Synthesis and Structural Characterization of ... - Jacobs University

Chapter 1
Introduction
Figure 1.17 Combined polyhedral/ball-and-stick representation of
[KP 8 W 48 O 184 (H 4 W 4 O 12 ) 2 Ln 2 (H 2 O) 10 ] 25− . Note that the K + ion is disordered over 2 positions,
and the two Ln 3+ ions are disordered over four positions (for details see reference 49). The
color code is as follows: tungsten octahedra WO 6 (red and yellow), lanthanide (blue),
potassium (grey), and oxygen (red).
1.7.3 Mixed lanthanide / d‐transition metal ions containing POMs
Few examples in literature on mixed incorporation of lanthanides and d-transition metal ions
into POMs (also known as 3d-4f heterometalic POMs) are known. 53−57 Krebs et al.
successfully synthesized [((VO) 2 Dy(H 2 O) 4 K 2 (H 2 O) 2 Na(H 2 O) 2 )(α-B-AsW 9 O 33 ) 2 ] 8− , which is
constructed from two trilacunary Keggin anions, two VO 2+ and one Dy 3+ ion forming a
sandwich-type structure with C 2v symmetry; the magnetic properties of this compound were
also studied. 53 Kögerler et al. reported two compounds, 54 [(CH 3 ) 2 NH 2 ] 6 H 2 [{α-
P 2 W 16 O 56 (OH) 2 }{Ce IV Mn IV 6O 9 (O 2 CCH 3 ) 8 }]·20H 2 O and K 36 Na 11 [{α-P 2 W 15 O 56 } 6 {Ce 3 Mn 2 (μ 3-
O) 4 (μ 2- OH) 2 } 3 (μ 2- OH) 2 (H 2 O) 2 (PO 4 )]·106H 2 O, which were synthesized by interaction of the
high oxidation state heterometallic clusters [CeMn 6 O 9 (O 2 CCH 3 ) 9 (NO 3 )(H 2 O) 2 ] and
[Ce IV 3 Mn IV 2 O 6 (OH) 2 ] 6+ respectively with the tri-vacant Wells-Dawson phosphotungstate [α-
33