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2.2.10 Synthesis of K 16 Li 2 [H 6 P 4 W 24 O 94 ]·33H 2 O 8 g of K 12 [α-H 2 P 2 W 12 O 48 ]·24H 2 O was dissolved in 250 mL of 1 M aqueous solution of LiCl acidified by 0.7 mL of CH 3 COOH. The solution was left for 4 hours at room temperature and then 50 mL of saturated KCl solution was added. The formed white precipitate was filtered off and washed with KCl solution and twice with ethanol. The precipitate was air dried overnight and It was than characterized by FTIR and 31 P-NMR spectroscopies and was compared with the published data [76]. 2.2.11 Synthesis of K 28 Li 5 [H 7 P 8 W 48 O 184 ]·92H 2 O 28 g of K 12 H 2 P 2 W 12 O 48·24H 2 O was dissolved in 1 litre of a mixture of LiCl (0.5 mol), LiOAc (0.5 mol) and CH 3 COOH (0.5 mol) in water. The solution was left open instead of being closed as published earlier. After 1 day white crystalline needles started appearing. The solution was left for a week for further crystallization. The crystalline material was filtered in a frit and kept for air drying. It was than characterized by FTIR and 31 P-NMR spectroscopies and was compared with the published data [76]. 2.2.12 Synthesis of Na 27 [NaAs 4 W 40 O 140 ]·60H 2 O 132 g (0.4 mol) of Na 2 WO 4·2H 2 O and 5.2 g (40 mmol) Na 2 AsO 3 were dissolved in 200 mL of distilled water at ∼80 ◦ C. 6 M HCl was added slowly with vigorous stirring until the final pH reached to 4.0. The solution was cooled and kept in refrigerator at ∼80 ◦ C , the solid crystalline product crystallizes slowly. One day is required for complete deposition. The white solid is collected on a filter paper and air dried. The synthesized product was characterized using FTIR spectroscopy and was compared with the published data [77]. 2.2.13 Synthesis of K 8 [γ-SiW 10 O 36 ]·20H 2 O To prepare γ-SiW 10 , at first β 2 -SiW 11 was prepared as follows 5.5 g (25 mMol)of Na 2 SiO 3·5H 2 O was dissolved in 50 mL of distilled water. (solution A) 91 g (0.25 mMol)of Na 2 WO 4·2H 2 O was dissolved in 150 mL of H 2 O in 1 liter beaker.(Solution B) 82.5 mL of 4 M HCl was added in 1 mL portion over 10 min. Solution A was added to solution B and the pH 23
was adjusted between 5-6 by addition of 4 M HCl for 100 min.( 1hr, 40 min) Later 4.45 g solid KCl was added to the resulting solution and stirred for 15 min to obtain solid white precipitate. This uncharacterized product is K salt of βSiW 11 . In order to obtain γ-SiW 10 , 15 g of K salt of βSiW 11 was dissolved in 150 mL of distilled water. Insoluble impurity was removed by filtering on a frit containing celite. The pH of the solution was adjusted to 9.1 with 2 M aqueous solution of K 2 CO 3 solution. The pH of this solution was kept at this value for exactly 16 minutes. 85 gm of KCl was added to it and stirred for 10 minutes. The pH was still maintained at 9.1. by adding 2 M aqueous solution of K 2 CO 3 solution. 40 g of solid KCl was added to obatin K-salt of γ-SiW 10 . The precipitate was dried overnight at 50 degree in hot air oven. It was characterized using FTIR spectroscopy and was compared with the published data [78]. 2.2.14 Synthesis of K 7 [PW 11 O 39 ]·14H 2 O To a solution of 181.5 g Na 2 WO 4·2H 2 O in 300 mL H 2 O was slowly added 50 mL of 1M H 3 P0 4 and 88 mL glacial acetic acid. This solution was refluxed for 1 hour and then cooled to room temperature. Addition of 60 g solid KCl leads to white precipitate which was collected after 10 minutes and air dried. The solid product was characterized using FTIR spectroscopy and was compared with the published data [79]. 2.2.15 Synthesis of K 14 [P 2 W 19 O 69 (H 2 O)]·24H 2 O The precursor was synthesized from the mixtures of K 7 PW 11 O 39 (aq) and Na 8 [HPW 9 O 34 ] (aq). A solution of Na 8 [HPW 9 O 34 ] (aq) (10.65 g , 3.75 mmol) was added to K 7 PW 11 O 39 (aq) (4.0 g 1.25 mmol), the pH reduced to 6-6.5 and the mixture was stirred and heated to 50 C. Solid KCl was added until a fine crystalline precipitate appeared . Further solid KCl about 3-4 g was then added. A white crystalline powder separated. Stirring was maintained until room temperature was reached. The product was then filtered off and washed with chilled water (10 mL). The solid product was characterized using FTIR spectroscopy and was compared with the published data [80]. 24
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: as Cs 6 [P 2 W 5 O 23 ]·7H 2 O by
Page 45 and 46: Chapter 3 Results 3.1 The hybrid or
Page 47 and 48: Fig. 3.2: FTIR spectra of compound
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
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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
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Fig. 3.47: 111 Cd NMR spectra of [C
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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
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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
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3.12.4 Conclusion We have synthesiz
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[37] D. Gatteschi, O. Kahn, J. Mill
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94:226403, 2005. [123] R. J. Hamers
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[206] I. Loose, E. Droste, M. Bösi
Page 149 and 150:
NMR Spectra Fig. 3.54: 13 C NMR spe
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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
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Fig. 3.62: 119 Sn NMR spectrum of p
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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
Page 169 and 170:
Fig. 3.80: FTIR spectra of compound
Page 171 and 172:
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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