1.1 Porphyrins - Friedrich-Alexander-Universität Erlangen-Nürnberg

More documents

Recommendations

Info

3 Discussion and Results vibration is shifted from 1735 to 1692 cm -1 . The other data can be found in the experimental section. For the following ring-closure, the same synthetic protocol was applied as for the conversion of 51 to 53 (see Scheme 43 and paragraphs 3.2.2.2 and 3.2.2.3). Also here the copper(II) complex was formed first, followed by the activation of the carboxylic acid and subsequent annulation. Then demetallation, achieved under analog acidic conditions, finally furnished 58 in 61 % yield based on 65. 96 As the results from optical and electrochemical investigations shall be surveyed together with the ones for the other mono-exocyclic systems 53 and 57 (paragraph 3.2.6.5), only the 1 H NMR data are to be discussed here. 78 O 2 7 N NH HN N β-pyrr 5 3 9.2 9.0 8.8 8.6 8.4 8.2 8.0 7.8 7.6 7.4 5 6 o-ArH m-ArH 5 5 * 1.60 1.58 1.56 9 8 7 6 5 4 3 2 1 0 -1 δ [ppm] -3 5 4 10 4 , 15 4 , 20 4 Figure 30. 1 H NMR spectrum of 58, 400 MHz, CDCl3, rt. Signals are numbered according to IUPAC recommendations. NH
Discussion and Results 3 At first sight, the spectrum displayed in Figure 30 seems to be comparable to the one of 53 as it shows the expected features like e.g. the appearance of seven β-pyrrolic resonances most downfield and three singlets around 1.58 ppm representing the three t-butyl groups in the periphery. Both facts nicely reflect the C1 symmetry pattern. While, analog to 53, the signal for the inner ring protons is strongly shifted to lower field, the shift appears extremely huge for 58. The signal, being observed at -0.56 ppm, is shifted over 2.1 ppm compared to the precursor 60 and also more than 1 ppm in comparison to 53. Thus, the electronic structure of the macrocycle appears strongly influenced by changing the size of the exocycle. Furthermore, a closer look reveals that the aromatic region is completely contrary to the situation observed for 53 as the protons on the non-annulated phenyl rings give solely rise to well resolved signals (o-/m-ArH) while surprisingly the resonances of the tethered phenyl ring appear significantly broadened (5 3-6 ). Additionally, the splitting pattern of the signals assigned to the freely rotatable phenyl rings looks like three sets of two doublets overlaying at about 8.0 and 7.7 ppm, respectively. This almost seems to equal the situation being observed in non-annulated symmetric porphyrin systems. Thus, it can be concluded, that in 58 the two half-spaces above and below the porphyrin plane are not distinguishable so that three pseudo-AB systems appear in the spectrum. These observations imply that six- membered ring analog 58 is not stable in configuration as the exocycle seems to be invertible. This is also supported by the line-broadening of the signal for β-pyrrolic proton on position 7 at the neighboring pyrrolic unit. Further discussion on structural details is provided together with those on the second model compound in paragraph 3.2.6.5. 79
Page 1 and 2:
Semi-Natural and Synthetic Chiral C
Page 3 and 4:
Die vorliegende Arbeit entstand in
Page 5 and 6:
Table of Contents 1 Introduction 1
Page 7:
n J j-coupling (constant) with n in
Page 10 and 11:
1 Introduction characteristics. For
Page 12 and 13:
1 Introduction 1.1 Porphyrins - A G
Page 14 and 15:
1 Introduction Especially interesti
Page 16 and 17:
1 Introduction 8 [H] 4 + 4 O H O H
Page 18 and 19:
1 Introduction complexes are usuall
Page 20 and 21:
1 Introduction transitions as it is
Page 22 and 23:
1 Introduction 1.2 Photodynamic The
Page 24 and 25:
1 Introduction Certainly, Photofrin
Page 26 and 27:
1 Introduction intact membranes bei
Page 28 and 29:
1 Introduction components, the limi
Page 30 and 31:
2 State of The Art & Aims They were
Page 32 and 33:
2 State of The Art & Aims 2.2 Aim o
Page 34 and 35:
3 Discussion and Results encapsulat
Page 36 and 37: 3 Discussion and Results diastereot
Page 38 and 39: 3 Discussion and Results 30 E ½ Re
Page 40 and 41: 3 Discussion and Results irradiatio
Page 42 and 43: 3 Discussion and Results 34 R 1 O N
Page 44 and 45: 3 Discussion and Results 3.2.2.1.2
Page 46 and 47: 3 Discussion and Results Table 4. S
Page 48 and 49: 3 Discussion and Results 3.2.2.2 FR
Page 50 and 51: 3 Discussion and Results 3.2.2.3 Ac
Page 52 and 53: 3 Discussion and Results 3.2.3.1 IR
Page 54 and 55: 3 Discussion and Results 3.2.3.2 NM
Page 56 and 57: 3 Discussion and Results 3.2.3.3 Va
Page 60 and 61: 3 Discussion and Results Obviously,
Page 62 and 63: 3 Discussion and Results Like Figur
Page 64 and 65: 3 Discussion and Results utilizatio
Page 66 and 67: 3 Discussion and Results has been d
Page 68 and 69: 3 Discussion and Results other TPP
Page 70 and 71: 3 Discussion and Results (being sup
Page 72 and 73: 3 Discussion and Results other band
Page 74 and 75: 3 Discussion and Results Table 10.
Page 76 and 77: 3 Discussion and Results voltammogr
Page 78 and 79: 3 Discussion and Results 3.2.5 Inhe
Page 80 and 81: 3 Discussion and Results effects 12
Page 82 and 83: 3 Discussion and Results 74 Δθ [m
Page 84 and 85: 3 Discussion and Results 3.2.6.2 10
Page 88 and 89: 3 Discussion and Results 3.2.6.4 Sy
Page 90 and 91: 3 Discussion and Results cyanomethy
Page 92 and 93: 3 Discussion and Results 3.2.6.5 Co
Page 94 and 95: 3 Discussion and Results phenyl sub
Page 98 and 99: 3 Discussion and Results 90 5 μA -
Page 100 and 101: 3 Discussion and Results 3.2.7 Appr
Page 102 and 103: 3 Discussion and Results (75 eq.) w
Page 104 and 105: 3 Discussion and Results 3.2.7.2 Sy
Page 106 and 107: 3 Discussion and Results of rotatio
Page 108 and 109: 3 Discussion and Results Thus, the
Page 110 and 111: 3 Discussion and Results Time-resol
Page 112 and 113: 3 Discussion and Results first redu
Page 114 and 115: 3 Discussion and Results correspond
Page 116 and 117: 3 Discussion and Results The remain
Page 118 and 119: 3 Discussion and Results 3.2.8.1 Us
Page 120 and 121: 3 Discussion and Results With all t
Page 122 and 123: 3 Discussion and Results The interm
Page 124 and 125: 3 Discussion and Results 116 HO 2 C
Page 126 and 127: 3 Discussion and Results nitro comp
Page 128 and 129: 3 Discussion and Results The effect
Page 132 and 133: 3 Discussion and Results 3.2.9 Pote
Page 134 and 135: 3 Discussion and Results peak at m/
Page 136 and 137:
3 Discussion and Results Table 25.
Page 138 and 139:
3 Discussion and Results 130
Page 140 and 141:
4 Summary As the characterization d
Page 142 and 143:
5 Zusammenfassung 5 Zusammenfassung
Page 144 and 145:
5 Zusammenfassung Da in guten Ausbe
Page 146 and 147:
6 Experimental Section UV/Vis spect
Page 148 and 149:
6 Experimental Section 6.2 Studied
Page 150 and 151:
6 Experimental Section 13 C NMR (10
Page 152 and 153:
6 Experimental Section (cyanomethyl
Page 154 and 155:
6 Experimental Section 6.2.4 AB3-Ty
Page 156 and 157:
6 Experimental Section 6.2.4.3 5 4
Page 158 and 159:
Page 160 and 161:
Page 162 and 163:
Page 164 and 165:
6 Experimental Section 6.2.4.11 10
Page 166 and 167:
6 Experimental Section EA: C57H56N4
Page 168 and 169:
6 Experimental Section 6.2.4.15 10
Page 170 and 171:
6 Experimental Section 6.2.5 A2B2-T
Page 172 and 173:
Page 174 and 175:
6 Experimental Section 6.2.5.5 αβ
Page 176 and 177:
6 Experimental Section 6.2.5.7 αβ
Page 178 and 179:
6 Experimental Section 6.2.5.9 αα
Page 180 and 181:
6 Experimental Section 6.2.5.11 α
Page 182 and 183:
6 Experimental Section 6.2.5.13 α
Page 184 and 185:
Page 186 and 187:
6 Experimental Section 6.2.6 AB2C-T
Page 188 and 189:
Page 190 and 191:
6 Experimental Section UV/Vis (CH2C
Page 192 and 193:
Page 194 and 195:
6 Experimental Section UV/Vis (CH2C
Page 196 and 197:
6 Experimental Section broad signal
Page 198 and 199:
7 References 16 H. Fischer, K. Zeil
Page 200 and 201:
7 References 57 S. Schwartz, K. Abs
Page 202 and 203:
7 References 89 (a) R. C. Fuson, J.
Page 204 and 205:
7 References 131 (a) J. Perdew, Phy
Page 206 and 207:
S. Jasinski, N. Jux, “Investigati
Page 208 and 209:
Ein großer Dank gilt auch den Ange
Page 210 and 211:
Cirruculum vitae Stefan Jasinski Ge
Page 212 and 213:
204 56 57 58 59 60 61 62 63 64 65 6
show all

1.1 Porphyrins - Friedrich-Alexander-Universität Erlangen-Nürnberg

Create successful ePaper yourself

Delete template?

Save as template?