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Chapter 3 Published Results [Ln 2 (H 2 O) 11 W 28 O 93 (OH) 2 ] 14− {W 28 }, this work Early lanthanides (La–Gd) WO 4 2- Ln 3+ containing solutions (pH~2) Late lanthanides (Tb–Lu) [Ln 2 (H 2 O) 10 W 22 O 72 (OH) 2 ] 8– {W 22 } Kortz 2008 10 Figure 3.16. Representation of the two structures of the {W 11 } units containing lanthanides. The color code is as follows: WO 6 octahedra (red and green); Ln (blue); H 2 O (pink), O (red). The single crystals of the La, Ce, Pr, Nd and Gd analogues of 11 and 12 were not of sufficient quality to finalize the refinements, but the data allowed to identify the heavy atoms (W and Ln) and enough oxygens to conclude that these polyanions are isostructural with 11 and 12. 13 On the other hand, the samarium (11) and europium (12) analogues were fully characterized by single-crystal XRD (see Table 3.3). The neodymium and gadolinium 87
Chapter 3 Published Results analogues of the {Ln 2 W 28 } family have almost the same unit cell parameters as Na-11, and the lanthanum, cerium and praseodymium analogues have also similar unit cell parameters. All compounds of the {Ln 2 W 28 } family (Ln = La, Ce, Pr, Nd, Sm, Eu and Gd) have similar IR spectra (see Figure 3.14). As mentioned above, the {W 28 } unit is an assembly comprising three distinct building blocks (see Figure 3.17): two undecatungstate subunits {W 11 } (red color) and a hexatungstate {W 6 } subunit (green color). The former consists of four distinct ‘elementary blocks’: one tetratungstate {W 4 } fragment formed from four edge-shared WO 6 octahedra connected through a μ 4 -oxo bridge, one tritungstate {W 3 } fragment formed from three edge-shared WO 6 octahedra connected through a μ 3 -hydroxo bridge, and two ditungstate {W 2 } fragments, each formed from two edge-shared WO 6 which share corners on one side. The hexatungstate {W 6 } subunit comprises six edge-shared WO 6 octahedra two of which have three fac terminal oxygens. These building blocks have been reported previously. The undecatungstate [H 4 W 11 O 38 ] 6– and hexatungstate [H 3 W 6 O 22 ] 5− subunits were first reported by Fuchs et al. in 1988 and 1993, respectively. 14 Recently Cronin’s group reported isopolyanions composed of two or three {W 11 } units. 15 However, to the best of our knowledge the 28-isopolyoxotungstate {W 28 }, which comprises two {W 11 } and one {W 6 } fragment linked via four oxo bridges, has not been reported yet. Notably, the two {W 11 } subunits in {W 28 } are analogous to the framework geometry of {W 22 } in our {Ln 2 W 22 } family (see Figure 3.12). 10 However, they are arranged in C s symmetry with the extra {W 6 } acting as a bridge in between them as opposed to C i symmetry in {W 22 }. The {W 28 } isopoly unit as such offers seven sites coordinating to the two Ln 3+ centers. Polyanions 11 and 12 represent the largest lanthanide-containing isopolytungstates to date. 88
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