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Chapter 3 Published Results Table 3.1. (continued): Crystal Data and Structure Refinement for NaLa-1 – Na-10. Code Na-6 Na-7 Na-8 NaLu-9 Na-10 Empirical formula H 112Er 2Na 8O 128W 22 H 104Tm 2Na 8O 125W 22 H 114Yb 2Na 8O 130W 22 H 110Lu 3Na 5 O 128W 22 H 114Y 2Na 8O 130W 22 MW 6723.73 6671.02 6769.30 6843.13 6601.35 Crystal system Triclinic Triclinic Triclinic Triclinic Triclinic Space group (no.) P1̅ (2) P1̅ (2) P1̅ (2) P1̅ (2) P1̅ (2) aÅ 12.546(4) 12.5155(11) 12.5045(6) 12.172(3) 12.5441(17) bÅ 14.124(5) 12.6622(14) 12.6590(7) 12.465(3) 14.107(2) cÅ 17.720(6) 18.3682(17) 18.3630(11) 19.469(5) 17.689(3) ° 72.166(18) 98.285(6) 98.284(4) 78.041(13) 71.931(9) ° 75.056(17) 95.498(5) 95.477(3) 77.672(15) 75.018(8) ° 83.375(16) 93.339(6) 93.339(3) 86.625(11) 83.382(7) V/Å 3 2885.7(16) 2859.6(5) 2855.6(3) 2823.0(12) 2872.5(8) Z 1 1 1 1 1 T/ ºC -100(2) -100(2) -100(2) -100(2) -100(2) λÅ 0.71073 0.71073 0.71073 0.71073 0.71073 D/ Mg m -3 3.88 3.93 3.85 3.88 3.82 μ/ mm -1 23.42 23.71 23.82 24.18 23.08 R[I >2sigma(I)] a 0.106 0.049 0.043 0.048 0.034 R w (all data) b 0.280 0.127 0.123 0.122 0.088 a R = ∑|F o | – |F c | |∑| |F o |. b R= ∑w(F o 2 | – |F c 2 ) 2 | /∑w(F o 2 ) 2 ] 1/2 . 57
Chapter 3 Published Results 3.A.1.4. Results and Discussion The ten novel lanthanide containing isopolytungstates [Ln 2 (H 2 O) 10 W 22 O 71 (OH) 2 ] 8− (Ln = La (1), Ce (2), Tb (3), Dy (4), Ho (5), Er (6), Tm (7), Yb (8), Lu (9), Y (10)) have been prepared by reaction of WO 2- 4 and lanthanide ions in a ratio of 11:1 in aqueous medium at pH 2.2. We discovered that three parameters are crucial for the successful formation of pure salts of 1-10: reaction temperature, concentration of reagents, and pH of the solution. For example, the lanthanum analogue 1 forms only if the solution is heated. If the synthesis is performed at room temperature, a different product is formed as based on IR which has not been fully characterized yet but appears to be {W 56 } based on preliminary crystal structures (vide infra). On the other hand, the cerium analogue 2 forms only at room temperature and is isolated as a second batch using fractional crystallization. The first crop of crystals appears to be identical with the room temperature product of the La synthesis described above, as based on IR. If the synthesis solution of 2 is heated, the well-known metatungstate ion [H 2 W 12 O 40 ] 6− is formed. Polyanions 3–10 also form upon heating, but the yield is much higher at room temperature. The yield is also affected by the concentration of the starting material. A tungstate concentration as high as 1.5 M is needed to obtain a pure crystalline product. Lower concentrations result in lower yields and non-crystalline powder as the main product. It is interesting that formation of a considerable amount of unidentified precipitate was also detected during the optimal synthetic procedure, which partially accounts for the low yields observed. This precipitate had an IR signature different from 1–10. Finally, we discovered that the pH of the reaction solution affects the formation and yields of compounds 1–10. A pH window of 2.0-3.5 can be considered for a successful synthetic procedure, with a pH of 2.2 being optimal. A pH lower than 2.0 did not result in any product, and a pH higher than 3.5 produced paradodecatungstate ([H 2 W 12 O 42 ] 10− ) as the main product. 58
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