Chapter 4 - Jacobs University

Figure 5.4 ORTEP view of the asymmetric unit of the centrosymmetric polyanion 3 with atom
labeling (50% probability displacement ellipsoids; H atoms have been omitted for
clarity)……………………………………………………………………………….97
Figure 5.5 Side-view of 3 showing that the four organoruthenium units are grafted near the rim
of the central cavity, with the hydrophobic p-cymene groups protruding away from
the hydrophilic polyanion……………………………………………………………99
Figure 5.6 Solution 31 P NMR spectrum of 3a in D 2 O at room temperature…………………...102
Figure 6.1 FTIR of 4a prepared as KBr disk (showing only the POM fingerprint region)……110
Figure 6.2 Thermogram of 4a from room temperature to 900 °C under N 2 gas……………….110
Figure 6.3. Combined polyhedral/ball and stick representations of 4. The side- view (upper)
shows the U-shaped “P 6 W 36 ” POM ligand into which the two neutral [(UO 2 )(O 2 )] 4
units are incorporated. The top-down view (lower) from the “open” side of 4 (with
the central “P 2 W 12 ” POM fragment in the back removed for clarity) highlights that
the two uranyl-peroxo clusters are (i) connected via four potassium ions (K1, K2,
K3, K4) and (ii) displaced towards one side of the “P 6 W 36 ” POM. The concave
surface of the “outer” [(UO 2 )(O 2 )] 4 unit is capped by the square-pyramidal Li1
whereas the “inner” [(UO 2 )(O 2 )] 4 unit is capped by the seven-coordinate K8. Color
code: WO 6 octahedra (red), PO 4 tetrahedra (yellow), uranium (green), phosphorus
(yellow), potassium (pink), lithium (blue) and oxygen (red)…………………. ….114
Figure 6.4 Ball-and-stick representations of the two uranium-peroxo squares in 4. The upper
[(UO 2 )(O 2 )] 4 is located at the “top” of 4 (i.e. capped by Li1) whereas the lower
[(UO 2 )(O 2 )] 4 is located at the “bottom” of 4 (i.e. capped by K8). The color code is
the same as in Figure 6.3…………………………………………………………...116
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