Jozef Hodyl PhD Thesis - Theses - Flinders University

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it should be borne in mind that previous comparisons of solution 13 C NMR arisingfrom guest anions and host guest complexes of this type have always revealed almostnegligible chemical shift perturbation for the host carbon atom resonances, butusually some quite significant perturbation to the chemical shift values of the guestresonances. Proceeding on this basis it is then reasonable to postulate that the newresonance in spectrum D (compared to C) at 182.2 ppm is from C1 of the guest(183.0 ppm in B), the new resonance at 167.9 ppm is from C3 (166.7 ppm in B), thenew shoulder at 138.0 ppm is from C5 (139.7 ppm in B) and the new broadresonance at 110.2 is from a merging of C4 and C2 (113.0 and 108.3 ppm in B).Thus there seems little doubt that not only is 2,6-dihydroxybenzoate present in thesample used to produce spectrum D, but that the altered chemical shift values for theguest indicate a more intimate association than just a physical mixture of the twospecies.The preceding spectra are for a host-guest combination where the very highestuptake of the guest occurred (95%) so examination of the solid state NMR spectrafrom a lower percentage uptake combination is also illustrative as a basis forcomparison. The guest species, m-methoxybenzoate, with 55% inclusion in Si-GPS-[Cd(Trac)](ClO 4 ) 2 , 94, was chosen for this purpose.The acquired spectra aredepicted in Figure 6.8.Spectrum A, for m-methoxybenzoate, shows splitting of all of the singleresonances found in the solution spectrum. This spectrum when viewed incombination with spectrum B does display evidence for inclusion of m-methoxybenzoate in Si-GPS-[Cd(Trac)](ClO 4 ) 2 , 94, as depicted in spectrum C, withsome bands for this guest molecule clearly visible, particularly C1 which movesfrom 183.0 ppm in A to 184.1 ppm in C.115
A1 46 7532 Anionic Guest8BCHostHost-GuestFigure 6.813 C CP MAS NMR spectra for (A) sodium m-methoxybenzoate, (B) Si-GPS-[Cd(Trac)](ClO 4 ) 2 and (C) Si-GPS-[Cd(Trac)(m-methoxybenzoate)](ClO 4 ). All spectraare shown with line broadening.However, overall the comparison is not as convincing as that seen in Figure 6.7and this is completely in line with uptake of m-methoxybenzoate by 94 beingmeasured as 55% instead of 96%. Resonances from carbon atoms C2 to C7 inspectrum C are either superimposed or appear only with a barely discernible signal tonoise ratio.To confirm that high percent inclusion materials would display bands for hostmaterial with included guest species another high inclusion material, sodium 2, 4, 6-trihydroxybenzoate, 94%, was analysed. The relevant spectra for this material aredisplayed in Figure 6.9.As sodium 2, 4, 6-trihydroxybenzoate is a high binding guest its spectral bandsare quite prominent in spectrum C for the host-guest material. The band for thecarboxylate carbon C1 is clearly visible at 183.0 ppm. A large band for the ipsocarbon C2 in spectrum A at 101.7 ppm is distinguishable, but broadened and muchsmaller at 100.2 ppm in spectrum C. Additional bands between 150.0 ppm and 169.0ppm for C3, C4 and C5 are shifted downfield in spectrum C.116
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Silica Immobilised MetalIon Activat
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ABSTRACTImmobilisation of functiona
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DECLARATIONI certify that this thes
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EtOHGPDMSGPDMESGPSGPTSethanolglycid
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CHAPTER ONEINTRODUCTION
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The focus of this work was to prepa
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sequestering anions has proved to b
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ange of pH due to its high basicity
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nitrophenol or p-nitrophenolate wit
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It has been shown by NMR and crysta
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within the cavity of a p-tert-butyl
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60 in 0.5% DMSO-MeCN (v/v). 82 The
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synthesised bi- tri- and tetra - π
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adopt a trans-III conformation, whe
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amide oxygen atoms on the pendant a
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apparent there is, nonetheless, evi
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However, hetero-N-substitution on t
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Si-OH +- OH SiO - + H 2 OFor surfac
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35This material was obtained with a
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OOSiOHOROR OSiOHOOOSiOSiOSiOSiOSiOS
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Tetraaza metal complexes immobilise
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CHAPTER TWOSYNTHESIS OF MACROCYCLIC
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In addition, successful immobilisat
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3233Figure 2.3Reaction of 3-(glycid
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The methodology chosen was adapted
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agreed with literature values. 109R
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XS HO O H61, n = 262, n = 3n+ClOSO6
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anhydrous ethanol, Scheme 2.7. The
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75Figure 2.5 Structure of (S)-(-)-p
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metal ion coordination the pendant
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CHAPTER THREEGUEST MOLECULE INCLUSI
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3.1 where K A is the association, o
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0.5cχG∆δ∆δGbaχ GFigure 3.1S
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χG∆δ∆δGFigure 3.4 Job's Plot
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The downfield movement of the guest
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arm framework. The relative magnitu
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This phenomenon correlates well wit
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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: A1 3542Neutral GuestBAnionic GuestH
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
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Si-GPS-[Cd(Trac)(2,5-diydroxybenzoa
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REFERENCES
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15. D. Tzalis and Y. Tor, Tetrahedr
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42. A. P. Davis and R. S.Wareham, A
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69. R. J. Bergeron, M. A. Channing
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93. C. B. Smith, A. K. W. Stephens,
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118. D. D. Dischino, E. J. Delaney,
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144. X. Huang, X. Chang, Q. He, Y.
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169. J. M. Klunder, T. Onami and K.
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197. K. A. Connors, Binding Constan
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221. J. Blumel, J. Am. Chem. Soc.,
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247. W. Likussar and D. F. Botz, An
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Jozef Hodyl PhD Thesis - Theses - Flinders University

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