Shape Modulation of Octanuclear Cu(I) or Ag(I) Dichalcogeno Template Clusters with Respect to the Nature of their Encapsulated Anions: A Combined Theoretical and Experimental Investigation
| Autor: | Chen-Wei Liu, Ping-Kuei Liao, Eric Furet, Ching-Shiang Fang, Camille Latouche, Jérôme Cuny, Jean-Yves Saillard, Yan-Ru Lin, Samia Kahlal |
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| Přispěvatelé: | Institut des Sciences Chimiques de Rennes (ISCR), Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA), Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), 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) |
| Rok vydání: | 2013 |
| Předmět: |
010405 organic chemistry
Ligand Hydride Inorganic chemistry Oxide Ionic bonding Nitride 010402 general chemistry 01 natural sciences 0104 chemical sciences [CHIM.THEO]Chemical Sciences/Theoretical and/or physical chemistry Inorganic Chemistry chemistry.chemical_compound Crystallography chemistry Octahedron Covalent bond Density functional theory Physical and Theoretical Chemistry |
| Zdroj: | Inorganic Chemistry Inorganic Chemistry, American Chemical Society, 2013, 52 (13), pp.7752-7765. ⟨10.1021/ic400959a⟩ Inorganic Chemistry, 2013, 52 (13), pp.7752-7765. ⟨10.1021/ic400959a⟩ |
| ISSN: | 1520-510X 0020-1669 |
| DOI: | 10.1021/ic400959a |
| Popis: | International audience; M8L6 clusters (M = Cu(I), Ag(I); L = dichalcogeno ligand) are known for their ability to encapsulate various kinds of saturated atomic anions. Calculations on the models [M8(E2PH2)6]2+ (M = Cu(I), Ag(I); E = S, Se) and the ionic or neutral [M8(X)(E2PH2)6]q (X = H, F, Cl, Br, O, S, Se, N, P, C) indicate that the cubic M8L6 cage adapts its shape for maximizing the host-guest bonding interaction. The interplay between size, covalent and ionic bonding favors either a cubic, tetracapped tetrahedral, or bicapped octahedral structure of the metal framework. Whereas the large third- and fourth-row main group anions maintain the cubic shape, a distortion toward a tetracapped tetrahedral arrangement of the metals occurs in the case of hydride, fluoride, and oxide. The distortion is strong in the case of hydride, weak in the case of fluoride, and intermediate in the case of oxide. Density functional theory (DFT) calculations predict a bicapped octahedral architecture in the case of nitride and carbide. These computational results are supported by X-ray structures, including those of new fluorine- and oxygen-containing compounds. It is suggested that other oxygen-containing as well as so far unknown nitride-containing clusters should be feasible. For the first time, the dynamical behavior of the encapsulated hydride has been investigated by metadynamics simulations. Our results clearly demonstrate that the interconversion mechanism between two identical tetracapped tetrahedral configurations occurs through a succession of M-H bonds breaking and forming which present very low activation energies and which involve a rather large number of intermediate structures. This mechanism is full in accordance with 109Ag and 1H state NMR measurements. |
| Databáze: | OpenAIRE |
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