Ag 13 OsO 6 : A Silver Oxide with Interconnected Icosahedral Ag 13 4+ Clusters and Dispersed [OsO 6 ] 4− Octahedra
2003; Wiley; Volume: 42; Issue: 36 Linguagem: Inglês
10.1002/anie.200351740
ISSN1521-3773
AutoresSascha Ahlert, Wilhelm Klein, O. Jepsen, O. Gunnarsson, O. K. Andersen, Martin Jansen,
Tópico(s)Polyoxometalates: Synthesis and Applications
ResumoAngewandte Chemie International EditionVolume 42, Issue 36 p. 4322-4325 Communication Ag13OsO6: A Silver Oxide with Interconnected Icosahedral Ag134+ Clusters and Dispersed [OsO6]4− Octahedra† Sascha Ahlert, Sascha Ahlert Max-Planck-Institut für Festkörperforschung, Heisenbergstrasse 1, 70567 Stuttgart, Germany, Fax: (+49) 711-689-1502Search for more papers by this authorWilhelm Klein Dr., Wilhelm Klein Dr. Max-Planck-Institut für Festkörperforschung, Heisenbergstrasse 1, 70567 Stuttgart, Germany, Fax: (+49) 711-689-1502Search for more papers by this authorOve Jepsen Dr., Ove Jepsen Dr. Max-Planck-Institut für Festkörperforschung, Heisenbergstrasse 1, 70567 Stuttgart, Germany, Fax: (+49) 711-689-1502Search for more papers by this authorOlle Gunnarsson Dr., Olle Gunnarsson Dr. Max-Planck-Institut für Festkörperforschung, Heisenbergstrasse 1, 70567 Stuttgart, Germany, Fax: (+49) 711-689-1502Search for more papers by this authorOle Krogh Andersen Prof. Dr., Ole Krogh Andersen Prof. Dr. Max-Planck-Institut für Festkörperforschung, Heisenbergstrasse 1, 70567 Stuttgart, Germany, Fax: (+49) 711-689-1502Search for more papers by this authorMartin Jansen Prof. Dr., Martin Jansen Prof. Dr. [email protected] Max-Planck-Institut für Festkörperforschung, Heisenbergstrasse 1, 70567 Stuttgart, Germany, Fax: (+49) 711-689-1502Search for more papers by this author Sascha Ahlert, Sascha Ahlert Max-Planck-Institut für Festkörperforschung, Heisenbergstrasse 1, 70567 Stuttgart, Germany, Fax: (+49) 711-689-1502Search for more papers by this authorWilhelm Klein Dr., Wilhelm Klein Dr. Max-Planck-Institut für Festkörperforschung, Heisenbergstrasse 1, 70567 Stuttgart, Germany, Fax: (+49) 711-689-1502Search for more papers by this authorOve Jepsen Dr., Ove Jepsen Dr. Max-Planck-Institut für Festkörperforschung, Heisenbergstrasse 1, 70567 Stuttgart, Germany, Fax: (+49) 711-689-1502Search for more papers by this authorOlle Gunnarsson Dr., Olle Gunnarsson Dr. Max-Planck-Institut für Festkörperforschung, Heisenbergstrasse 1, 70567 Stuttgart, Germany, Fax: (+49) 711-689-1502Search for more papers by this authorOle Krogh Andersen Prof. Dr., Ole Krogh Andersen Prof. Dr. Max-Planck-Institut für Festkörperforschung, Heisenbergstrasse 1, 70567 Stuttgart, Germany, Fax: (+49) 711-689-1502Search for more papers by this authorMartin Jansen Prof. Dr., Martin Jansen Prof. Dr. [email protected] Max-Planck-Institut für Festkörperforschung, Heisenbergstrasse 1, 70567 Stuttgart, Germany, Fax: (+49) 711-689-1502Search for more papers by this author First published: 17 September 2003 https://doi.org/10.1002/anie.200351740Citations: 26 † The authors would like to thank the chemical service group, Eva Brücher, Gisela Siegle, and Dr. Reinhard K. Kremer for determining the electric and magnetic properties of the material. Read the full textAboutPDF ToolsRequest permissionExport citationAdd to favoritesTrack citation ShareShare Give accessShare full text accessShare full-text accessPlease review our Terms and Conditions of Use and check box below to share full-text version of article.I have read and accept the Wiley Online Library Terms and Conditions of UseShareable LinkUse the link below to share a full-text version of this article with your friends and colleagues. Learn more.Copy URL Graphical Abstract The tendency for silver-rich compounds to form higher agglomerates of silver atoms or ions is well known. The synthesis of Ag13OsO6 represents the first compound in the Ag/Os/O system. Besides [OsO6]4− octahedra, the compound contains icosahedrally shaped Ag134+ clusters (see picture), which are observed for the first time in solid silver oxides. References 1C. Linke, M. Jansen, Z. Anorg. Allg. Chem. 1997, 623, 1441. 2M. Jansen, Habilitationsschrift, Universiät Gießen, 1978. 3M. Jansen, J. Less-Common Met. 1980, 76, 285. 4M. Jansen, Angew. Chem. 1987, 99, 1136; Angew. Chem. Int. Ed. Engl. 1987, 26, 1098. 5C. Friebel, M. Jansen, Z. Naturforsch. B 1984, 39, 739. 6B. U. Köhler, M. Jansen, W. Weppner, J. Solid State Chem. 1985, 57, 227. 7P. Behrens, S. Aßmann, U. Bilow, C. Linke, M. Jansen, Z. Anorg. Allg. Chem. 1999, 625, 111. 8G. Argay, F. Naray-Szabo, Acta Chim. Acad. Sci. Hung. 1966, 329. 9W. Beesk, P. G. Jones, H. Rumpel, E. Schwarzmann, G. M. Sheldrick, J. Chem. Soc. Chem. Commun. 1981, 644. 10C. Linke, M. Jansen, Inorg. Chem. 1994, 33, 2614. 11M. Jansen, C. Linke, Angew. Chem. 1992, 104, 618; Angew. Chem. Int. Ed. Engl. 1992, 31, 653. 12M. Jansen, C. Linke, Z. Anorg. Allg. Chem. 1992, 616, 95. 13H. G. von Schnering, K. Häusler, Rev. Chim. Miner. 1976, 13, 71. 14M. Schreyer, M. Jansen, Angew. Chem. 2002, 114, 665; Angew. Chem. Int. Ed. 2002, 41, 643. 15Crystal data of Ag13OsO6: 0.1×0.1×0.1 mm3; cubic, Fmc, a=13.1712(5) Å; V=2284.95(15) Å3; Z=8, μ=32.797 mm−1; ρcalcd=9.817 g cm−3; Bruker AXS Smart CCD 1000, MoKα, λ=0.71073 Å; measurement range 3.09=θ=34.96°; T=293(2) K; 2367 independent reflections out of 7622 measured (I>2σ(I)); solved by direct methods and subsequently refined by full-matrix, least-squares calculations based on F2 (SHELXTL-V5.12); max./min. residual electron density +1.60/−4.84 e Å−3, R1=0.0319, wR2=0.0650, GOF=1.360. Further details on the crystal structure investigations may be obtained from the Fachinformationszentrum Karlsruhe, 76344 Eggenstein-Leopoldshafen, Germany (fax: (+49) 7247-808-666; e-mail: [email protected]), on quoting the depository number CSD-413193. 16T. Betz, R. Hoppe, Z. Anorg. Allg. Chem. 1985, 524, 17. 17K. E. Stitzer, M. D. Smith, H.-C. zur Loye, Solid State Sci. 2002, 4, 311. 18 18aJ. A. A. Ketelaar, J. Chem. Phys. 1937, 5, 668; 18bE. Zintl, W. Hauke, Nature 1937, 139, 717; 18cD. P. Shoemaker, R. E. March, F. J. Ewing, L. Pauling, Acta Crystallogr. 1952, 5, 637. 19The band-structure calculation was performed with the GGA Perdew–Wang density functional and the Stuttgart TB LMTO code. The sphere radii in pm were: 127 (Os), 110 (O), 99 (E), 157 (Ag(2)), and 160 (Ag(1)). The E spheres were placed at the faces of the octahedra, at the Wyckoff 64 g sites with x=0.1633. The basis set included the Ag and Os s, p, and d LMTOs, the O p LMTOs, and the E s and p LMTOs. The O s and d partial waves were downfolded. Spin–orbit coupling was neglected in this scalar relativistic calculation; its inclusion would cause a t2g band to split by (3/2)ζd∼0.3 eV into a lower fourfold and an upper twofold degenerate band. 20The charges obtained from the occupations of our orthonormal LMTOs are: Os+2.62, O−0.86=(O + E)/6, Ag(1)−0.32, and Ag(2)+0.24). 21R. Dronskowski, P. E. Blöchl, J. Phys. Chem. 1993, 97, 8617. 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