical Properties

Author: Jianyu Wei, Desmond MacLeod Carey, Jean-François Halet, Samia Kahlal, Jean-Yves Saillard, Alvaro Muñoz-Castro, 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), Universidad Autonoma de Chile, National Institute for Materials Science (NIMS), Laboratory for Innovative Key Materials and Structures (LINK), Saint-Gobain-National Institute of Materials Science-Centre National de la Recherche Scientifique (CNRS), Universidad San Sebastian, The authors are grateful to the Chilean-French ECOS-CONYCYT program (Project C18E04, and ECOS180004) and the Chilean-French International Research Program 'IRP-CoopIC.' The GENCI (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. D.M.C. acknowledges support from FONDECYT-Chile grant 1221904. A.M.-C. acknowledges support from FONDECYT-Chile grant 1221676.
Subjects: Inorganic Chemistry, [CHIM.THEO]Chemical Sciences/Theoretical and/or physical chemistry, [CHIM.COOR]Chemical Sciences/Coordination chemistry, Physical and Theoretical Chemistry
Abstract: International audience; The iconic W@Au(12) icosahedral bare cluster reaches the favorable closed-shell superatomic electron configuration 1S(2) 1P(6) 1D(10), making it an 18-cluster electron (18-ce) superatom. Here, we pursue the evaluation of a ligand-protected counterpart based on the construction of a fully phosphine-protected [W@Au(12)(dppm)(6)] cluster strongly related to the characterized [Au(13)(dppm)(6)](5+) homometallic counterpart. The later cluster has the same total number of valence electrons as the former but is considered an 8-ce superatom with 1S(2) 1P(6) configuration. The fundamental differences between 8- and 18-ce species are investigated. The character of the frontier orbitals varies from 1P/1D in the 8-ce case to a 1D/ligand for 18-ce species, enabling an efficient charge transfer toward the ligands upon irradiation, being interesting for electron injection in optoelectronic devices and black absorbers applications. Excited-state properties are also revisited, showing different geometrical and electronic structure variations between 8- and 18-ce species. Moreover, the continuum between the 8- and 18-ce limits has been explored by varying the nature of the encapsulated dopant between group 6 and group 11. The transition between the 8- and 18-ce counts can be formally situated between Pt (8-ce) and Ir (18-ce). Thus, 18-ce derivatives obtained as doped counterparts of homometallic gold clusters can introduce useful alternatives to achieve different properties in related structural motifs, which can be further explored owing to their extension of the well-established versatility of current gold nanoclusters.
Published: 2023
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16. Experimental and Theoretical Evaluation of Four NLO‐Active Divalent Transition‐Metal Complexes Supported by an Enantiomerically Pure Tetradentate Schiff Base Ligand

Author: Salvador Celedón, Paul Hamon, Vania Artigas, Mauricio Fuentealba, Samia Kahlal, Isabelle Ledoux‐Rak, David Carrillo, Jean‐Yves Saillard, Carolina Manzur, Jean‐René Hamon, Universidad de Las Américas [Ecuador] (UDLA), 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), Pontificia Universidad Católica de Valparaíso (PUCV), Université Paris-Saclay, and Financial support from the Fondo Nacional de Desarrollo Científico y Tecnológico (FONDECYT), Chile (grant 1090310) and FONDEQUIP EQM130154 and EQM120095], the Vicerrectoría de Investigación y Estudios Avanzados, Pontificia Universidad Católica de Valparaíso, Chile (VRIEA-PUCV), the Centre National de la Recherche Scientifique (CNRS) and the Université de Rennes 1 is gratefully acknowledged. S.C. thanks VRIEA-PUCV for a postdoctoral financing.
Subjects: Inorganic Chemistry, Chiral Schiff bases, Nonlinear optics, density functional calculations, Transition metals, [CHIM.INOR]Chemical Sciences/Inorganic chemistry, X-ray diffraction
Abstract: International audience; This paper reports on a series of five chiral Schiff base push-pull compounds derived from enantiomerically pure (1R,2R)-(−)-1,2-diaminocyclohexane. The NiII, CuII, ZnII and PdII complexes supported by a ferrocene-containing unsymmetrically-substituted N2O2 quadridentate Schiff base ligand were prepared via template reactions and isolated in 74-87% yields. A combination of EA, IR, UV/vis and 1H/13C{1H} NMR spectroscopy, HRMS spectrometry, cyclic voltammetry and single-crystal X-ray analysis (for the proligand 2 and its NiII derivative 3), together with computational methods (DFT and TD-DFT) was used to fully characterize and study the properties of all products. Both 2 and 3 crystallize in the orthorhombic non-centrosymmetric space group P212121, with two (R,R)-(−)-chiral carbon atoms in their structure. Second-order nonlinear polarizabilities β have been measured by using Harmonic Light Scattering at 1.91 μm, with the Pd(II) species showing the higher NLO response of 460 x 10-30 esu.
Published: 2022
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17. Surface Modifications of eight-electron Pd/Ag Superatomic Alloys

Author: Subrat Barik, Chih-Yuan Chen, Tzu-Hao Chiu, Yu-Rong Ni, Franck Gam, Isaac Chantrenne, Samia Kahlal, Jean-Yves Saillard, and chen-wei liu
Abstract: Atomically precise thiolate-protected noble metal nanoclusters and their alloys are far more numerous than their selenium congeners, the synthesis of which remains extremely challenging. Herein, we account the synthesis of a series of atomically defined dithiophosph(in)ate protected eight-electron superatomic Pd/Ag nanoalloys [PdAg20{S2PR2}12], 2a-c (where R = OiPr, a; OiBu, b; Ph, c) via ligand exchange and/or co-reduction methods. The ligand exchange reaction on [PdAg20{S2P(OnPr)2}12], 1, with [NH4{Se2PR2}12] (where R = OiPr, or OnPr) leads to the formation of [PdAg20{Se2P(OiPr)2}12] (3) and [PdAg20{Se2P(OnPr)2}12] (4), respectively. Solid state structures of 2a, 2b, 3 and 4 unravel different PdAg20 metal frameworks from their parent cluster, originating from the different distributions of the eight-capping silver(I) atoms around a Pd@Ag12 centered icosahedron with C2, D3, Th and Th symmetries, respectively. Surprisingly ambient temperature crystallization of the reaction product 3 obtained by the ligand exchange reaction on 1 has resulted in the co-crystallization of two isomers in the unit cell with overall T (3a) and C3 (3b) symmetries, respectively. This is the first ever characterized isomeric pair among the selenolate-protected NCs. Density functional theory (DFT) studies further rationalize the preferred geometrical isomerism of the PdAg20 core.
Published: 2022
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18. On Heteronuclear Isoelectronic Alternatives to [Au13(dppe)5Cl2]3+: Electronic and Optical Properties of the 18-Electron Os@[Au12(dppe)5Cl2] Cluster from Relativistic Density Functional Theory Computations

Author: Jean-Yves Saillard, Jianyu Wei, Alvaro Muñoz-Castro, Jean-François Halet, P.L. Rodríguez-Kessler, and Samia Kahlal
Subjects: 010405 organic chemistry, Chemistry, Superatom, 010402 general chemistry, 01 natural sciences, Molecular physics, Homonuclear molecule, 0104 chemical sciences, Nanoclusters, Inorganic Chemistry, Heteronuclear molecule, Atom, Cluster (physics), Density functional theory, Molecular orbital, Physical and Theoretical Chemistry
Abstract: The development of well-defined atomically precise heteronuclear nanoclusters passivated by protecting ligands is presently a booming area, owing to the fact that doping well-known homonuclear nanostructures allows fine-tuning of their properties. Here, we explore by means of density functional theory calculations the possibility of doping the central gold atom in the classical [Au13(dppe)5Cl2]3+cluster (1) by Os. Although both [Au13(dppe)5Cl2]3+ and [Os@Au12(dppe)5Cl2] have the same total number of electrons, we show that they are not isoelectronic within the formalism of the superatom model, being respectively an 8- and an 18-electron species. It results that they exhibit similar structures but present significantly different optical behaviors (ultraviolet/visible and circular dichroism). Similar results are obtained for the Ru and Fe relatives. Emission properties indicate some redshift of the T1→S1 decay with respect to [Au13(dppe)5Cl2]3+, involving an equatorial distortion of the Au12Cl2 core in the T1 state, rather than the axial distortion afforded by 1. The sizable highest occupied molecular orbital-lowest unoccupied molecular orbital gaps found for the three doped species suggest that further experimental exploration of different stable doped species derived from the ligand-protected Au12Cl2 core should be encouraged.
Published: 2021
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19. Cyclometallated 2‐Phenylpyrimidine Derived Platinum Complexes: Synthesis and Photophysical Properties

Author: Samia Kahlal, Julien Boixel, Sylvain Achelle, Thierry Roisnel, Françoise Robin-le Guen, Jean-Yves Saillard, Mariia Hruzd, Sébastien Gauthier, Michaela Fecková, Filip Bureš, Pascal Le Poul, Institut des Sciences Chimiques de Rennes (ISCR), Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA), University of Pardubice, France Region Bretagne, Conseil Departemental des Cotes d'Armor, France, 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: Phosphorescence, 010405 organic chemistry, Chemistry, Ligand, Substituent, chemistry.chemical_element, Heterocycles, [CHIM.INOR]Chemical Sciences/Inorganic chemistry, 010402 general chemistry, Ring (chemistry), 01 natural sciences, 0104 chemical sciences, Inorganic Chemistry, Crystallography, chemistry.chemical_compound, N ligands, Pyrimidine, Absorption band, Pyridine, Platinum (II) complexes, [CHIM]Chemical Sciences, Platinum, HOMO/LUMO
Abstract: International audience; A series of five platinum (II) complexes based on 2-phenylpyrimidine ligands have been designed. Pyridine and chloride were used as auxiliary ligands. These complexes exhibit a slightly distorted square-planar geometry. The nature and position of substituent on the phenyl ring was thoroughly studied. The presence of an electron-donating substituent on the phenyl ring in the para position of the platinum atom leads to a red shift of the lowest-energy absorption band, which corresponds to the HOMO -> LUMO transition and permits to obtain phosphorescence in deoxygenated CH2Cl2 solution. All compounds are emissive in the solid state with a significant redshift for complexes bearing electron-donating substituent on the phenyl ring of phenylpyrimidine ligand.
Published: 2021
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20. Hydride-Containing Eight-Electron Pt/Ag Superatoms: Structure, Bonding, and Multi-NMR Studies

Author: Tzu-Hao Chiu, Jian-Hong Liao, Franck Gam, Ying-Yann Wu, Xiaoping Wang, Samia Kahlal, Jean-Yves Saillard, C. W. Liu, National Dong Hwa University (NDHU), 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), Institute of Chemistry [Taipei], Academia Sinica, Oak Ridge National Laboratory [Oak Ridge] (ORNL), UT-Battelle, LLC, Ministry of Science and Technology of Taiwan [MOST 109-2113-M-259-008], France-Taiwan ANR-MOST program [ANR-18-CE09-0037-01], GENCI French National Computer Resource Center [A0030807367], DOE Office of Science User Facility [DE-AC05-00OR22725], Academia Sinica Core Facility and Innovative Instrument Project [AS-CFII-111-214], and ANR-18-CE09-0037,Nanoalloys,Alliages superatomiques et de structure précise riches en argent et en cuivre(2018)
Subjects: [CHIM.THEO]Chemical Sciences/Theoretical and/or physical chemistry, Colloid and Surface Chemistry, [CHIM.COOR]Chemical Sciences/Coordination chemistry, General Chemistry, Biochemistry, Catalysis
Abstract: International audience; Recent reports on hydride-doped noble metal nanoclusters strongly suggest that the encapsulated hydride is a part of the superatom core, but no accurate location of the hydride could be experimentally proved, so far. We report herein a hydride-doped eight-electron platinum/silver alloy nanocluster in which the position of four-coordinated hydride was determined by neutron diffraction for the first time. X-ray structures of [PtHAg19(dtp/desp)(12)] (dtp = S2P((OPr)-Pr-n)(2), 1; dsep = Se2P((OPr)-Pr-i)(2), 2) describe a central platinum hydride (PtH) unit encapsulated within a distorted Ag-12 icosahedron, the resulting (PtH)@Ag-12 core being stabilized by an outer sphere made up of 7 capping silver atoms and 12 dichalcogenolates. Solid-state structures of 1 and 2 differ somewhat in the spatial configuration of their outer spheres, resulting in overall different symmetries, C-1 and C-3, respectively. Whereas the multi-NMR spectra of 2 in solution at 173 K reveal that the structure of C-3 symmetry is the predominant one, H-1 and Pt-195 NMR spectra of 1 at the same temperature disclose the presence of isomers of both C-1 and C-3 symmetry. DFT calculations found both isomers to be very close in energy, supporting the fact that they co-exist in solution. They also show that the [PtH@Ag-12](5+) kernel can be viewed as a closed-shell superatomic core, the mu(4)-hydride electron contributing to its eight-electron count. On the other hand, the 1s(H) orbital contributes only moderately to the superatomic orbitals, being mainly involved in the building of a Pt-H bonding electron pair with the 5d(z)(2)(Pt) orbital.
Published: 2022
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21. 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
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22. DFT Investigation of the η6 ⇌ η6-Inter-ring Haptotropic Rearrangement of the Group 8 Metals Complexes [(graphene)MCp]+ (M = Fe, Ru, Os)

Author: Yuri F. Oprunenko, Franck Gam, Igor P. Gloriozov, Nikolay S. Zhulyaev, Piotr I. Dem'yanov, Jean-Yves Saillard, Aleksey E. Kuznetsov, Mikhail S. Nechaev, Lomonosov Moscow State University (MSU), A.V. Topchiev Institute of Petrochemical Synthesis (TIPS), Russian Academy of Sciences [Moscow] (RAS), 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), Universidad Tecnica Federico Santa Maria [Valparaiso] (UTFSM), 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), 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: chemistry.chemical_classification, Fullerene, 010405 organic chemistry, Chemistry, Graphene, 010402 general chemistry, 01 natural sciences, Transition state, 0104 chemical sciences, Catalysis, law.invention, [CHIM.THEO]Chemical Sciences/Theoretical and/or physical chemistry, Crystallography, Hydrocarbon, Transition metal, law, Intramolecular force, [CHIM]Chemical Sciences, [CHIM.COOR]Chemical Sciences/Coordination chemistry, Density functional theory, Physical and Theoretical Chemistry
Abstract: International audience; Metalcyclopentadienyl complexes (MCp) (M = Fe, Ru, Os) bound to the large polyaromatic hydrogenated hydrocarbon (PAH) CH used as a model for pristine graphene have been studied using a density functional theory (DFT) generalized gradient approximation (PBE functional) to reveal their structural features and dynamic behavior. The inter-ring haptotropic rearrangements (IRHRs) for these complexes were shown to occur via two transition states and one intermediate. The energy barriers of the η ⇌ η IRHRs of the (MCp) unit were found to be 30, 27, and 29 kcal/mol for M = Fe, Ru, and Os, respectively. These values are significantly lower than the values found previously for smaller PAHs. Both polar and nonpolar solvents were found not to affect significantly the energy barrier heights. Investigated transition metal complexes could be used in general as catalysts in the design of novel derivatives or materials with promising properties. Metalcyclopentadienyl complexes (MCp) of PAHs show catalytic properties mainly due to their structural details as well as their important characteristic of inter-ring haptotropic rearrangement. IRHRs take place usually by intramolecular mechanisms. During IRHRs, the ML organometallic groups (OMGs) undergo shifting along the PAH plane and could coordinate additional reagents, which is important for catalysis. Large PAHs such as graphene, fullerenes, and nanotubes possess intrinsic anticancer activity, and numerous arene complexes of Ru and Os have been proven to have anticancer properties as well. We suppose that coordinating Ru or Os to very large PAHs could synergistically increase the anticancer activity of resulting complexes.
Published: 2020
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23. Polyhydrido Copper Nanoclusters with a Hollow Icosahedral Core: [Cu 30 H 18 {E 2 P(OR) 2 } 12 ] (E=S or Se; R= n Pr, i Pr or i Bu)

Author: Chun‐Yen Wu, Tzu-Hao Chiu, Shou‐Chih Huo, Jean-Yves Saillard, Xiaoping Wang, Jian-Hong Liao, Subrat Kumar Barik, Chen-Wei Liu, and Samia Kahlal
Subjects: 010405 organic chemistry, Chemistry, Icosahedral symmetry, Ligand, Hydride, Organic Chemistry, Neutron diffraction, chemistry.chemical_element, General Chemistry, 010402 general chemistry, 01 natural sciences, Copper, Catalysis, Square pyramidal molecular geometry, 0104 chemical sciences, Crystallography, Single displacement reaction, Bimetallic strip
Abstract: Although atomically precise polyhydrido copper nanoclusters are of prime interest for a variety of applications, they have so far remained scarce. Herein, this work describes the synthesis of a dithiophosphate-protected copper(I) hydride-rich nanocluster (NC), [Cu30 H18 {S2 P(OnPr)2 }12 ] (1H ), fully characterized by various spectroscopic methods and single-crystal X-ray diffraction. The X-ray structure of 1H reveals an unprecedented central Cu12 hollow icosahedron. Six faces of this icosahedron are capped by Cu3 triangles, the whole Cu30 core being wrapped by twelve dithiophosphate ligands and the whole cluster has ideal S6 symmetry. The locations of the 18 hydrides in 1H were ascertained by a single-crystal neutron diffraction study. They are composed of three types: capping μ3 -H, interstitial μ4 -H (seesaw) and μ5 -H ligands (square pyramidal), in good agreement with the DFT simulations. The numbers of hydrides and ligand resonances in the 1 H NMR spectrum of 1H are in line with their coordination environment in the solid state, retaining the S6 symmetry in solution. Furthermore, two new Se-protected polyhydrido copper nanoclusters, [Cu30 H18 {Se2 P(OR)2 }12 ] (2H : R=iPr 3H : R=iBu) were synthesized from their sulfur relative 1H via ligand displacement reaction and their X-ray structures feature the exceptional case where both the NC shape and size are fully conserved during the course of ligand exchange. DFT and TD-DFT calculations allow understanding the bonding and optical properties of clusters 1H -3H . In addition, the reaction of 1H with [Pd(PPh3 )2 Cl2 ] in the presence of terminal alkynes led to the formation of new bimetallic Cu-Pd alloy clusters [PdCu14 H2 {S2 P(OnPr)2 }6 (C≡CR)6 ] (4: R=Ph; 5: R=C6 H4 F).
Published: 2020
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24. Electron count and electronic structure of bare icosahedral Au32and Au33ionic nanoclusters and ligated derivatives. Stable models with intermediate superatomic shell fillings

Author: Alvaro Muñoz-Castro, Jean-François Halet, Qi Wang, Samia Kahlal, and Jean-Yves Saillard
Subjects: Materials science, Passivation, 010405 organic chemistry, Ligand, Icosahedral symmetry, Shell (structure), General Physics and Astronomy, Ionic bonding, Electronic structure, 010402 general chemistry, 01 natural sciences, 0104 chemical sciences, Nanoclusters, Crystallography, Cluster (physics), Physical and Theoretical Chemistry
Abstract: DFT calculations were carried out on bare Au32 and Au33 nanoclusters with various charges, in order to analyze their stability with respect to different cluster electron numbers. Results indicate that in addition to the neutral Au32 hollow species, significant HOMO–LUMO gaps are computed for [Au32]8+ (hollow) and [Au32]4+ (two-shell structure). Species with smaller HOMO–LUMO gaps can reach stability upon “passivation” by a ligand shell, as experimentally exemplified. Icosahedral frameworks of Ih or lower symmetry are favored for the cationic nanoclusters whereas different structures are computed for the anionic ones.
Published: 2020
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25. Insight Into the Stability and Electronic and Optical Properties of N-Heterocyclic Carbene Analogues of Halogen/Phosphine-Protected Au-13 Superatomic Clusters

Author: Jianyu Wei, Samia Kahlal, Jean-François Halet, Jean-Yves Saillard, Alvaro Muñoz-Castro, Institut des Sciences Chimiques de Rennes (ISCR), Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), National Institute for Materials Science (NIMS), Laboratory for Innovative Key Materials and Structures (LINK), Saint-Gobain-National Institute of Materials Science-Centre National de la Recherche Scientifique (CNRS), Universidad Autonoma de Chile, Chilean-French ECOSCONYCYT Program [C18E04], French Chilean International Associated Laboratory for \'Multifunctional Molecules and Materials\' (LIA-CNRS) [1027], GENCI (Grand Equipment National de Calcul Intensif) [a0010807367], China Scholarship Council China Scholarship Council, and FondecytComision Nacional de Investigacion Cientifica y Tecnologica (CONICYT) CONICYT FONDECYT [1180683]
Subjects: [CHIM]Chemical Sciences, Physical and Theoretical Chemistry
Abstract: International audience; Atomically precise gold nanoclusters (AuNCs) belong to a relevant area oflering useful templates with tunable properties toward functional nanostructures. In this work, we explored the feasible incorporation of N-heterocyclic carbenes (NHCs), as part of the protecting-ligand shell in AuNCs. Our results, which are based on the substitution of phosphine ligands in experimentally characterized AuNCs by NHCs in various eight-electron superatoms Au-13 and M4Au9 (M = Cu, Ag), indicate similar electronic structure and stability but somewhat diflerent optical properties. These findings support the feasible obtention of novel targets for explorative synthetic eflorts featuring NHC ligands on medium-sized species based on the recurrent Au-13 icosahedral core. The hypothetical species appear to be interesting templates for building blocks in nanostructured materials with tuned properties, which encourage experimental exploration of ligand versatility in homo-and heterometallic superatomic clusters.
Published: 2022
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26. Luminescent cyclometalated alkynylplatinum(ii) complexes with 1,3-di(pyrimidin-2-yl)benzene ligands: synthesis, electrochemistry, photophysics and computational studies

Author: Mariia Hruzd, Nicolas le Poul, Marie Cordier, Samia Kahlal, Jean-Yves Saillard, Sylvain Achelle, Sébastien Gauthier, Françoise Robin-le Guen, 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, Electrochimie Moléculaires et Chimie Analytique (CEMCA), Université de Brest (UBO)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut Brestois Santé Agro Matière (IBSAM), Université de Brest (UBO), Region Bretagne, France Region Bretagne, and Conseil Departemental des Cotes d'Armor, France
Subjects: Inorganic Chemistry, [CHIM.THEO]Chemical Sciences/Theoretical and/or physical chemistry, [CHIM.COOR]Chemical Sciences/Coordination chemistry
Abstract: International audience; In this article, we report on a series of cyclometalated chloro- and alkynyl-platinum(ii) complexes bearing various tridentate NCN-cyclometalated ligands derived from 1,3-bis(pyrimidin-2-yl)benzene. The X-ray crystal structures of two alkynyl-platinum(ii) complexes were determined and other structures were DFT-calculated. Electrochemical and DFT-computational studies suggest a ligand-centred reduction on the R-1-substituted NCN ligand, whereas oxidation likely occurs either on the Pt-phenylacetylide moiety and/or the cyclometalated ligand. In CH2Cl2 solution at room temperature, the complexes show phosphorescent emissions ranging from green to orange, depending on the R-1 and R-2 substituents on the ligands. In KBr solid state matrix, excluding complexes bearing a trifluoromethyl substituted ligand, all compounds exhibit red emission. The presence of an alkynyl ancillary ligand has limited influence on absorption and emission spectra except in the case of the complex with the strongly electron-donating diphenylamino R-2 substituent on the alkynyl ligand, for which a significant red-shift was observed. The alkynyl Pt(ii) complex with OMe groups as both R-1 and R-2 substituents shows the best emission quantum yield (0.81 in CH2Cl2 solution) in this series. The full series of DFT calculated band gaps correlated generally well with the electrochemical and absorption data and reasonably model the impact of the substituents on the electronics of these complexes.
Published: 2022
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27. Non-covalent interactions in hexanuclear polyoxidometalates [V(6)(IV)B(20)O(50)H8](8-) An experimental and theoretical approach

Author: Eric Le Fur, Kerry Wrighton-Araneda, Karina Muñoz-Becerra, Jean-Yves Saillard, Olivier Cador, Verónica Paredes-García, Samia Kahlal, Diego Venegas-Yazigi, Universidad de Santiago de Chile [Santiago] (USACH), University of Aconcagua, Partenaires INRAE, Universidad Tecnológica Metropolitana (UTEM), 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), Centro para el Desarrollo de la Nanociencia y Nanotecnología (CEDENNA), Universidad Andrés Bello [Santiago] (UNAB), FONDECYT Comision Nacional de Investigacion Cientifica y Tecnologica (CONICYT) CONICYT FONDECYT [1201249, 3180509], Financiamiento Basal Comision Nacional de Investigacion Cientifica y Tecnologica (CONICYT) CONICYT PIA/BASAL [AFB180001], FONDEQUIP [EQM140060, EQM130086], Chilean-French International Associated laboratory \'Multi-functional Molecules and Materials\' (LIA M3-CNRS) [1207], 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: Non-covalent interactions, 02 engineering and technology, 010402 general chemistry, Ring (chemistry), DFT calculations, 01 natural sciences, Spectral line, Inorganic Chemistry, Magnetic properties, Materials Chemistry, Polyoxidometalates, [CHIM]Chemical Sciences, Absorption (logic), Physical and Theoretical Chemistry, chemistry.chemical_classification, Chemistry, Charge (physics), Chromophore, 021001 nanoscience & nanotechnology, Coupling (probability), 0104 chemical sciences, Crystallography, Spectroscopic properties, 0210 nano-technology, Energy (signal processing)
Abstract: International audience; A complete study of the optical and magnetic properties of three new {V6-type} polyoxidometalates (NH3CH2CH2CH2NH3)(4){V6B20O50H8}center dot 4H(2)O 1, K-2(NH3CH2CH2NH3)(2.5)(NH3CH2CH2NH2){V6B20O50H8}center dot 2H(2)O 2, and K-2(NH3CH2CH2CH2NH3)(2)(H3O)(2){V(6)B(20)O(5)0H(8)}center dot 8H(2)O 3 is presented. Using TD-DFT calculations, the assignment of the experimental UV-Visible spectra was established with four absorption bands: a higher in energy assigned to metal-to-metal charge transfer and the remaining associated principally to d-d transitions, demonstrating that the {(V6O18)-O-IV}(12-) ring is the principal chromophore for these systems and that the surrounding packing does not have an influence on it. On the other hand, the differences observed in the magnetic properties are caused by the influence of the non-covalent interactions between the potassium ions with some oxygen atoms of the V-IV coordination spheres, thus modifying the V-IV-V-IV exchange coupling. This effect was demonstrated using a simplified binuclear DFT model that predicts a higher V-IV-V-IV antiferromagnetic coupling when the K cations become closer to the oxygen bridge atoms that link the VIV centres of the {(V6O18)-O-IV}(12-) ring.
Published: 2022
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28. Alloying dichalcogenolate-protected Ag

Author: Franck, Gam, Isaac, Chantrenne, Samia, Kahlal, Tzu-Hao, Chiu, Jian-Hong, Liao, C W, Liu, and Jean-Yves, Saillard
Abstract: The isoelectronic doping of dichalcogenolato nanoclusters of the type [Ag
Published: 2021

29. Innentitelbild: Reactivities of Interstitial Hydrides in a Cu 11 Template: En Route to Bimetallic Clusters (Angew. Chem. 2/2022)

Author: Rhone P. Brocha Silalahi, Qi Wang, Jian‐Hong Liao, Tzu‐Hao Chiu, Ying‐Yann Wu, Xiaoping Wang, Samia Kahlal, Jean‐Yves Saillard, and C. W. Liu
Subjects: General Medicine
Published: 2021
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30. Inside Cover: Reactivities of Interstitial Hydrides in a Cu 11 Template: En Route to Bimetallic Clusters (Angew. Chem. Int. Ed. 2/2022)

Author: Rhone P. Brocha Silalahi, Qi Wang, Jian‐Hong Liao, Tzu‐Hao Chiu, Ying‐Yann Wu, Xiaoping Wang, Samia Kahlal, Jean‐Yves Saillard, and C. W. Liu
Subjects: General Chemistry, Catalysis
Published: 2021
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31. C-H and Si-H Activation Reactions at Ru/Ga Complexes: A Combined Experimental and Theoretical Case Study on the Ru-Ga Bond

Author: Maximilian Muhr, Raphael Bühler, Hao Liang, Jonas Gilch, Christian Jandl, Samia Kahlal, Jean‐Yves Saillard, Christian Gemel, Roland A. Fischer, Technische Universität München = Technical University of Munich (TUM), 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 was funded by the German Research Foundation (DFG) within a Reinhard Koselleck Project (FI-502/44-1), the TUM Graduate School and the GENCI French national computer resource center (grant A0030807367). H.L. thanks the China Scholarship Council for a Ph.D. grant.
Subjects: Density functional calculations, Mass spectrometry, Intermetallic compounds, Organic Chemistry, [CHIM]Chemical Sciences, Bond Activation, General Chemistry, Research Article, Research Articles, bond activation, cluster intermediates, density functional calculations, intermetallic compounds, mass spectrometry, Cluster intermediates, Catalysis, ddc
Abstract: International audience; Treatment of [Ru(COD)(MeAllyl) 2 ] and [Ru(COD)(COT)] with GaCp* under hydrogenolytic conditions leads to reactive intermediates which activate Si-H or C-H bonds, respectively. The product complexes [Ru(GaCp*) 3 (SiEt 3 )H 3 ] ( 1 ) and [Ru(GaCp*) 3 (C 7 H 7 )H 3 ] ( 2 ) are formed with HSiEt 3 or with toluene as the solvent, respectively. While 1 was isolated and fully characterized by NMR, MS, IR and SC-XRD, 2 was too labile to be isolated and was observed and characterized in-situ by using mass spectrometry, including labelling experiments for the unambiguous assignment of the elemental composition. The structural assignment was confirmed by DFT computations. The relative energies of the four isomers possible upon toluene activation at the ortho -, meta -, para - and CH 3 -positions have been determined and point to aromatic C-H activation. The Ru-Ga bond was analyzed by EDA and QTAIM and compared to the Ru-P bond in the analogue phosphine compound. Bonding analyses indicate that the Ru-GaCp* bond is weaker than the Ru-PR 3 bond.
Published: 2021
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32. Reactivities of Interstitial Hydrides in a Cu

Author: Rhone P Brocha, Silalahi, Qi, Wang, Jian-Hong, Liao, Tzu-Hao, Chiu, Ying-Yann, Wu, Xiaoping, Wang, Samia, Kahlal, Jean-Yves, Saillard, and C W, Liu
Abstract: In sharp contrast to surface hydrides, reactivities of interstitial hydrides are difficult to explore. When treated with a metal ion (Cu
Published: 2021

33. Bonding analysis in ytterbium(II) distannyl and related tetryls

Author: Jean-François Carpentier, Yann Sarazin, Jean-Yves Saillard, Peter M. Chapple, Marie Cordier, Julien Cartron, Ghanem Hamdoun, Samia Kahlal, Hassan Oulyadi, 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), Euromed University Fez, Chimie Organique et Bioorganique : Réactivité et Analyse (COBRA), Institut de Chimie Organique Fine (IRCOF), Université de Rouen Normandie (UNIROUEN), Normandie Université (NU)-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)-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 Normand de Chimie Moléculaire Médicinale et Macromoléculaire (INC3M), Université de Caen Normandie (UNICAEN), Normandie Université (NU)-Normandie Université (NU)-École Nationale Supérieure d'Ingénieurs de Caen (ENSICAEN), Normandie Université (NU)-Université Le Havre Normandie (ULH), Normandie Université (NU)-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)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université de Caen Normandie (UNICAEN), 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)-Centre National de la Recherche Scientifique (CNRS), P.M.C thank the Agence Nationale de la Recherche for the provision of a research grant (ANR-17-CE07-0017-01). The GENCI (Grand Equipment National de Calcul Intensif) is acknowledged for HPC resources (Project A0050807367). H.O. and G.H. would like to thank the Region Normandie, Rouen University, CNRS, INSA of Rouen, ERDF and the Labex SynOrg (ANR-11-LABX-0029)., ANR-17-CE07-0017,POLCADE,Polymères siliconés par catalyse de couplages déshydrogénants(2017), ANR-11-LABX-0029,SYNORG,Synthèse Organique : des molécules au vivant(2011), Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA), Institut Normand de Chimie Moléculaire Médicinale et Macromoléculaire (INC3M), Institut de Chimie du CNRS (INC)-École Nationale Supérieure d'Ingénieurs de Caen (ENSICAEN), Institut National des Sciences Appliquées (INSA)-Normandie Université (NU)-Institut National des Sciences Appliquées (INSA)-Université Le Havre Normandie (ULH), Normandie Université (NU)-Centre National de la Recherche Scientifique (CNRS)-Université de Caen Normandie (UNICAEN), Normandie Université (NU)-Institut de Chimie du CNRS (INC)-École Nationale Supérieure d'Ingénieurs de Caen (ENSICAEN), Normandie Université (NU)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie Organique Fine (IRCOF), and Institut National des Sciences Appliquées (INSA)-Normandie Université (NU)-Institut National des Sciences Appliquées (INSA)-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS)
Subjects: Ytterbium, Materials science, 010405 organic chemistry, Ionic bonding, chemistry.chemical_element, Nuclear magnetic resonance spectroscopy, 010402 general chemistry, 01 natural sciences, 0104 chemical sciences, Inorganic Chemistry, chemistry.chemical_compound, Crystallography, Atomic orbital, chemistry, Covalent bond, [CHIM]Chemical Sciences, Derivative (chemistry), Electronic properties
Abstract: International audience; The syntheses of the ytterbium(II) distannyl [Yb{Sn(SiMe(3))(3)}(2)·(thf)(4)] (Yb-Sn) and of its digermyl analogue [Yb{Ge(SiMe(3))(3)}(2)·(thf)(3)] (Yb-Ge) are presented. The compounds were characterised by multinuclear high-resolution solution NMR spectroscopy, including (171)Yb NMR, and by X-ray diffraction crystallography. The bonding and electronic properties of the two complexes, along with those of the known ytterbium(II) disilyl derivative [Yb{Si(SiMe(3))(3)}(2)·(thf)(3)] (Yb-Si) and those of the congeneric calcium distannyl [Ca{Sn(SiMe(3))(3)}(2)·(thf)(4)] (Ca-Sn), were investigated in detail by DFT calculations. This analysis points at a primarily ionic Yb-tetrel bonding, with a small covalent contribution, attributed principally to the 5d(Yb) participation. This weak covalent character is found to be larger for the distannyl Yb-Sn than for its lighter Si- and Ge-derivatives. The covalent component is also found to be greater in Yb-Sn than in Ca-Sn, due to the availability of the 5d(Yb) orbitals for bonding.
Published: 2021
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34. Nickel(II)-Based Building Blocks with Schiff Base Derivatives: Experimental Insights and DFT Calculations

Author: Samia Kahlal, Jean Yves Saillard, Jean René Hamon, Thierry Roisnel, Néstor Novoa, David Carrillo, Carolina Manzur, Universidad de Concepción - University of Concepcion [Chile], Pontificia Universidad Católica de Valparaíso (PUCV), 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), Fondo Nacional de Desarrollo Cientifico y Tecnologico [FONDECYT (Chile)] Comision Nacional de Investigacion Cientifica y Tecnologica (CONICYT) CONICYT FONDECYT [1190034], GENCI French national computer center [a0090807367], Universidad de Concepción [Chile], Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), and Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA)
Subjects: Materials science, Dimer, Pharmaceutical Science, chemistry.chemical_element, Sonogashira coupling, Organic chemistry, Schiff base complexes, 010402 general chemistry, DFT calculations, 01 natural sciences, Article, Analytical Chemistry, Sonogashira cross coupling, chemistry.chemical_compound, nickel, QD241-441, Drug Discovery, [CHIM]Chemical Sciences, Physical and Theoretical Chemistry, Schiff base, 010405 organic chemistry, Ligand, Nuclear magnetic resonance spectroscopy, X-ray crystal structure, 0104 chemical sciences, Nickel, Crystallography, chemistry, Chemistry (miscellaneous), Molecular Medicine, Density functional theory, Ternary operation
Abstract: We have recently reported a series of neutral square planar tridentate Schiff base (L) complexes of the general formula [(L)M(py)], showing relatively high first-order hyperpolarizabilities and NLO redox switching behavior. In the present study, new members of this family of compounds have been prepared with the objective to investigate their potential as building blocks in the on-demand construction of D-π-A push–pull systems. Namely, ternary nickel(II) building blocks of general formula [(LA/D)Ni(4-pyX)] (4–7), where LA/D stands for an electron accepting or donating dianionic O,N,O-tridentate Schiff base ligand resulting from the monocondensation of 2-aminophenol or its 4-substituted nitro derivative and β-diketones R-C(=O)CH2C(=O)CH3 (R = methyl, anisyl, ferrocenyl), and 4-pyX is 4-iodopyridine or 4-ethynylpyridine, were synthesized and isolated in 60–78% yields. Unexpectedly, the Sonogashira cross-coupling reaction between the 4-iodopyridine derivative 6 and 4-ethynylpyridine led to the formation of the bis(4-pyridyl) acetylene bridged centrosymmetric dimer [{(LD)Ni}2(µ2-py-C≡C-py)] (8). Complexes 4–8 were characterized by elemental analysis, FT-IR and NMR spectroscopy, single crystal X-ray diffraction and computational methods. In each compound, the four-coordinate Ni(II) metal ion adopts a square planar geometry with two nitrogen and two oxygen atoms as donors occupying trans positions. In 8, the Ni…Ni separation is of 13.62(14) Å. Experimental results were proved and explained theoretically exploiting Density Functional Theory calculations.
Published: 2021
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35. Doping effect on the structure and properties of eight-electron silver nanoclusters

Author: Jian-Hong Liao, Franck Gam, Tzu-Hao Chiu, Chen-Wei Liu, Jean-Yves Saillard, Samia Kahlal, Yu-Jie Zhong, National Dong Hwa University (NDHU), 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), This work was supported by the Ministry of Science and Technology of Taiwan (MOST, Grant Nos. 109-2113-M-259-008 and 108-2923-M-259-001), the France–Taiwan ANR-MOST program (project Nanoalloys), and the GENCI French national computer resource center (Grant No. A0090807367)., ANR-18-CE09-0037,Nanoalloys,Alliages superatomiques et de structure précise riches en argent et en cuivre(2018), 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: [PHYS]Physics [physics], Materials science, Absorption spectroscopy, 010405 organic chemistry, Metal ions in aqueous solution, Doping, General Physics and Astronomy, chemistry.chemical_element, 010402 general chemistry, 01 natural sciences, Copper, 0104 chemical sciences, Ion, Nanoclusters, [CHIM.THEO]Chemical Sciences/Theoretical and/or physical chemistry, Crystallography, chemistry, [CHIM]Chemical Sciences, Physical and Theoretical Chemistry, Absorption (chemistry), Bimetallic strip
Abstract: International audience; The bimetallic M(20) and M(21) compounds, {[Cu(3)Ag(17){S(2)P(O(i)Pr)(2)}(12)](0.5) [Cu(4)Ag(16){S(2)P(O(i)Pr)(2)}(12)](0.5)} ({[1a](0.5)[1b](0.5)}) and [Cu(4)Ag(17){S(2)P(O(i)Pr)(2)}(12)](PF(6)) (2), have been structurally characterized, in which the Cu(I) ions are randomly distributed on the eight outer positions capping the eight-electron [Ag(13)](5+) core. DFT calculations show that the statistical disorder results from the nearly neutral preference of copper to occupy any of the eight outer positions. Surprisingly, the UV-Vis absorption spectra of the M(20) and M(21) bimetallic nanoclusters display an almost identical absorption profile as that of their homometallic [Ag(20){S(2)P(O(i)Pr)(2)}(12)] and [Ag(21){S(2)P(O(i)Pr)(2)}(12)](+) relatives. This is rationalized by TD-DFT calculations, which show that the frontier orbitals of such eight-electron alloys are largely independent from the nature of the capping metal ions. A blue-shifted absorption is observed upon replacing by Au the central Ag atom in 2, forming the trimetallic compound [Cu(4)AuAg(16){S(2)P(O(i)Pr)(2)}(12)](PF(6)) (3).
Published: 2021
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36. Homoleptic Platinum/Silver Superatoms Protected by Dithiolates: Linear Assemblies of Two and Three Centered Icosahedra Isolobal to Ne2 and I3–

Author: Isaac Chantrenne, Jean-Yves Saillard, Samia Kahlal, C. W. Liu, Tzu-Hao Chiu, Jian-Hong Liao, and Franck Gam
Subjects: 010405 organic chemistry, Chemistry, chemistry.chemical_element, Isolobal principle, General Chemistry, 010402 general chemistry, 01 natural sciences, Biochemistry, Catalysis, 3. Good health, 0104 chemical sciences, Nanoclusters, chemistry.chemical_compound, Crystallography, Colloid and Surface Chemistry, Dipropyl dithiophosphate, Cluster (physics), Homoleptic, Platinum, Bimetallic strip
Abstract: Three bimetallic platinum/silver nanoclusters, PtAg20(dtp)12 (1), Pt2Ag33(dtp)17 (2), and Pt3Ag44(dtp)22 (3) (dtp: dipropyl dithiophosphate), with cluster electron counts of 8, 16, and 22, respecti...
Published: 2019
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37. DFT study of inter-ring haptotropic rearrangement in CpRu+ complexes of polycyclic aromatic ligands

Author: Franck Gam, Kirill V. Zaitsev, Mikhail S. Nechaev, Jean-Yves Saillard, Yuri F. Oprunenko, Igor P. Gloriozov, Lomonosov Moscow State University (MSU), A.V. Topchiev Institute of Petrochemical Synthesis (TIPS), Russian Academy of Sciences [Moscow] (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), Region Bretagne [ARED NANOCLU 9334], 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: Activation energy, DFT calculations, 010402 general chemistry, Ring (chemistry), 01 natural sciences, Biochemistry, law.invention, Catalysis, Inorganic Chemistry, chemistry.chemical_compound, Transition metal, law, Computational chemistry, Materials Chemistry, [CHIM.COOR]Chemical Sciences/Coordination chemistry, Physical and Theoretical Chemistry, inter-ring haptotropic rearrangement, Naphthalene, 010405 organic chemistry, Chemistry, Graphene, Organic Chemistry, Ruthenium complexes of polyaromatics, 0104 chemical sciences, 3. Good health, [CHIM.THEO]Chemical Sciences/Theoretical and/or physical chemistry, Organometallic complexes of graphene
Abstract: International audience; Inter-ring haptotropic rearrangements (IRHRs) of different types are well-known phenomena in organometallic and catalytic chemistry. So far, they are reported for transition metal complexes with carbo-and heterocyclic polyaromatic hydrocarbons (PAH) of small and medium size. Here, we report DFT studies of RuCp+ shifts between neighboring six-membered rings (eta(6) reversible arrow eta(6)-IRHR) on an extra-large PAH as a model for graphene and compare it to naphthalene. Our calculations predict that eta(6) reversible arrow eta(6)-IRHRs proceed with much lower activation energy barrier of rearrangement in the case of the RuCp+ complex of eta(6)-graphene model.
Published: 2019
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38. Synthesis of Bimetallic Copper‐Rich Nanoclusters Encapsulating a Linear Palladium Dihydride Unit

Author: Kiran Kumarvarma Chakrahari, Rhone P. Brocha Silalahi, Tzu‐Hao Chiu, Xiaoping Wang, Nadia Azrou, Samia Kahlal, Yu‐Chiao Liu, Ming‐Hsi Chiang, Jean‐Yves Saillard, and C. W. Liu
Subjects: General Medicine
Published: 2019
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39. Organometallic chemistry of new carbon materials. Structure and dynamic behavior of group 6 metal tricabonyl complexes of graphene and perforated graphene: a DFT study

Author: N. S. Zhulyaev, Yu. F. Oprunenko, Mikhail S. Nechaev, Jean-Yves Saillard, Franck Gam, Igor P. Gloriozov, Lomonosov Moscow State University (MSU), A.V. Topchiev Institute of Petrochemical Synthesis (TIPS), Russian Academy of Sciences [Moscow] (RAS), 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), Alexander von Humboldt-Stiftung, 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_element, 02 engineering and technology, 010402 general chemistry, 01 natural sciences, Catalysis, law.invention, metal tricarbonyl complexes, Metal, interring haptotropic rearrangements 2, chemistry.chemical_compound, Chromium, PAHs, law, Materials Chemistry, [CHIM.COOR]Chemical Sciences/Coordination chemistry, density functional theory, Organometallic chemistry, Graphene, graphene, General Chemistry, 021001 nanoscience & nanotechnology, Coronene, 0104 chemical sciences, [CHIM.THEO]Chemical Sciences/Theoretical and/or physical chemistry, chemistry, visual_art, Kekulene, visual_art.visual_art_medium, Physical chemistry, Density functional theory, 0210 nano-technology, Carbon
Abstract: International audience; The mechanism of inter-ring haptotropic rearrangements (IRHRs) was investigated by DFT for the tricarbonyl eta(6)-complexes of group 6 metals (M = Cr, Mo, W) of coronene (I-M), kekulene (II-M) and a model graphene (III-M). The computed eta(6),eta(6)-IRHR activation barriers in the middle size PAHs I-M and II-M were calculated to be substantially lower than those in the case of complexes of relatively small size PAHs such as naphthalene chromium tricarbonyl (Delta G approximate to 20-25 kcal mol(-1)vs. approximate to 30 kcal mol(-1)). The barrier is further lowered in the case of the model graphene complex III-Cr (Delta G approximate to 13 kcal mol(-1)). An even lower barrier is found for III-Mo (Delta G approximate to 10 kcal mol(-1)), whereas it slightly increases for III-W (Delta G approximate to 14 kcal mol(-1)).
Published: 2019
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40. Potential to stabilize 16-vertex tetrahedral coinage-metal cluster architectures related to Au20

Author: Ramiro Arratia-Pérez, Franck Gam, Alvaro Muñoz-Castro, Samia Kahlal, Jean-Yves Saillard, Universidad Andrés Bello [Santiago] (UNAB), 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), Universidad Autonoma de Chile, Chilean-French International Associated Laboratory for 'Multifunctional Molecules and Materials' (LIA-CNRS) [1027], FONDECYT [1180683, 1140359, 1150629], MILLENNIUM Project [RC12001], GENCI French national computer resource [a0010807367], Region Bretagne (ARED NANOCLU) [9334], Universidad Andres Bello, 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 Universidad Andrés Bello - UNAB (CHILE)
Subjects: Materials science, Jellium, General Physics and Astronomy, 02 engineering and technology, 010402 general chemistry, 021001 nanoscience & nanotechnology, 01 natural sciences, Redox, Homonuclear molecule, 0104 chemical sciences, Vertex (geometry), Metal, Crystallography, Heteronuclear molecule, visual_art, Tetrahedron, Cluster (physics), visual_art.visual_art_medium, [CHIM]Chemical Sciences, Physical and Theoretical Chemistry, 0210 nano-technology, ComputingMilieux_MISCELLANEOUS
Abstract: DFT calculations were carried out on a series of tetrahedral 16-atom superatomic clusters having 20 or 18 jellium electrons (je) and structurally related to Au20, namely, [M16]4−/2− (M = Cu, Ag, and Au) and [M4′M12′′]0/2+ (M′ = Zn, Cd, Hg; M′′ = Cu, Ag, Au). While the bare homonuclear 20-je species required further stabilization to be isolated, their 18-je counterparts exhibited better stability. Lowering the electron count led to structural modification from a compact structure (20-je) to a hollow sphere (18-je). Such a change could be potentially controlled by tuning redox properties. Among the 20-je heteronuclear [M4′M12′′] neutral series, [Zn4Au12] appeared to meet the best stability criteria, but their 18-je relatives [M4′M12′′]+, in particular [Zn4Cu12]2+ and [Cd4Au12]2+, offered better opportunities for obtaining stable species. Such species exhibit the smallest models for the M(111) surface of fcc metals, which expose designing rules towards novel high-dopant-ratio clusters as building blocks of nanostructured materials.
Published: 2019
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41. Redox-switching of ternary Ni(<scp>ii</scp>) and Cu(<scp>ii</scp>) complexes: synthesis, experimental and theoretical studies along with second-order nonlinear optical properties

Author: Carolina Manzur, Françoise Robin-le Guen, Samia Kahlal, Jean-René Hamon, Jean-Yves Saillard, Thierry Roisnel, Isabelle Ledoux-Rak, Néstor Novoa, Nolwenn Cabon, Vincent Dorcet, David Carrillo, Universidad de Concepción [Chile], Pontificia Universidad Católica de Valparaíso (PUCV), Institut des Sciences Chimiques de Rennes (ISCR), Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA), Laboratoire de Photonique Quantique et Moléculaire (LPQM), École normale supérieure - Cachan (ENS Cachan)-CentraleSupélec-Centre National de la Recherche Scientifique (CNRS), Fondo Nacional de Desarrollo Cientifico y Tecnologico [FONDECYT (Chile)] [1130105], Vicerrectoria de Investigacion y Estudios Avanzados, Pontificia Universidad Catolica de Valparaiso, Chile, CNRS, Universite de Rennes 1, GENCI French national computer center [a0050807367], CONICYT (Chile), BECAS-CHILE, Universidad de Concepción - University of Concepcion [Chile], 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: Schiff base, Ligand, Dimer, chemistry.chemical_element, 02 engineering and technology, General Chemistry, 010402 general chemistry, 021001 nanoscience & nanotechnology, 01 natural sciences, Redox, Catalysis, Square pyramidal molecular geometry, 0104 chemical sciences, Metal, chemistry.chemical_compound, Crystallography, Nickel, chemistry, visual_art, Materials Chemistry, visual_art.visual_art_medium, [CHIM]Chemical Sciences, 0210 nano-technology, Ternary operation
Abstract: International audience; Four new ternary Ni(ii) and Cu(ii) complexes of ONO tridentate Schiff base and pyridylmethylenepyran (PyMP) ligands [(R-ONO)M(PyMP)] (R = anisyl = An M = Ni 1, Cu 2; R = ferrocenyl = Fc M = Ni 3, Cu 4) have been synthesized under facile reaction conditions starting from R-ONOH2, metal(ii) nitrate salts, and PyMP; R-ONOH2 stands for the Schiff base ligand precursors obtained by condensation of either 1-anisyl- or 1-ferrocenyl-butan-1,3-dione and 2-aminophenol. They have been thoroughly characterized with the help of various physicochemical tools, such as CHN analyses, IR and UV-vis spectra, H-1 NMR for diamagnetic Ni(ii) derivatives 1 and 3, and HRMS for paramagnetic Cu(ii) species 2 and 4. The molecular structures of 1-3 were authenticated by single-crystal X-ray diffraction methods, along with that of the doubly phenoxide-bridged dimer [Cu-2(mu-ONO-Fc)(2)(PyMp)(2)] (4 '), resulting from the recrystallization of 4. In 1-3, the four-coordinate nickel and copper atoms adopt a square planar geometry, whereas in 4 ' the Cu-II metal ion is five-coordinated in a square pyramidal environment with the pyridyl nitrogen occupying the apex. Electrochemical studies reveal two well-separated redox waves. The spin density distribution analyses reveal that the initial oxidation process is associated with a ligand-based level, with some ferrocenyl participation for the heterobimetallic compounds 3 and 4. Reversible redox switching can be established for 1 and 3 by time-resolved spectroelectrochemistry under thin-layer conditions where electrochemical cycling is associated with a significant modification of the UV-vis spectra of the chromophores. The second-order nonlinear optical responses of 1-4 along with those of assumed bispyrylium dimeric species 5 and 6, generated by chemical oxidation of 1 and 3, respectively, have been determined by harmonic light scattering measurements in dichloromethane solutions at 1.91 mu m incident wavelength. Rather high beta values ranging from 270-530 x 10(-30) esu were determined for 1-4. The beta value of 5 (800 x 10(-30) esu) was found to be almost twice that of its monomeric precursor 1, whereas the beta value of 6 (160 x 10(-30) esu) is reduced by half with respect to that of 3. In 5 the anisyl retains its donor ability whereas in 6 the electron-donating character of the oxidized ferrocenyl moiety is cancelled. Optimized geometries of the four compounds 1-4 as well as their electronic structures and that of their respective cations 1(+)-4(+) have been analyzed through DFT calculations, while TD-DFT computation has been used to interpret the major features of the UV-vis spectra.
Published: 2019
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42. Bonding in Barium Boryloxides, Siloxides, Phenoxides and Silazides. A comparison with the lighter alkaline earths

Author: Marie Cordier, Yann Sarazin, Jean-François Carpentier, Vincent Dorcet, Jean-Yves Saillard, Thierry Roisnel, Samia Kahlal, Joanna Hammoud, Erwann Le Coz, Institut des Sciences Chimiques de Rennes (ISCR), Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA), Agence Nationale de la Recherche. Grant Number: ANR-17-CE07-0003-01, ANR-17-CE07-0003,ALCACAT,Métaux alcalino-terreux pour la fonctionnalisation C–O(2017), Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), and Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)
Subjects: Steric effects, Alkaline earth metal, 010405 organic chemistry, Ligand, Coordination number, Organic Chemistry, Siloxide, Ionic bonding, Bridging ligand, General Chemistry, O-based ligands, 010402 general chemistry, 01 natural sciences, DFT, Catalysis, 0104 chemical sciences, chemistry.chemical_compound, Crystallography, chemistry, Barium, [CHIM]Chemical Sciences, alkaline-earth metals, Homoleptic, Bonding analysis
Abstract: Barium complexes ligated by bulky boryloxides [OBR2 ]- (where R=CH(SiMe3 )2 , 2,4,6-i Pr3 -C6 H2 or 2,4,6-(CF3 )3 -C6 H2 ), siloxide [OSi(SiMe3 )3 ]- , and/or phenoxide [O-2,6-Ph2 -C6 H3 ]- , have been prepared. A diversity of coordination patterns is observed in the solid state for both homoleptic and heteroleptic complexes, with coordination numbers ranging between 2 and 4. The identity of the bridging ligand in heteroleptic dimers [Ba(μ2 -X1 )(X2 )]2 depends largely on the given pair of ligands X1 and X2 . Experimentally, the propensity to fill the bridging position increases according to [OB{CH(SiMe3 )2 }2 )]
Published: 2021
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43. Inside Back Cover: A Two-Electron Silver Superatom Isolated from Thermally Induced Internal Redox Reaction of A Silver(I) Hydride (Angew. Chem. Int. Ed. 23/2021)

Author: Jian-Hong Liao, Jean-Yves Saillard, Tzu-Hao Chiu, Che-Jen Lin, C. W. Liu, Samia Kahlal, Yu-Jie Zhong, National Dong Hwa University (NDHU), Institut des Sciences Chimiques de Rennes (ISCR), Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), and Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA)
Subjects: Chemistry, Hydride, Superatom, [CHIM]Chemical Sciences, Cover (algebra), General Chemistry, Electron, Photochemistry, Redox, Catalysis, ComputingMilieux_MISCELLANEOUS, 3. Good health
Abstract: International audience
Published: 2021
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44. On Heteronuclear Isoelectronic Alternatives to [Au

Author: Jianyu, Wei, Peter L, Rodríguez-Kessler, Jean-François, Halet, Samia, Kahlal, Jean-Yves, Saillard, and Alvaro, Muñoz-Castro
Abstract: The development of well-defined atomically precise heteronuclear nanoclusters passivated by protecting ligands is presently a booming area, owing to the fact that doping well-known homonuclear nanostructures allows fine-tuning of their properties. Here, we explore by means of density functional theory calculations the possibility of doping the central gold atom in the classical [Au
Published: 2021

45. Metal-metal bonded alkaline-earth distannyls

Author: Yann Sarazin, Peter M. Chapple, Marie Cordier, Julien Cartron, Jean-Yves Saillard, Ghanem Hamdoun, Jean-François Carpentier, Samia Kahlal, Hassan Oulyadi, 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 Organique et Bioorganique : Réactivité et Analyse (COBRA), Institut de Chimie Organique Fine (IRCOF), Université de Rouen Normandie (UNIROUEN), Normandie Université (NU)-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)-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 Normand de Chimie Moléculaire Médicinale et Macromoléculaire (INC3M), Université de Caen Normandie (UNICAEN), Normandie Université (NU)-Normandie Université (NU)-École Nationale Supérieure d'Ingénieurs de Caen (ENSICAEN), Normandie Université (NU)-Université Le Havre Normandie (ULH), Normandie Université (NU)-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)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université de Caen Normandie (UNICAEN), 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)-Centre National de la Recherche Scientifique (CNRS), Agence National de la Recherche French National Research Agency (ANR) [ANR-17-CE070017-01], GENCI (Grand Equipment National de Calcul Intensif) [A0050807367], Labex SynOrg [ANR-11-LABX-0029], ANR-11-LABX-0029,SYNORG,Synthèse Organique : des molécules au vivant(2011), Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA), Institut Normand de Chimie Moléculaire Médicinale et Macromoléculaire (INC3M), Institut de Chimie du CNRS (INC)-École Nationale Supérieure d'Ingénieurs de Caen (ENSICAEN), Institut National des Sciences Appliquées (INSA)-Normandie Université (NU)-Institut National des Sciences Appliquées (INSA)-Université Le Havre Normandie (ULH), Normandie Université (NU)-Centre National de la Recherche Scientifique (CNRS)-Université de Caen Normandie (UNICAEN), Normandie Université (NU)-Institut de Chimie du CNRS (INC)-École Nationale Supérieure d'Ingénieurs de Caen (ENSICAEN), Normandie Université (NU)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie Organique Fine (IRCOF), and Institut National des Sciences Appliquées (INSA)-Normandie Université (NU)-Institut National des Sciences Appliquées (INSA)-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS)
Subjects: Diffraction, Alkaline earth metal, Materials science, 010405 organic chemistry, Chemical shift, Center (category theory), Ionic bonding, General Chemistry, Nuclear magnetic resonance spectroscopy, 010402 general chemistry, 01 natural sciences, 0104 chemical sciences, chemistry.chemical_compound, Crystallography, Chemistry, chemistry, Covalent bond, [CHIM]Chemical Sciences, Homoleptic
Abstract: The first families of alkaline-earth stannylides [Ae(SnPh3)2·(thf)x] (Ae = Ca, x = 3, 1; Sr, x = 3, 2; Ba, x = 4, 3) and [Ae{Sn(SiMe3)3}2·(thf)x] (Ae = Ca, x = 4, 4; Sr, x = 4, 5; Ba, x = 4, 6), where Ae is a large alkaline earth with direct Ae–Sn bonds, are presented. All complexes have been characterised by high-resolution solution NMR spectroscopy, including 119Sn NMR, and by X-ray diffraction crystallography. The molecular structures of [Ca(SnPh3)2·(thf)4] (1′), [Sr(SnPh3)2·(thf)4] (2′), [Ba(SnPh3)2·(thf)5] (3′), 4, 5 and [Ba{Sn(SiMe3)3}2·(thf)5] (6′), most of which crystallised as higher thf solvates than their parents 1–6, were established by XRD analysis; the experimentally determined Sn–Ae–Sn′ angles lie in the range 158.10(3)–179.33(4)°. In a given series, the 119Sn NMR chemical shifts are slightly deshielded upon descending group 2 from Ca to Ba, while the silyl-substituted stannyls are much more shielded than the phenyl ones (δ119Sn/ppm: 1′, −133.4; 2′, −123.6; 3′, −95.5; 4, −856.8; 5, −848.2; 6′, −792.7). The bonding and electronic properties of these complexes were also analysed by DFT calculations. The combined spectroscopic, crystallographic and computational analysis of these complexes provide some insight into the main features of these unique families of homoleptic complexes. A comprehensive DFT study (Wiberg bond index, QTAIM and energy decomposition analysis) points at a primarily ionic Ae–Sn bonding, with a small covalent contribution, in these series of complexes; the Sn–Ae–Sn′ angle is associated with a flat energy potential surface around its minimum, consistent with the broad range of values determined by experimental and computational methods., The complete series of heterobimetallic alkaline-earth distannyls [Ae{SnR3}2·(thf)x] (Ae = Ca, Sr, Ba) have been prepared for R = Ph and SiMe3, and their bonding and electronic properties have been comprehensively investigated.
Published: 2021
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46. Intercluster exchanges leading to hydride-centered bimetallic clusters: a multi-NMR, X-ray crystallographic, and DFT study

Author: Jean-Yves Saillard, Michael J. McGlinchey, Jian-Hong Liao, Tzu-Hao Chiu, Samia Kahlal, Yu-Jie Zhong, Ying-Yann Wu, Chen-Wei Liu, National Dong Hwa University (NDHU), Academia Sinica, Institut des Sciences Chimiques de Rennes (ISCR), Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA), University College Dublin [Dublin] (UCD), ANR MOST 108-2923-M-259-001, Ministry of Science and Technology, Taiwan, Agence Nationale de la Recherche, AS-CFII-108-112, Academia Sinica, ANR-18-CE09-0037,Nanoalloys,Alliages superatomiques et de structure précise riches en argent et en cuivre(2018), Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), and Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)
Subjects: Materials science, Hydride, 02 engineering and technology, Crystal structure, 010402 general chemistry, 021001 nanoscience & nanotechnology, Resonance (chemistry), 01 natural sciences, 0104 chemical sciences, Nanoclusters, Inorganic Chemistry, Crystallography, [CHIM]Chemical Sciences, 0210 nano-technology, Spectroscopy, Single crystal, Bimetallic strip, Two-dimensional nuclear magnetic resonance spectroscopy
Abstract: International audience; Encouraged by the successful syntheses of alloy nanoclusters (or nanoparticles) via intercluster (or interparticle) reactions, herein we apply this methodology to prepare a series of bimetallic hydride clusters. Mixing of two clusters, [Ag7(H){E2P(OiPr)2}6] (E = S, 1; Se, 3) and [Cu7(H){E2P(OiPr)2}6] (E = S, 2; Se, 4), yields two series of hydride-centered bimetallic clusters, [CuxAg7-x(H){E2P(OiPr)2}6] (x = 0-7; E = S, 5; Se, 6). Their compositions are fully characterized by positive-mode ESI-MS spectrometry, multi-NMR spectroscopy, and the structures of [Cu6Ag(H){S2P(OiPr)2}6] (5a) and [CuAg6(H){Se2P(OiPr)2}6] (6a) by single crystal X-ray diffraction. The presence of individual compounds in solution is the result of a (dynamic) chemical equilibrium primarily driven by metal exchanges. In fact, the process of inter-cluster exchange of 1 and 2 leading to hydride-centered bimetallic clusters 5 can be monitored by concentration-dependent 31P NMR spectroscopy of which the higher concentration of 1 in the reaction, the closer to its resonance will be the distribution, in accord with Le Chatelier’s principle. The dynamic equilibrium is further confirmed by 2D exchange spectroscopy that reveals a stepwise process involving one metal exchange at a time. DFT calculations on a model series of clusters 6 show that silver prefers occupying the inner tetrahedral positions, while copper favors capping positions, in full agreement with the crystal structure of 5a and 6a.
Published: 2021
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47. A Two-Electron Silver Superatom Isolated from Thermally Induced Internal Redox Reaction of A Silver(I) Hydride

Author: Jian-Hong Liao, Jean-Yves Saillard, Che-Jen Lin, Samia Kahlal, Tzu-Hao Chiu, Yu-Jie Zhong, Chen-Wei Liu, National Dong Hwa University (NDHU), 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), This work was supported by the Ministry of Science and Technology of Taiwan (MOST 109-2113-M-259-008, 108-2923-M-259-001), and the France-Taiwan ANR-MOST program (project Nanoalloys)., ANR-18-CE09-0037,Nanoalloys,Alliages superatomiques et de structure précise riches en argent et en cuivre(2018), 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: superatom, Materials science, Photoluminescence, 010405 organic chemistry, Reducing agent, Hydride, Superatom, hydride, General Chemistry, General Medicine, 010402 general chemistry, 01 natural sciences, Fluorescence, Redox, Catalysis, 3. Good health, 0104 chemical sciences, Trigonal bipyramidal molecular geometry, Crystallography, silver nanocluster, redox, [CHIM]Chemical Sciences, photoluminescence, Luminescence
Abstract: Rational syntheses under controllable reducing conditions in the preparation of superatoms with cluster electron not exceeding two are challenging. Herein a dithiolate-stabilized two-electron silver nanocluster, Ag 10 {S 2 P(O i Pr) 2 } 8 ( 1 ), is isolated via a self-redox reaction of Ag 7 (H){S 2 P(O i Pr) 2 } 6 without adding extra reducing agents. The metal framework of Ag 7 , a bicapped trigonal bipyramid, is highly correlated to that of Ag 10 , suggesting Ag 7 (H){S 2 P(O i Pr) 2 } 6 acts as both reducing agent and template in cluster growth. 1 is highly fluorescent at ambient temperature and TD-DFT calculations indicate that the emission is of 1Px ® 1S nature. 1 is highly luminescent at ambient temperature and its triplet emission origin, corresponding to a 1P x → 1S transition, is fully reproduced by TD-DFT calculations.
Published: 2021
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48. All-selenolate-protected eight-electron platinum/silver nanoclusters

Author: Tzu-Hao Chiu, Chen-Wei Liu, Samia Kahlal, Isaac Chantrenne, Jean-Yves Saillard, Franck Gam, Jian-Hong Liao, National Dong Hwa University (NDHU), 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), Ministry of Science and Technology, Taiwan [MOST 109-2113-M-259-008, 108-2923M-259-001], France-Taiwan ANR-MOST 2018 program (project Nanoalloys), GENCI French national computer resource center [A0030807367], ANR-18-CE09-0037,Nanoalloys,Alliages superatomiques et de structure précise riches en argent et en cuivre(2018), Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), and Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)
Subjects: Materials science, 010405 organic chemistry, Ligand, Icosahedral symmetry, chemistry.chemical_element, 010402 general chemistry, 01 natural sciences, 0104 chemical sciences, Nanoclusters, Metal, Crystallography, chemistry, visual_art, visual_art.visual_art_medium, [CHIM]Chemical Sciences, General Materials Science, Density functional theory, Emission spectrum, Platinum, HOMO/LUMO
Abstract: International audience; The first atomically and structurally precise platinum/silver superatoms protected by Se-donor ligands were synthesized in high yield by adopting ligand replacements on [PtAg20{S2P((OPr)-Pr-n)(2)}(12)] (3) with 12 equiv. of di-alkyl diselenophosph(in)ates. Structures of [PtAg20{Se2P(OR)(2)}(12)] (R = Pr-n (1a), Pr-i (1b)) and [PtAg20{Se2P (CH2CH2Ph)(2)}(12)] (2) were accurately determined by single-crystal X-ray diffraction to reveal an eight-electron [Pt@Ag-12](4+) icosahedral core embedded within a cube of eight silver(I) atoms and wrapped into a shell of 12 diselenophosph(in)ates. While the lowest energy absorption band of the Se derivatives is red-shifted to longer wavelengths in comparison with the S analogue, it is blue-shifted in the emission spectra. Density functional theory (DFT) and TD-DFT calculations rationalize the electronic structures as those of eight-electron superatoms, with their HOMO and LUMO being the 1P and 1D levels, respectively. The two UV-visible lowest bands are associated with 1P -> 1D metal to metal charge transfer (MMCT) transitions. The blue shift observed for the S analogue results from a larger HOMO-LUMO gap in the case of dithiolate ligands.
Published: 2021
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49. Electron Counting in Ligated High Nuclearity Late Transition Metal Clusters

Author: Jianyu Wei, Jean-Yves Saillard, Samia Kahlal, Jean-François Halet, Franck Gam, Institut des Sciences Chimiques de Rennes (ISCR), Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), National Institute for Materials Science (NIMS), Laboratory for Innovative Key Materials and Structures (LINK), Saint-Gobain-National Institute of Materials Science-Centre National de la Recherche Scientifique (CNRS), and Mingos, DMP
Subjects: Electron-counting rules, Materials science, Silver, Jellium, Electron, Nanoclusters, engineering.material, Alkali metal, Clusters, Superatoms, Transition metal, Chemical physics, Supermolecules, engineering, [CHIM]Chemical Sciences, Noble metal, Polyhedral skeletal electron pair theory, Gold, Jellium model, Electron counting, Copper, Palladium, Platinum
Abstract: International audience; Over the years, the development of large ligated transition metal clusters has been accompanied by the development of theories using conceptual ideas and models which resulted in a range of electron-counting rules. All of them aimed to understand and rationalize the relationship between the structure and the electron count. Among these rules, those relying on the spherical jellium approximation, initially employed to study simple spherical alkali clusters, have shown to be very powerful to chemists interested in viewing ligated noble metal nanoclusters as superatoms, supermolecules or specific nano-objects with "magic" electron counts. This review develops the basic theory and illustrates its applications for specific spherical and non-spherical ligand-protected nanoclusters containing metals from groups 10 and 11.
Published: 2021
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50. Reactivities of Interstitial Hydrides in a Cu-11 Template: En Route to Bimetallic Clusters

Author: Jean-Yves Saillard, Ying-Yann Wu, Samia Kahlal, Qi Wang, Chen-Wei Liu, Tzu-Hao Chiu, Rhone P. Brocha Silalahi, Jian-Hong Liao, Xiaoping Wang, National Dong Hwa University (NDHU), 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), Academia Sinica, Oak Ridge National Laboratory [Oak Ridge] (ORNL), UT-Battelle, LLC, Ministry of Science and Technology of Taiwan (MOST) [109-2113-M-259-008], France-Taiwan ANR-MOST program (project Nanoalloys), GENCI computing resource [A0090807367], China Scholarship Council China Scholarship Council, ANR-18-CE09-0037,Nanoalloys,Alliages superatomiques et de structure précise riches en argent et en cuivre(2018), 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: Neutron diffraction, chemistry.chemical_element, Hydride ligands, 010402 general chemistry, 01 natural sciences, Catalysis, Ion, Metal, neutron diffraction, [CHIM]Chemical Sciences, silver, Bimetallic strip, 010405 organic chemistry, Hydride, Superatom, General Medicine, General Chemistry, gold, Copper, 0104 chemical sciences, Crystallography, chemistry, visual_art, copper, visual_art.visual_art_medium, cluster compounds
Abstract: International audience; In sharp contrast to surface hydrides, reactivities of interstitial hydrides are difficult to explore. When treated with a metal ion (Cu+, Ag+, and Au+), the stable Cu-I dihydride template [Cu11H2{S2P((OPr)-Pr-i)(2)}(6)(C equivalent to CPh)(3)] (H2Cu11) generates surprisingly three very different compounds, namely [CuH2Cu11{S2P((OPr)-Pr-i)(2)}(6)(C equivalent to CPh)(3)](+) (1), [AgH2Cu14{S2P((OPr)-Pr-i)(2)}(6)((C equivalent to CPh)(6)](+) (2), and [AuCu11{S2P((OPr)-Pr-i)(2)}(6)(C equivalent to CPh)(3)Cl] (3). Compounds 1 and 2 are both M-I species and maintain the same number of hydride ligands as their H2Cu11 precursor. Neutron diffraction revealed the first time a trigonal-pyramidal hydride coordination mode in the AgCu3 environment of 2. 3 has no hydride and exhibits a mixed-valent [AuCu11](10+) metal core, making it a two-electron superatom.
Published: 2021
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