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Chapter 3 Published Results 3.A.2.4. Results and Discussion We have synthesized and structurally characterized the V-shaped polyanions [Ln 2 (H 2 O) 10 W 28 O 93 (OH) 2 ] 14− (Ln = Sm (11), and Eu (12)) by one-pot reactions of Ln 3+ and WO 4 2- in aqueous acidic medium. The sodium salt Na 14 [Sm 2 (H 2 O) 10 W 28 O 93 (OH) 2 ]·40H 2 O (Na-11) and the mixed sodium-europium salt Na 8 Eu 2 [Eu 2 (H 2 O) 10 W 28 O 93 (OH) 2 ]·47H 2 O (NaEu-12) have been characterized in the solid state by FTIR, single-crystal XRD, thermogravimetric analysis (TGA), and elemental analysis. The polyanions 11 and 12 comprise a novel isopolyanion [H 2 W 28 O 95 ] 20− unit and two {Ln(H 2 O) n } 3+ supporting groups (see Figure 3.12). The {W 28 } cluster, which consists of two undecatungstate {W 11 } fragments and a hexatungstate fragment {W 6 }, coordinates to the two Ln 3+ ions acting as a tri- and tetradentate ligand, respectively. The Ln 3+ ions of 11 and 12 are nine-coordinated with a distorted monocapped square antiprismatic geometry. One of the Ln 3+ ions is coordinated to the two {W 11 } subunits by four -oxo bridges with average Ln-O distances of 2.50(2) Å for 11 and 2.46(2) Å for 2. The other Ln 3+ ion is coordinated to the two {W 11 } subunits and the {W 6 } subunit by three -oxo bridges (one O atom from each subunit) with average Ln-O distances of 2.48(1) Å for 11 and 2.46(2) Å for 12. A fourth oxo-bridge acts as a linker to another {W 28 }, forming a {Ln 4 W 56 } assembly ([Ln 2 (H 2 O) 10 W 28 O 93 (OH) 2 ] 14− ) 2 , see Figure 3.13. The remaining coordination sphere is filled by aqua ligands. Hence the {Ln 4 W 56 } structure can be described as a dimeric entity composed of two half units of [Ln 2 (H 2 O) 10 W 28 O 93 (OH) 2 ] 14− related by an inversion center, resulting in point symmetry C i . 81
Chapter 3 Published Results Figure 3.12. Representation of the V-shaped polyanions [Ln 2 (H 2 O) 11 W 28 O 93 (OH) 2 ] 14− (Ln = Sm, 11; Eu, 12). The color code is as follows: WO 6 octahedra (red and geen); Ln (blue); H 2 O (pink); O (red). In the solid state the “red” oxo ligand links two {W 28 } units via an Ln–O–W’ bridge (see also Figure 3.13). The two types of subunits were colored differently for clarity. 82
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