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List of Figures 1.1 Polyhedral models of the three possible unions between two MO 6 octahedral units. A) corner-sharing,B) edge-sharing and C) face-sharing . . . . . . . . 3 1.2 Ball and stick represention of the α Keggin type cluster; the black balls represent tungsten and the red balls represent oxygen . . . . . . . . . . . . 5 1.3 Ball/stick and polyhedral representation of the alpha isomer of the Keggin structure with different types of oxygen. Color codes: The blue polyhedra represent the tungsten and the red balls represent oxygen . . . . . . . . . . 7 1.4 Combined polyhedral/ball and stick representation of [Cu 3 Na 3 (H 2 O) 9 (α- As III W 9 O 33 ) 2 ] 9− . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 8 1.5 Combined polyhedral/ball and stick representation of {(O 3 POPO 3 )Mo 6 O 18 } 4− 8 1.6 Ball and stick representation of the Lindqvist structure . . . . . . . . . . . 9 1.7 Polyhedron representation of the Anderson structure . . . . . . . . . . . . 9 1.8 Ball and stick representation of the Wells-Dawson structure . . . . . . . . . 10 1.9 Schematic representation of the formation of Keggin-type lacunary. Courtesy: Dr. Santiago C. Reinoso . . . . . . . . . . . . . . . . . . . . . . . . . 11 1.10 Schematic representation of the formation of Keggin- and Wells-Dawson type lacunary species in tungsto-phosphate system with respect to pH.Courtesy: Dr. Santiago C. Reinoso . . . . . . . . . . . . . . . . . . . . . . . . . . . . 13 1.11 Monomeric (left) and dimeric species (right) of monoorganotin containing polyoxotungstates. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 16 3.1 FTIR spectra of compound CsNa-1(red) and Na 9 [α-AsW 9 O 33 ] (blue) . . 27 3.2 FTIR spectra of compound CsNa-2(red) and Na 9 [α-SbW 9 O 33 ](blue) . . . 28 3.3 W 183 NMR spectra of (CsNa 4 [{Sn(CH 3 ) 2 } 3 O(H 2 O) 4 ( β-XW 9 O 33 )]·5H 2 O) ([X = As (top)CsNa-1, Sb (bottom)CsNa-2] . . . . . . . . . . . . . . . . 30 3.4 Sn 119 NMR spectra of (CsNa 4 [{Sn(CH 3 ) 2 } 3 O(H 2 O) 4 ( β-XW 9 O 33 )]·5H 2 O) [X = As (top)CsNa-1, Sb(bottom)CsNa-2] . . . . . . . . . . . . . . . . . 31 xii
3.5 Left: combined polyhedral and ball/stick representation of the 2-D solid state structure of (CsNa 4 [{Sn(CH 3 ) 2 } 3 O(H 2 O) 4 (β-XW 9 O 33 )]·5H 2 O) ∞ (X = As, CsNa-1; Sb, CsNa-2). The WO 6 octahedra are purple and the balls represent tin (green), arsenic/antimony (blue), oxygen (red) and carbon (yellow). Hydrogen atoms are omitted for clarity (left),Right: Side view of the 2-D solid state structure of (CsNa 4 [{Sn(CH 3 ) 2 } 3 O(H 2 O) 4 (β- XW 9 O 33 )]·5H 2 O) ∞ (X = As, CsNa-1; Sb, CsNa-2). . . . . . . . . . . . . 32 3.6 Left:Ball and stick representation of [{Sn(CH 3 ) 2 } 3 O(H 2 O) 4 (β-XW 9 O 33 )] 3− (X = As,1; Sb,2.(A) The balls represent tungsten (black), tin (green), arsenic/antimony (blue), oxygen (red), carbon (yellow) and hydrogen (small black); Right:Combined polyhedral/ball and stick representation of the [{Sn(CH 3 ) 2 } 3 O(H 2 O) 4 (β-XW 9 O 33 )] 3− (X = As, 1; Sb, 2).(B) The WO 6 octahedra are red and the color codes of balls are same as above . . . . . . 33 3.7 FTIR spectra of compound KLi-3(red) and K 16 Li 2 [H 6 P 4 W 24 O 94 ] (blue) . . 35 3.8 Ball and stick (left), Polyhedron (right) representation of polyanion 3 . . . 37 3.9 Ball and stick representation of the asymmetric unit of polyanion 3 . . . . 38 3.10 Cyclic voltammogram of 2 × 10 −4 M solution of 3 in a pH 4 medium (1 M CH 3 COOLi + CH 3 COOH). The scan rate was 10 mV.s −1 , the working electrode was glassy carbon and the reference electrode was SCE. (A) The whole voltammetric pattern(left), (B) The voltammetric pattern restricted to the first redox processes (right) . . . . . . . . . . . . . . . . . . . . . . . 40 3.11 Comparison of the cyclic voltammograms of 2 × 10 −4 M solution of 3 in a pH 4 medium (1 M CH 3 COOLi + CH 3 COOH). The scan rate was 10 mV.s −1 , the working electrode was glassy carbon and the reference electrode was SCE. (A) Comparison of the voltammetric patterns of 3 and [H 2 P 4 W 24 O 94 ] 22− (left)(B) Comparison of the voltammetric patterns of 3 and [H 7 P 8 W 48 O 184 ] 33 (right) . . . . . . . . . . . . . . . . . . . . . . . . . . 41 3.12 FTIR spectra of compound CsNa-4(red) and Na 9 [(A-α-PW 9 O 34 )](blue,) . 44 3.13 Ball/stick (left) and Polyhedron (right) representation of polyanion 4 . . . 46 3.14 The central core of Sn(CH 3 ) 2 2+ connected to each other by three (µ 2 -OH) bridges . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 48 3.15 Cyclic voltammogram of 2 × 10 −4 M solution of 4 in a pH 4 medium (1 M CH 3 COOLi + CH 3 COOH). The scan rate was 10 mV.s −1 , the working electrode was glassy carbon and the reference electrode was SCE. (A) Superposition of the CVs restricted to the first redox pattern for trimer and A-α-PW 9 O 34 respectively.(left), (B) Complete CV for the trimer showing the presence of a second irreversible wave close to the electrolyte discharge. (right) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 49 xiii
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: Bibliography . . . . . . . . . . .
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 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
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electrochemical set-up was an EG &
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Fig. 3.14: The central core of Sn(C
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of these fragments [88, 90]. For co
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diffractometer using Mo K α radiat
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Fig. 3.18: Side view of [{Sn(CH 3 )
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host−guest systems with large cav
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X-ray Crystallography Single crysta
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3.5.2 Results and discussions Polya
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Fig. 3.26: Ball and stick represent
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can distinguish between different m
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Fig. 3.28: STM pictures of {Sn(CH 3
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Fig. 3.31: Size distribution by int
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3.6 The bis-phenyltin substituted,
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Table 3.7: Crystal Data and Structu
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tral belt in-between the two tin at
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Fig. 3.35: 183 W NMR spectra of com
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whereas they are five-coordinated (
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investigated by scanning tunneling
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3.8 The di-titanium substituted, lo
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Fig. 3.37: Ball/stick (left), polyh
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[As 2 W 19 O 67 (H 2 O)] 14− , [A
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3.9 The cyclic trimeric-titanium su
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Table 3.9: Crystal Data and Structu
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Fig. 3.40: FTIR spectra of compound
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Fig. 3.42: Side-view of compound 11
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11 by 183 W-NMR (at 16.66 MHz on a
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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
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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
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Fig. 3.49: Combined polyhedral/ball
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Fig. 3.50: 183 W NMR spectrum of [I
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(17) are isostructural. They consis
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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
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NMR Spectra Fig. 3.54: 13 C NMR spe
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Fig. 3.56: 31 P NMR spectrum of pol
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Fig. 3.58: 13 C NMR spectrum of pol
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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
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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
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Publications 1. Observation of a Ha
Page 175 and 176:
PAPERS IN CONFERENCE/ SYMPOSIA / WO
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