Thirty electrons 'trapped' in a spherical matrix: A molybdenum oxide- based nanostructured Keplerate reduced by 36 electrons

Angewandte Chemie - International Edition

Volumn 39, Issue 9, 2000, Pages 1614-1616

  Müller, Achim ^a   Shah, Syed Qaiser Nazir ^a   Bögge, Hartmut ^a   Schmidtmann, Marc ^a   Kögerler, Paul ^a   Hauptfleisch, Björn ^a   Leiding, Stefan ^a   Wittler, Kai ^a  

^a BIELEFELD UNIVERSITY   (Germany)

Author keywords

Electronic structure; Mixed valence compounds; Molybdenum; Polyoxometalates; Supramolecular chemistry

Indexed keywords

MOLYBDENUM; OXIDE;

ARTICLE; ELECTRON; MACROMOLECULE; NANOPARTICLE; STRUCTURE ANALYSIS; SYNTHESIS; ULTRASTRUCTURE;

EID: 1642586146     PISSN: 14337851     EISSN: None     Source Type: Journal    
DOI: 10.1002/(SICI)1521-3773(20000502)39:9<1614::AID-ANIE1614>3.0.CO;2-9     Document Type: Article

References (22)

1. a) A. Müller, S. Polarz, S. K. Das, E. Krickemeyer, H. Bögge, M. Schmidtmann, B. Hauptfleisch, Angew. Chem. 1999, 111, 3439-3443; Angew. Chem. Int. Ed. 1999, 38, 3241-3245;
2. a) A. Müller, S. Polarz, S. K. Das, E. Krickemeyer, H. Bögge, M. Schmidtmann, B. Hauptfleisch, Angew. Chem. 1999, 111, 3439-3443; Angew. Chem. Int. Ed. 1999, 38, 3241-3245;
3. b) A. Müller, S. Sarkar, S. O. N. Shah, H. Bögge, M. Schmidtmann, Sh. Sarkar, P. Kögerler, B. Hauptfleisch, A. X. Trautwein, V. Schünemann, Angew. Chem. 1999, 111, 3435-3439; Angew. Chem. Int. Ed. 1999, 38, 3238-3241.
4. b) A. Müller, S. Sarkar, S. O. N. Shah, H. Bögge, M. Schmidtmann, Sh. Sarkar, P. Kögerler, B. Hauptfleisch, A. X. Trautwein, V. Schünemann, Angew. Chem. 1999, 111, 3435-3439; Angew. Chem. Int. Ed. 1999, 38, 3238-3241.
5. 5] pentagons, where many orientations are possible. The denomination "Keplerate", used in this paper for an anionic species, should be also used for neutral species when the topology of the system is in accordance with the definition (see ref. [1b]).
6. 5] pentagons, where many orientations are possible. The denomination "Keplerate", used in this paper for an anionic species, should be also used for neutral species when the topology of the system is in accordance with the definition (see ref. [1b]).
7. 3. Structure graphics were produced with the DIAMOND 2.1 program (K. Brandenburg, Crystal Impact GbR, 1999). Due to disorder, not all positions of the water molecules inside the sphere and in the crystal lattice were localized. The same note applies to the acetate ligands. Cristallographic data (excluding structure factors) for the structure reported in this paper have been deposited with the Cambridge Crystallographic Data Centre as supplementary publication no. CCDC-138289. Copies of the data can be obtained free of charge on application to CCDC, 12 Union Road, Cambridge CB2 1EZ, UK (fax: (+44) 1223-336-033; e-mail: deposit@ccdc.cam.ac.uk).
8. a) M. B. Robin, P. Day, Inorg. Chem. Radiochem. 1967, 10, 247-422; to emphasize the significance of the relevant class of species, see also
9. b) Mixed Valence Systems: Application in Chemistry, Physics and Biology (Ed.: K. Prassides), Kluwer, Dordrecht, 1992.
10. a) This is in agreement with the presence of a neutral cluster. b) The EHMO calculations are based on the atomic positions from the X-ray structure analysis (the proton positions were modeled and disordered acetate ligands were replaced by water ligands) using standard parameters of the bind program (G. A. Landrum, W. V. Glassey, bind (version 3.0); http://overlap.chem.cornell.edu:8080/yaehmop.html). Detailed data on the electronic structure and the magnetism in the context of the dominating Temperature-Independent Paramagnetism (TIP), and the extremely strong exchange interactions responsible for the ESR behavior will be published elsewhere (A. Müller, D. Gatteschi, W. Jeitschko et al., unpublished results).
11. a) A. Müller, S. Q. N. Shah, H. Bögge, M. Schmidtmann, Nature 1999, 397, 48-50;
12. b) A. Müller, M. Koop, H. Bögge, M. Schmidtmann, C. Beugholt, Chem. Commun. 1998, 1501-1502;
13. c) A. Müller, S. K. Das, V. P. Fedin, E. Krickemeyer, C. Beugholt, H. Bögge, M. Schmidtmann, B. Hauptfleisch, Z. Anorg. Allg. Chem. 1999, 625, 1187-1192;
14. d) A. Müller, S. K. Das, H. Bögge, C. Beugholt, M. Schmidtmann, Chem. Commun. 1999, 1035-1036;
15. e) A. Müller, C. Beugholt, M. Koop, S. K. Das, M. Schmidtmann, H. Bögge, Z. Anorg. Allg. Chem. 1999, 625, 1960-1962.
16. H. K. Chae, W. G. Klemperer, T. A. Marquart, Coord. Chem. Rev. 1993, 128, 209-224.
17. A. Müller, F. Peters, M. T. Pope, D. Gatteschi, Chem. Rev. 1998, 98, 239-271.
18. a) Gmelins Handbuch der Anorganischen Chemie, Molybdän, Verlag Chemie, Berlin, 1935, pp. 134-147;
19. b) Gmelin Handbook of Inorganic Chemistry, Molybdenum Suppl., Vol. B3a, 8th ed., Springer, Berlin, 1987, pp. 61-68;
20. c) A. Müller, C. Serain, Acc. Chem. Res. 2000, 33, 2-10.
21. a) H. So, M. T. Pope, in Electron and Proton Transfer in Chemistry and Biology (Studies in Physical and Theoretical Chemistry) (Eds.: A. Müller, H. Ratajczak, M. T. Pope, W. Junge, E. Diemann), Elsevier, Amsterdam, 1992, chap. "Electron Hopping and Delocalisation in Mixed-Valence Metal-Oxygen Clusters";
22. see also: b) F. A. Cotton, G. Wilkinson, Advanced Inorganic Chemistry, 4th ed., Wiley, New York, 1980, p. 861.