Synthesis and Structural Characterization of ... - Jacobs University

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Chapter 5 Published Results resulting in icosahedral geometry. Since then some other POMs containing faceshared octahedra have been reported, but this feature still remains rare. 15 - One ditungstate {W 2 } subunit (pink in Figure 5.4) made of two edge-shared [WO 6 ] octahedra connected through two μ 2 -oxo bridges. These two types of the ditungstate subunits (face- and edge-shared octahedra) are connected through an edge and a corner forming a tetratungstate {W 4 } fragment (see Figure 5.4). - Three monotungstate {W 1 } fragments (red in Figure 5.4), which are connected to each other or to other fragments through corners. The {W 3 } subunit shares two corners with each of two adjacent {W 1 } subunits, one of them shares a corner with the {W 4 } subunit and the other one with the third {W 1 } subunit to build up the decatungstate {W 10 } unit, of which two are present in 26 (see Figures 5.3 and 5.4). Polyanion 26 represents the first example of a tellurium-containing polyanion exhibiting face-shared WO 6 octahedra and a coordination number of four for Te. Each tellurium(IV) ion is linked to the {W 10 } unit through three -oxo bridges and to the other {W 10 } unit through another -oxo bridge (see Figure 5.2). The eight -oxo bridges of the two tellurium(IV) ions can be described as follows: - A bridge to the {W 3 } subunit. - A bridge to the {W 2 } subunit (face-shared octahedra). - A bridge to the {W 2 } subunit (edge-shared octahedra). - Three bridges to the three {W 1 } subunits. - And two bridges to two {W 1 } subunits of the other {W 10 } unit. As shown in Figure 5.3, one tellurium(IV) ion is linked to two {W 2 } subunits and to one {W 1 } subunit. The other tellurium(IV) ion is linked to two other {W 1 } subunits and to the {W 3 } subunit. All these individual fragments are well-known. However, the {W 10 } unit in 26, which represents an assembly of distinct ‘building blocks’ (see Figure 5.4), has not been reported before. Most of the known polyanions containing face-shared octahedra are 175
Chapter 5 Published Results polymolybdates. Hence, 26 combines three important features previously unknown for tungstotellurate anions. First, the structure involves face-shared WO 6 octahedra; second, the {W 10 } unit coordinated to tellurium(IV) atoms is novel; and third, the tellurium atoms adopt a see-saw configuration. Another novel tungstotellurate(IV), [NaTeW 15 O 54 ] 13− (27), is present in a mixture of products if the synthesis solution of 26 is heated. Single-crystal X-ray diffraction analysis revealed that [NaTeW 15 O 54 ]·26H 2 O (Na-27) crystallizes in the orthorhombic space group Pccn. Polyanion 27 is composed of a triangular assembly of 15 edge- and corner-shared WO 6 octahedra, surrounding a trigonal-pyramidal tellurium(IV) center located in the central cavity and a capping sodium ion (Figure 5.5). The tellurium and the sodium atom, both closely associated with the polyanion, are disoredered showing 50 % occupancy for each. Polyanion 27 is composed of three identical {W 5 } building-blocks which are made up of five WO 6 octahedra. Figure 5.5. Ball-and-stick representations of [NaTeW 15 O 54 ] 13− (27). The color code is as the same as Figure 5.2. 176
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