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Chapter 5 Unpublished Results Each {Te 12 Mo 22 } unit can be considered as an assembly of three types of ‘building blocks’ (see Figure 5.11 and 5.12) and this unit can be considered as two caps and a belt. Each cap (a hexamolybdate {Mo 6 } subunit) consists of three building blocks: - One trimolybdate {Mo 3 } fragment (green in Figure 5.12) made of three edge-shared [MoO 6 ] octahedra connected via a μ 3 -oxo bridge. This fragment can be viewed as a single ‘triad’ of the well-known Keggin and Wells-Dawson structures. 1a - One dimolybdate {Mo 2 } subunit (red in Figure 5.12) made of two edge-shared [MoO 6 ] octahedra connected through two μ 2 -oxo bridges. - One monomolybdate {Mo 1 } subunit (blue in Figure 5.12). These three subunits ({Mo 3 }, {Mo 2 }, and {Mo 1 }) are connected to each other via three corners forming a hexamolybdate {Mo 6 } subunit. The {Mo 3 } subunit shares two corners with the adjacent {Mo 2 } and a corner with the {Mo 1 } subunit to build up this {Mo 6 } subunit. Belt ({Mo 10 } subunit) consists of two building blocks: - Two tetramolybdates {Mo 4 } subunits (red in Figure 5.12) made of four edge-shared [MoO 6 ] octahedra connected through six μ 2 -oxo bridges. - Two monomolybdate {Mo 1 } subunits (blue in Figure 5.12). These two types of the subunits ({Mo 4 } and {Mo 1 }) are connected to each other via corners forming a decamolybdate {Mo 10 } subunit. The two caps {Mo 6 } and the belt {Mo 10 } units are connected to each other via Te−O−Mo μ 2 - oxo bridges, through six Te 4+ ions each. The Te atoms have coordination number three and four leading to a trigonal-pyramidal and a see-saw coordination geometry. 191
Chapter 5 Unpublished Results {Mo 6 } unit {Mo 10 } unit {Mo 3 } unit {Mo 4 } unit {Mo 2 } unit {Mo 1 } unit {Mo 1 } units Figure 5.12. Polyhedral representation of the building blocks forming the hexa- and decamolybdates, {Mo 6 } and {Mo 10 }, units. The color code is as follow: Mo 3 (green), Mo 2 (red), Mo 1 (light blue), Mo 4 (red). The four subunits were colored differently for clarification. 192
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