Synthesis and Structural Characterization of ... - Jacobs University
Synthesis and Structural Characterization of ... - Jacobs University
Synthesis and Structural Characterization of ... - Jacobs University
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Chapter 5<br />
Unpublished Results<br />
5.A.2. Tellurium‐Containing Polyoxomolybdates:<br />
The 44‐Molybdo‐24‐Tellurate(IV), [H2Te24Mo44O198] 34−<br />
5.A.2.1. Introduction<br />
Polyoxometalates (POMs) represent a large class <strong>of</strong> nanosized metal-oxygen cluster anions.<br />
POMs are remarkable not only in terms <strong>of</strong> molecular <strong>and</strong> electronic structural versatility, but<br />
also due to their applications in many fields such as catalysis, medicine, electronics,<br />
multifunctional materials, <strong>and</strong> analytical chemistry. 1 In recent years there has been developing<br />
interest in these remarkable compounds <strong>of</strong> tungsten, molybdenum, vanadium, niobium, <strong>and</strong><br />
tantalum. POM clusters have been known for a long time (first prepared in 1826 by Berzelius)<br />
but the mechanism <strong>of</strong> their formation is still not completely understood, <strong>and</strong> is <strong>of</strong>ten described<br />
as “self-assembly”. 1a<br />
POMs are formed through condensation reactions <strong>of</strong> metalate ions in acidified solutions<br />
(usually aqueous), via aggregation <strong>of</strong> octahedral [MO 6 ] building blocks sharing corners, edges,<br />
<strong>and</strong> rarely faces. Many <strong>of</strong> the reported POMs are based on the well-known Keggin ion<br />
([XM 12 O 40 ] n– ), or lacunary fragments <strong>of</strong> that structure, where X is the central heteroatom <strong>and</strong><br />
M the addenda atom. The heteroatom can be one <strong>of</strong> many elements <strong>of</strong> the periodic table, most<br />
commonly P, As, Si, Ge or B.<br />
Also tellurium can act as a heteroatom, but the number <strong>of</strong> such POMs is rather limited. In<br />
1948 Evans reported the first structure <strong>of</strong> a tellurium containing polyanion, [TeMo 6 O 24 ] 6 . 2<br />
Many other inorganic salts <strong>of</strong> the Anderson-Evans type molybdotellurate(VI) [TeMo 6 O 24 ] 6–<br />
have been reported ever since. 3 Molybdotellurates containing organic counter-cations have<br />
also been described. 4<br />
The first examples <strong>of</strong> the Anderson-Evans type tungstotellurate<br />
[TeW 6 O 24 ] 6– were reported by Ganelina <strong>and</strong> Ripan. 5 Some examples <strong>of</strong> tellurium(IV)<br />
containing polymolybdates are also known. The manganese derivative <strong>of</strong> the classical<br />
184