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Chapter 3 Unpublished Results Sb 2 W 22 precursor with transition metal ions or organometallic species at a proper pH is known to result in disubstituted products based on the Sb 2 W 20 framework. 5,6 For example, our group has already reported species with the organo-Ru-supported tungstoantimonates [Sb 2 W 20 O 70 (RuL) 2 ] 10– (L = benzene, p-cymene) 6g and organic–inorganic hybrid compounds based on dmso-coordinated heteropolytungstates. 6h A high concentration of NaCl (1.0 M) was also needed in order to obtain the desired crystalline products. The same reactions performed in water did not result in any crystalline product. The presence of sodium ions in the synthesis medium is therefore crucial for the successful synthesis and isolation of polyanions 15–20. Hence, the reaction procedures reported here were successful for the late lanthanide ions (Yb and Lu), and also for the early 4d metal ion yttrium. In contrast, the same synthetic procedures as 15–17 and 18–20 were tried for the early (La and Ce) and middle (Eu and Gd) lanthanide ions, but so far our attempts have not been successful. Polyanions 18–20 consist of two SbW 9 subunits sandwiching two tungsten ions forming Sb 2 W 20 unit which is coordinated to two lanthanide(III) ions leading to a structure with C 2h symmetry (see Figure 3.31). Hence this structure can be described as a dimeric molecular entity composed of two {LnSbW 10 } half units related by an inversion center. Each Ln 3+ is linked to the SbW 9 units through three -oxo bridges, two bridges to one SbW 9 half-unit and one bridge to the other half-unit through one WO 6 octahedral of the rotated triad (yellow in Figure 3.31). The two lanthanide ions are seven-coordinated with an average Ln−O distance of 2.274(12) Å, resulting in a pentagonal-bipyramidal coordination geometry. Both lanthanide ions have three terminal aqua ligands each. The coordination sphere of each lanthanide ion is completed through a Ln–O–W’ bridge, where W’ belongs to a neighbouring polyanion, leading to an 1-D chain formation in the solid state (see Figure 3.32). BVS calculations indicate that no oxygen atoms of 18–20 are protonated. 125
Chapter 3 Unpublished Results Figure 3.31. Polyhedral (left) and ball-and-stick (right) representation of [Ln 2 (H 2 O) 6 Sb 2 W 20 O 70 )] 8− (Ln = Yb (18), Lu(19), Y(20)). The color code is the same as in Figure 3.29. Figure 3.32. Polyhedral representation of polyanions 16-20 forming a 1D chain in the solid state. The color code is as follows: WO 6 octahedra (red), Sb (green), Ln (blue), H 2 O (pink), O (red). 126
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