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Chapter 5 Unpublished Results [6] G. Bo, L. Shuxia, X. Linhua, Y. Miao, Z. Chundan, S. Chunyan, C. Haiyan, J. Solid State Chem. 2006, 179, 1681. [7] D. Drewes, E. M. Limanski, B. Krebs, Dalton Trans. 2004, 2087. [8] A. H. Ismail, N. H. Nsouli, M. H. Dickman, U. Kortz, J. Clust. Sc. 2009, 20, 453. [9] D. Altermatt, I. D. Brown, Acta. Crystallogr. 1985, B41, 244. [10] G. M. Sheldrick, Acta. Crystallogr. 2008, A64, 112. 197
Chapter 5 Published Results 5.B. Transition Metal‐Containing Heteropolytungstates: Copper‐, Cobalt‐, and Manganese‐Containing 17‐Tungsto‐2‐Germanates N. H. Nsouli, A. H. Ismail, I. S. Helgadottir, M. H. Dickman, J. M Clemente-Juan, U. Kortz, Inorg. Chem. 2009, 48, 5884 5.B.1. Introduction Polyoxometalates (POMs) are metal-oxide clusters formed of early d-block elements in high oxidation states (e.g., W 6+ , V 5+ ), and they constitute a unique class of inorganic compounds. POMs were discovered in 1826 by Berzelius when he noted the formation of a yellow precipitate after the reaction of ammonium molybdate with phosphoric acid. 1 The chemistry of POMs is a rapidly growing field because they exhibit a combination of tunable properties, including composition, size, shape, charge density, redox potentials, and solubility. 2 As a result, POMs have potential applications in many fields such as catalysis, medicine, photochemistry, electrochemistry, and magnetism. 3 The mechanism of formation of polyanions is not well understood and is usually described as self-assembly. One important goal in POM synthesis is the incorporation of transition metals, lanthanides, organometallic entities, or any other functional unit(s) into lacunary (i.e., vacant) polyanion precursors, leading to a tremendous diversity of structures. In particular, polytungstates are of importance in this respect, as a large number of stable lacunary precursors are known (as opposed to polymolybdates or polyvanadates). From a magnetic point of view, POMs containing more than one paramagnetic transition metal ion in close proximity may exhibit exchange-coupled spins. Polyanions with high-spin ground states and magnetic anisotropy are of technical interest in areas such as data storage and magnetic switches and so on. 4 In the past decades, much attention has been devoted to the synthesis of transition-metal substituted POMs with multiple, spin-coupled magnetic centers in the area known as molecular magnetism. 5 198
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