School of Engineering and Science - Jacobs University

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Table of Contents Abstract . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . List of Figures . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . List of Tables . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . i xi xvi 1 Introduction 1 1.1 Historical perspectives . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1 1.1.1 The clathrate-like structure . . . . . . . . . . . . . . . . . . . . . . 4 1.1.2 Chemical elements taking part in POMs . . . . . . . . . . . . . . . 4 1.1.3 Features of POMs . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5 1.2 Geometric Structures of representative types of Polyanions: Keggin, Lindqvist, Anderson-Evans and Wells-Dawson . . . . . . . . . . . . . . . . . . . . . . 6 1.3 Lacunary Species . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 10 2 Experimental 18 2.0.1 Reagents . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 18 2.1 Instrumentation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 18 2.1.1 Infrared spectroscopy . . . . . . . . . . . . . . . . . . . . . . . . . . 18 2.1.2 Single crystal X-ray diffraction . . . . . . . . . . . . . . . . . . . . . 18 2.1.3 Multinuclear magnetic resonance spectroscopy . . . . . . . . . . . . 19 2.1.4 Cyclic voltametry . . . . . . . . . . . . . . . . . . . . . . . . . . . . 19 2.1.5 Elemental analyses and thermogravimetric analysis . . . . . . . . . 19 2.2 Preparation of starting materials . . . . . . . . . . . . . . . . . . . . . . . 20 2.2.1 Synthesis of Na 9 [AsW 9 O 33 ]·27H 2 O . . . . . . . . . . . . . . . . . . 20 2.2.2 Synthesis of Na 9 [SbW 9 O 33 ]·27H 2 O . . . . . . . . . . . . . . . . . . . 20 2.2.3 Synthesis of K 14 [As 2 W 19 O 67·(H 2 O)] . . . . . . . . . . . . . . . . . . 20 2.2.4 Synthesis of A & B Na 8 [HAsW 9 O 34 ]·11H 2 O (A & B-Type AsW 9 O 34 ) 21 2.2.5 Synthesis of A-Na 9 [PW 9 O 34 ]·7H 2 O . . . . . . . . . . . . . . . . . . 21 2.2.6 Synthesis of Cs 6 [P 2 W 5 O 23 ]·H 2 O . . . . . . . . . . . . . . . . . . . . 21 2.2.7 Synthesis of Cs 7 [PW 10 O 36 ]·H 2 O . . . . . . . . . . . . . . . . . . . . 22 2.2.8 Synthesis of Na 20 [P 6 W 18 O 79 ]·37.5H 2 O . . . . . . . . . . . . . . . . . 22 viii
2.2.9 Synthesis of K 12 [H 2 P 2 W 12 O 48 ]·24H 2 O . . . . . . . . . . . . . . . . . 22 2.2.10 Synthesis of K 16 Li 2 [H 6 P 4 W 24 O 94 ]·33H 2 O . . . . . . . . . . . . . . . 23 2.2.11 Synthesis of K 28 Li 5 [H 7 P 8 W 48 O 184 ]·92H 2 O . . . . . . . . . . . . . . . 23 2.2.12 Synthesis of Na 27 [NaAs 4 W 40 O 140 ]·60H 2 O . . . . . . . . . . . . . . . 23 2.2.13 Synthesis of K 8 [γ-SiW 10 O 36 ]·20H 2 O . . . . . . . . . . . . . . . . . . 23 2.2.14 Synthesis of K 7 [PW 11 O 39 ]·14H 2 O . . . . . . . . . . . . . . . . . . . 24 2.2.15 Synthesis of K 14 [P 2 W 19 O 69 (H 2 O)]·24H 2 O . . . . . . . . . . . . . . . 24 3 Results 26 3.1 The hybrid organic-inorganic 2-D material (CsNa 4 [{Sn(CH 3 ) 2 } 3 O(H 2 O) 4 (β-XW 9 O 33 )]·5H 2 O) ∞ (X = As III , Sb III ) and its solution properties . . . . . . . . . . . . . . . . 26 3.1.1 Experimental . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 26 3.1.2 Results and discussion . . . . . . . . . . . . . . . . . . . . . . . . . 30 3.1.3 Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 34 3.2 The tetrakis-dimethyltin containing tungstophosphate ({Sn(CH 3 ) 2 } 4 {H 2 P 4 W 24 O 92 } 2 ) 28− evidence for lacunary Preyssler ion . . . . . . . . . . . . . . . . . . . . . . 35 3.2.1 Experimental . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 35 3.2.2 Results and discussion . . . . . . . . . . . . . . . . . . . . . . . . . 37 3.2.3 Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 43 3.3 The trimeric-dimethyltin containing bowl shaped tungstophosphate(V): Cs 12 Na 6 {Sn(CH 3 ) 2 (OH)} 3 (Sn(CH 3 ) 2 ) 3 {A-PW 9 O 34 } 3·14H 2 O . . . . . . . . . . . . . . . . . . . . . . . 44 3.3.1 Experimental . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 44 3.3.2 Results and discussion . . . . . . . . . . . . . . . . . . . . . . . . . 46 3.3.3 Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 50 3.4 The tetrameric, chiral tungstoarsenate(III), ({Sn(CH 3 ) 2 (H 2 O)} 2 {Sn(CH 3 ) 2 }As 3 {α-AsW 9 O 33 } 4 ) 21− . . . . . . . . . . . 51 3.4.1 Experimental . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 51 3.4.2 Results and discussion . . . . . . . . . . . . . . . . . . . . . . . . . 52 3.4.3 Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 55 3.5 The gigantic, ball-shaped heteropolytungstates ({Sn(CH 3 ) 2 (H 2 O)} 24 {Sn(CH 3 ) 2 } 12 (A-XW 9 O 34 ) 12 ) 36− (X= P V , As V ) . . . . 56 3.5.1 Experimental . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 56 3.5.2 Results and discussions . . . . . . . . . . . . . . . . . . . . . . . . . 60 3.5.3 STM studies of Cs-6 . . . . . . . . . . . . . . . . . . . . . . . . . . 63 3.5.4 HPPS measurement . . . . . . . . . . . . . . . . . . . . . . . . . . . 67 ix
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: Paris-Sud, Orsay Cedex, France) for
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 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
Page 119 and 120:
472(w), 444(w) cm −1 . This proce
Page 121 and 122:
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
Page 129 and 130:
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
Page 163 and 164:
were applied and an absorption corr
Page 165 and 166:
Fig. 3.75: Size distribution by num
Page 167 and 168:
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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