Experimental Section - New Synthetic Routes to Polyoxometalate Containing Ionic Liquids - page 110

For the synthesis of (Q 7 ) 4 [ D -PW 11 O 39 Fe(H 2 O)] 5.00 g (1.61 mmol) of K 7 [PW 11 O 39 ] ڄ 9H 2 O
were dissolved in 100 ml of warm water (T = 60 °C). 0.456g (1.69 mmol, 1.05 eq.) of
FeCl 3 ڄ 6H 2 O were added in 20 ml of water and the reaction mixture stirred at 60 ι C for
1 h. For the phase transfer 3.10 g (6.34 mmol, 3.95 eq.) of Q 7 Br were dissolved in 80 ml
of toluene and added to the cooled down reaction mixture. The organic layer was
separated, the solvent removed under reduced pressure and the yellow highly viscous
product dried under vacuum for 24 h with several times lyophilizing.
Yield: 2.627 g (0.55 mmol, 39.6% based on Na 2 WO 4 ڄ 2H 2 O)
EA in wt. - % (calculated values in brackets): C 31.56 (30.61), H 5.68 (5.55), N 1.23 (1.28)
IR (characteristic bands in cm -1 ): 3471 (m), 2955/2928/2857 (s), 1481 (m), 1460 (m),
1379 (m), 1069 (m), 962 (s), 885 (m), 812 (m), 725 (w), 671 (w), 662 (w), 594 (w), 517
(w)
5.3.1.7 (Q 7 ) 6/7 [ D -BW 11 O 39 M(H 2 O)] M = Cu II /Fe III
For the synthesis of (Q 7 ) 7 [ D -BW 11 O 39 Cu(H 2 O)] the [ D -BW 11 O 39 Cu(H 2 O)] cluster was
isolated as K 7 [BW 11 O 39 Cu(H 2 O)] prior to its phase transfer in a second step. For the
formation of the cluster 18.15 g (0.055 mol) Na 2 WO 4 ڄ 2H 2 O were dissolved in 90 ml H 2 O
and the solutions pH adjusted to 6.3 with HNO 3 . 1.50 g (0.024 mol) of H 3 BO 3 were
added as solid and the solution heated to 85 ι C. After addition of 1.21 g (0.005 mol)
Cu(NO 3 ) 2 ڄ 3H 2 O the reaction mixture was stirred for 10 minutes at 85 ι C which formed a
green precipitate that slowly dissolved upon further heating at 85 ι C for 10 min. The
warm mixture was filtered through a folded paper filter and allowed to stand at room
temperature for two hours which caused the formation of light green crystals. These
were filtered off and the mother liquor salted out with 10 g of KCl. The resulting
turquoise-green precipitate was filtered off, washed with water and dried in the
exsiccator under reduced pressure for 5 days.
Yield K 7 [BW 11 O 39 Cu(H 2 O)]: 9.46 g (3.14 mmol, 29% based on Na 2 WO 4 ڄ 2H 2 O)