Jozef Hodyl PhD Thesis - Theses - Flinders University

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groups and guest species are augmented by some level of π-π interaction. Therefore,synthesising the molecular receptor model, 49, was essential in examining whetherthree pendant arms would adequately provide a binding cavity capable of includingaromatic anionic species, as well as in developing a synthetic strategy that could alsobe used for silica attached receptors.2.2 Synthetic strategyThe strategy to accomplish the synthesis of both the silica attached receptors 94, 95and 96 and the model receptor, 49, requires preparation of tri-N-substituted cyclenprecursor ligands 46, 47 and 48, Figure 2.2. This necessitates attachment of thependant arms, to a mono-N-protected cyclen synthon. Literature precedent suggestedthat the mono-carbamate, 50, would be useful for this purpose, Figure 2.2. 10950 46, R = H47, R = (OCH 2 CH 2 ) 2 OH48, R = (OCH 2 CH 2 ) 3 OHFigure 2.2Mono-protected cyclen synthon, 50, and tri-N-substituted cyclen derivatives, 46, 47 and48.Anchorage of 46 - 48 to silica could then be effected by reaction with a silicasurface silanised with an appropriate alkoxysilane linker. In this work racemic 3-(glycidoxypropyl)trimethoxysilane, 32, (hereafter GPTS) was used to attach asuitably reactive linker to the silica surface, as shown in Figure 2.3.37
3233Figure 2.3Reaction of 3-(glycidoxypropyl)trimethoxysilane, 32, with silica to provide thesilanised surface capable of subsequently reacting with 46 - 48 to immobilise thereceptor on the surface.Preparation of model receptor, 49, requires attachment of a 2-hydroxyalkylpendant arm to the unsubstituted fourth aza group on the tri-N-substituted cyclenderivative 46. For this work the (S)-2-hydroxypropyl group was chosen. The opticalpurity of this group is essential if only a single diastereomer of the product, 51, is tobe formed.512.3 Synthesis of mono-protected cyclen synthonIn accord with the aims of this project a synthetic strategy was devised to prepare amono-protected cyclen synthon to facilitate tri-N-alkylation of cyclen withappropriately functionalised pendant arms. This is shown in Scheme 2.138
Page 1 and 2: Silica Immobilised MetalIon Activat
Page 3 and 4: ABSTRACTImmobilisation of functiona
Page 5: DECLARATIONI certify that this thes
Page 8 and 9: EtOHGPDMSGPDMESGPSGPTSethanolglycid
Page 10: CHAPTER ONEINTRODUCTION
Page 13 and 14: The focus of this work was to prepa
Page 15 and 16: sequestering anions has proved to b
Page 17 and 18: ange of pH due to its high basicity
Page 19 and 20: nitrophenol or p-nitrophenolate wit
Page 21 and 22: It has been shown by NMR and crysta
Page 23 and 24: within the cavity of a p-tert-butyl
Page 25 and 26: 60 in 0.5% DMSO-MeCN (v/v). 82 The
Page 27 and 28: synthesised bi- tri- and tetra - π
Page 29 and 30: adopt a trans-III conformation, whe
Page 31 and 32: amide oxygen atoms on the pendant a
Page 33 and 34: apparent there is, nonetheless, evi
Page 35 and 36: However, hetero-N-substitution on t
Page 37 and 38: Si-OH +- OH SiO - + H 2 OFor surfac
Page 39 and 40: 35This material was obtained with a
Page 41 and 42: OOSiOHOROR OSiOHOOOSiOSiOSiOSiOSiOS
Page 43 and 44: Tetraaza metal complexes immobilise
Page 45 and 46: CHAPTER TWOSYNTHESIS OF MACROCYCLIC
Page 47: In addition, successful immobilisat
Page 51 and 52: The methodology chosen was adapted
Page 53 and 54: agreed with literature values. 109R
Page 55 and 56: XS HO O H61, n = 262, n = 3n+ClOSO6
Page 57 and 58: anhydrous ethanol, Scheme 2.7. The
Page 59 and 60: 75Figure 2.5 Structure of (S)-(-)-p
Page 61 and 62: metal ion coordination the pendant
Page 63 and 64: CHAPTER THREEGUEST MOLECULE INCLUSI
Page 65 and 66: 3.1 where K A is the association, o
Page 67 and 68: 0.5cχG∆δ∆δGbaχ GFigure 3.1S
Page 69 and 70: χG∆δ∆δGFigure 3.4 Job's Plot
Page 71 and 72: The downfield movement of the guest
Page 73 and 74: arm framework. The relative magnitu
Page 75 and 76: This phenomenon correlates well wit
Page 77 and 78: non-classical hydrogen bonding is g
Page 79 and 80: The full set of logK values obtaine
Page 81 and 82: such that they would indicate precl
Page 83 and 84: CHAPTER 4MODIFICATION OF THE SILICA
Page 85 and 86: Chemical modification of the silica
Page 87 and 88: GPTSGPDMESFigure 4.4Schematic depic
Page 89 and 90: GPS, 33, linker material with an ex
Page 91 and 92: free νOHτSiOHνSi-O-SiδH 2 Oasym
Page 93 and 94: 224, 225the surface silanol groups.
Page 95 and 96: esonances, the spectrum for Si-GPS-
Page 97 and 98: increase in surface coverage from t
Page 99 and 100:
and, more so due to the larger size
Page 101 and 102:
CHAPTER 5METAL ION UPTAKE STUDIES W
Page 103 and 104:
Scheme 5.1 Metal(II) ion coordinati
Page 105 and 106:
linker material, Si-GPS, 33; endcap
Page 107 and 108:
[Cd(Trac)](ClO 4 ) 2 , 94, or Si-GP
Page 109 and 110:
CHAPTER 6GUEST MOLECULE INCLUSION S
Page 111 and 112:
and D-histidinate. Guest inclusion
Page 113 and 114:
Table 6.2Percent inclusion data for
Page 115 and 116:
contains two hydroxy groups in the
Page 117 and 118:
methoxy group, as portrayed by the
Page 119 and 120:
these guest molecules with receptor
Page 121 and 122:
only about half of that taken up by
Page 123 and 124:
Percent inclusion values for these
Page 125 and 126:
Table 6.7Percent guest inclusion of
Page 127 and 128:
6.1.7 Guest inclusion studies with
Page 129 and 130:
A1 3542Neutral GuestBAnionic GuestH
Page 131 and 132:
A1 46 7532 Anionic Guest8BCHostHost
Page 133 and 134:
extent, meta-positioned hydroxy gro
Page 135 and 136:
δ obs (ppm)6.2146.2136.2126.2116.2
Page 137 and 138:
CHAPTER 7EXPERIMENTAL7.1 General Ex
Page 139 and 140:
inding constants (logK values) and
Page 141 and 142:
delay time of 4 s. 13 C CPMAS NMR s
Page 143 and 144:
C, -CH 2 - CH 2 OSO 2 ); 68.11 (1 C
Page 145 and 146:
A solution of 69 (2.00 g, 10.1 mmol
Page 147 and 148:
Bn, meta); 127.79 (1 C, Bn, para);
Page 149 and 150:
added in a single portion. The mixt
Page 151 and 152:
dioxane): δ 158.67 (1 C, C=O); 135
Page 153 and 154:
1-(benzyloxycarbonyl)-4,7,10-tris-(
Page 155 and 156:
1,4,7-tris-((S)-2-hydroxy-3-phenoxy
Page 157 and 158:
1,4,7-tris(S)-2-hydroxy-3-[4-((2-(2
Page 159 and 160:
1,4,7-tris(S)-2-hydroxy-3-[4-(2-(2-
Page 161 and 162:
1-(2-hydroxypropyl)-4,7,10-tris-((S
Page 163 and 164:
7.11 Preparation of the silica mate
Page 165 and 166:
To a suspension of 33 (1.48 g, 1.1
Page 167 and 168:
gel-like suspension that was cooled
Page 169 and 170:
Si-GPS-Tri-Trac, 4545The title comp
Page 171 and 172:
APPENDIX ABINDING CONSTANT DETERMIN
Page 173 and 174:
1.01000.880δ obs (ppm)0.60.4logK =
Page 175 and 176:
APPENDIX BDETERMINATION OF STOICHIO
Page 177 and 178:
0.5χG∆δGFigure B.2χ GSimulated
Page 179 and 180:
13 C CPMAS NMR SPECTRA OF SOME HIGH
Page 181 and 182:
Si-GPS-[Cd(Trac)(2,5-diydroxybenzoa
Page 183 and 184:
REFERENCES
Page 185 and 186:
15. D. Tzalis and Y. Tor, Tetrahedr
Page 187 and 188:
42. A. P. Davis and R. S.Wareham, A
Page 189 and 190:
69. R. J. Bergeron, M. A. Channing
Page 191 and 192:
93. C. B. Smith, A. K. W. Stephens,
Page 193 and 194:
118. D. D. Dischino, E. J. Delaney,
Page 195 and 196:
144. X. Huang, X. Chang, Q. He, Y.
Page 197 and 198:
169. J. M. Klunder, T. Onami and K.
Page 199 and 200:
197. K. A. Connors, Binding Constan
Page 201 and 202:
221. J. Blumel, J. Am. Chem. Soc.,
Page 203:
247. W. Likussar and D. F. Botz, An
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Jozef Hodyl PhD Thesis - Theses - Flinders University

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