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(54.0)% FTIR spectra for (CsNa 4 [{Sn(CH 3 ) 2 } 3 O(H 2 O) 4 (β-AsW 9 O 33 )]·5H 2 O) ∞ (CsNa- 1)(KBr disk): 954, 909, 870, 829, 760, 727, 688, 518, 476, 430 cm −1 (CsNa 4 [{Sn(CH 3 ) 2 } 3 O(H 2 O) 4 (β-SbW 9 O 33 )]·5H 2 O) ∞ (CsNa-2) The synthesis was iden- Fig. 3.1: FTIR spectra of compound CsNa-1(red) and Na 9 [α-AsW 9 O 33 ] (blue) tical to that of CsNa-1, with the exception that 2.0 g (0.80 mmol) Na 9 [α-SbW 9 O 33 ] was used instead of Na 9 [α-AsW 9 O 33 ]. In this case a total of 2.0 g (yield 79%) of crystalline product was obtained. Elemental analysis calcd. (found) for (CsNa 4 [{Sn(CH 3 ) 2 } 3 O(H 2 O) 4 (β- SbW 9 O 33 )]·5H 2 O) ∞ (MW = 3153.8): Cs 4.2 (3.9), Na 2.9 (2.8), Sn 11.3 (11.2), Sb 3.9 (3.8), W 52.5 (53.4)%. FTIR spectra for (CsNa 4 [{Sn(CH 3 ) 2 } 3 O(H 2 O) 4 ( β-SbW 9 O 33 )]·5H 2 O) ∞ (KBr disk): 951, 865, 820, 747, 677, 520, 473, 457, 422 cm −1 . All elemental analyses were performed by Kanti Labs Ltd. in Mississauga, Canada. The FTIR spectra were recorded on a Nicolet Avatar FTIR spectrophotometer in a KBr pellet. X-ray Crystallography Crystal data and structure refinement details for (CsNa 4 [{Sn(CH 3 ) 2 } 3 O(H 2 O) 4 (β-AsW 9 O 33 )] ·5H 2 O) ∞ CsNa-1 and (CsNa 4 [{Sn(CH 3 ) 2 } 3 O(H 2 O) 4 (β-SbW 9 O 33 )]·5H 2 O) ∞ CsNa-2 are summarized in Table 3.1. The respective crystals were mounted on a glass fiber for indexing and intensity data collection at 173 K on a Bruker D8 SMART APEX CCD single- 27
Fig. 3.2: FTIR spectra of compound CsNa-2(red) and Na 9 [α-SbW 9 O 33 ](blue) crystal diffractometer using Mo K α radiation (λ = 0.71073 Å). Direct methods were used to solve the structure and to locate the heavy atoms (SHELXS97). Then the remaining atoms were found from successive difference maps (SHELXL97). Routine Lorentz and polarization corrections were applied and an absorption correction was performed using the SADABS program.[81] Crystallographic data are summarized in Table 3.1. Solution NMR Solution NMR appears to be the most elegant technique to prove or disprove the existence of 1 and 2 in solution. It is well known that NMR of the addenda atoms (in this case tungsten) is the most sensitive analytical tool to obtain structural information of polyoxoanions in solution. The polymeric compounds CsNa-1 and CsNa- 2 are ideal for a multinuclear NMR study, because they contain several NMR-active, spin 1/2 nuclei and they are diamagnetic. Therefore we performed 183 W-, 119 Sn-, 1 H- and 13 C-NMR studies on (a) freshly synthesized solutions of CsNa-1 and CsNa-2 (see Experimental Section) and (b) solid CsNa-1 and CsNa-2 redissolved in water. Interestingly we obtained exactly the same results in both cases. NMR (D 2 O, 293 K) for 28
Page 1 and 2: Hybrid Organic-Inorganic Polyoxomet
Page 3 and 4: Abstract Polyoxometalates (POMs) ar
Page 5 and 6: the cubic system (space group I m¯
Page 7 and 8: AsW 9 O 32 OH) 2 ]·36H 2 O (RbNa-1
Page 9 and 10: Paris-Sud, Orsay Cedex, France) for
Page 11 and 12: 2.2.9 Synthesis of K 12 [H 2 P 2 W
Page 13 and 14: Bibliography . . . . . . . . . . .
Page 15 and 16: 3.5 Left: combined polyhedral and b
Page 17 and 18: 3.33 Combined polyhedron and ball/s
Page 19 and 20: List of Tables 1.1 Selected M-M dis
Page 21 and 22: MO 6 octahedra surrounding a centra
Page 23 and 24: 1.1.1 The clathrate-like structure
Page 25 and 26: 7(MoO 4 ) 2− + 8H + → [Mo 7 O 2
Page 27 and 28: Fig. 1.4: Combined polyhedral/ball
Page 29 and 30: This planar structure was originall
Page 31 and 32: [X 2 M 18 O 62 ] 6− , the D 3h We
Page 33 and 34: [P 2 W 19 O 68 (HO)] 14− , [P 2 W
Page 35 and 36: Fig. 1.11: Monomeric (left) and dim
Page 37 and 38: Chapter 2 Experimental 2.0.1 Reagen
Page 39 and 40: 2.2 Preparation of starting materia
Page 41 and 42: as Cs 6 [P 2 W 5 O 23 ]·7H 2 O by
Page 43 and 44: was adjusted between 5-6 by additio
Page 45: Chapter 3 Results 3.1 The hybrid or
Page 49 and 50: Fig. 3.3: W 183 NMR spectra of (CsN
Page 51 and 52: Fig. 3.5: Left: combined polyhedral
Page 53 and 54: formed upon crystallization and bot
Page 55 and 56: X-ray Crystallography A crystal of
Page 57 and 58: the presence of the four (CH 3 ) 2
Page 59 and 60: Fig. 3.10: Cyclic voltammogram of 2
Page 61 and 62: as a function of electrolyte compos
Page 63 and 64: was observed that could be traced t
Page 65 and 66: electrochemical set-up was an EG &
Page 67 and 68: Fig. 3.14: The central core of Sn(C
Page 69 and 70: of these fragments [88, 90]. For co
Page 71 and 72: diffractometer using Mo K α radiat
Page 73 and 74: Fig. 3.18: Side view of [{Sn(CH 3 )
Page 75 and 76: host−guest systems with large cav
Page 77 and 78: X-ray Crystallography Single crysta
Page 79 and 80: 3.5.2 Results and discussions Polya
Page 81 and 82: Fig. 3.26: Ball and stick represent
Page 83 and 84: can distinguish between different m
Page 85 and 86: Fig. 3.28: STM pictures of {Sn(CH 3
Page 87 and 88: Fig. 3.31: Size distribution by int
Page 89 and 90: 3.6 The bis-phenyltin substituted,
Page 91 and 92: Table 3.7: Crystal Data and Structu
Page 93 and 94: tral belt in-between the two tin at
Page 95 and 96: Fig. 3.35: 183 W NMR spectra of com
Page 97 and 98:
whereas they are five-coordinated (
Page 99 and 100:
investigated by scanning tunneling
Page 101 and 102:
3.8 The di-titanium substituted, lo
Page 103 and 104:
Fig. 3.37: Ball/stick (left), polyh
Page 105 and 106:
[As 2 W 19 O 67 (H 2 O)] 14− , [A
Page 107 and 108:
3.9 The cyclic trimeric-titanium su
Page 109 and 110:
Table 3.9: Crystal Data and Structu
Page 111 and 112:
Fig. 3.40: FTIR spectra of compound
Page 113 and 114:
Fig. 3.42: Side-view of compound 11
Page 115 and 116:
11 by 183 W-NMR (at 16.66 MHz on a
Page 117 and 118:
3.11 Structure and solution propert
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472(w), 444(w) cm −1 . This proce
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MHz in 10 mm tubes and the 111 Cd N
Page 123 and 124:
Fig. 3.47: 111 Cd NMR spectra of [C
Page 125 and 126:
in aqueous solution, so that the nu
Page 127 and 128:
of cadmium ions in 12 and 13 and it
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doubtedly 183 W-NMR, but the parama
Page 131 and 132:
K): (relative intensities in parent
Page 133 and 134:
Fig. 3.49: Combined polyhedral/ball
Page 135 and 136:
Fig. 3.50: 183 W NMR spectrum of [I
Page 137 and 138:
(17) are isostructural. They consis
Page 139 and 140:
Fig. 3.53: 183 W NMR spectrum of [I
Page 141 and 142:
3.12.4 Conclusion We have synthesiz
Page 143 and 144:
[37] D. Gatteschi, O. Kahn, J. Mill
Page 145 and 146:
94:226403, 2005. [123] R. J. Hamers
Page 147 and 148:
[206] I. Loose, E. Droste, M. Bösi
Page 149 and 150:
NMR Spectra Fig. 3.54: 13 C NMR spe
Page 151 and 152:
Fig. 3.56: 31 P NMR spectrum of pol
Page 153 and 154:
Fig. 3.58: 13 C NMR spectrum of pol
Page 155 and 156:
Fig. 3.60: 1 H NMR spectrum of poly
Page 157 and 158:
Fig. 3.62: 119 Sn NMR spectrum of p
Page 159 and 160:
Fig. 3.66: 1 H NMR spectrum of poly
Page 161 and 162:
Fig. 3.70: 13 C NMR spectrum of pol
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were applied and an absorption corr
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Fig. 3.75: Size distribution by num
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Table 3.16: Crystal Data and Struct
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Fig. 3.80: FTIR spectra of compound
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FIRASAT HUSSAIN International Unive
Page 173 and 174:
Publications 1. Observation of a Ha
Page 175 and 176:
PAPERS IN CONFERENCE/ SYMPOSIA / WO
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