1.1 Porphyrins - Friedrich-Alexander-Universität Erlangen-Nürnberg

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3 Discussion and Results corresponding mono-annulated compound 53. Thus, although the BCKPs are slightly easier accessible synthetically, it has to be focused on mono-annulated derivatives for the further development of 3 rd generation photosensitizing systems as their characteristics are significantly more promising. Concerning the chirality of those systems, also investigations via chiral HPLC-CD coupling are aimed at. First results were obtained for C2 symmetric, 3-17 αβ-bis-annulated 69. The corresponding atropo-enantiomers could be resolved on a Phenomenex® Chirex 3010 column using a rising solvent gradient (CH2Cl2/hexanes). Thereby, the elugrams clearly show two eluting fraction in a 1 : 1 ratio of retention times of 69.3 and 76.7 min, respectively. Online-CD spectroscopy delivered also mirror-inverted CD-spectra analog to those of 53 shown in paragraph 3.2.5.2, p. 74. The data is not displayed here, as further verification and CD spectroscopy at higher sample concentrations is currently worked on in cooperation with the group of G. BRINGMANN. 3.2.7.9 Cycloketo-<strong>Porphyrins</strong> with Higher Annulation Patterns The obtained good results for bis-annulated systems delivered the question, if even more annulations are possible. The next well accessible higher homologue of JUX’s building blocks thereto is represented by tetrakis-o-(bromomethyl) substituted porphyrin 49 being displayed in Scheme 25. Accordingly, the already described procedures 70b,96 were applied to firstly give the corresponding o-(cyanomethyl) substituted system 78 and finally porphyrin tetra-ethanoic acid derivative 79 like it is depicted in Scheme 48. Br 106 Br N NH HN N Br Br CN a. NC N NH HN b. N CN NC HO 2 C CO 2 H N NH HN N 49 78 79 HO 2 C CO 2 H Scheme 48. Synthesis of porphyrin tetra-ethanoic acid 79. Applied conditions: a. 1. Zn(OAc)·2 H2O, CH2Cl2/MeOH, rt, 24h; 2. KCN (100 eq.), PEG400, rt, 24h; 3. aq. HCl, CH2Cl2, rt, 10 min; b. AcOH/H2SO4/H2O, 95 °C, 96h.
9.0 8.8 8.6 8.4 8.2 8.0 7.8 Discussion and Results 3 Since all those systems are of high symmetry (D2h), the corresponding NMR spectra appear quite simple. Furthermore are 49 and 79 already known to literature 69,70b , so that the discussion will focus on 78 whose 1 H NMR spectrum is displayed in Figure 43. The data on 79 is included in the experimental section. 3, 7, 13, 17 2, 8, 12, 18 * m-Ar’H o-ArH m-ArH CH 2 9 8 7 6 5 4 3 2 1 0 -1 δ [ppm] -3 10 4 20 4 5 4 15 4 * NC CN N NH HN Figure 43. 1 H NMR spectrum of 78 measured at 400 MHz in CDCl3 at rt. Signals are numbered according to IUPAC recommendations. (Ar’ = functionalized phenyl rings) The β-pyrrolic as well as the arylic protons on the non-functionalized meso-substituents give rise to two doublets each with characteristic couplings of 3 J = 4.8 Hz (β-pyrr.) and 3 J = 8.3 Hz (arylic), respectively, which is completely in line with the D2h symmetry pattern. The signal for the methylene group carrying the functionality is detected as a singlet at 3.29 ppm, i. e. shifted upfield by 0.78 ppm compared to the o-bromomethyl substituted precursor (4.07 ppm) analog to the other compound series under investigation. The t-butyl groups are observed as two singlets in a 1 : 1 ratio at 1.67 and 1.63 ppm being also typical for that substitution pattern. Finally, most upfield, the resonance for the inner ring amine protons is found at -2.62 ppm. N NC CN NH 107
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Semi-Natural and Synthetic Chiral C
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Die vorliegende Arbeit entstand in
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Table of Contents 1 Introduction 1
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n J j-coupling (constant) with n in
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1 Introduction characteristics. For
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1 Introduction 1.1 Porphyrins - A G
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1 Introduction Especially interesti
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1 Introduction 8 [H] 4 + 4 O H O H
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1 Introduction complexes are usuall
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1 Introduction transitions as it is
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1 Introduction 1.2 Photodynamic The
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1 Introduction Certainly, Photofrin
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1 Introduction intact membranes bei
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1 Introduction components, the limi
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2 State of The Art & Aims They were
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2 State of The Art & Aims 2.2 Aim o
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3 Discussion and Results encapsulat
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3 Discussion and Results diastereot
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3 Discussion and Results 30 E ½ Re
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3 Discussion and Results irradiatio
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3 Discussion and Results 34 R 1 O N
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3 Discussion and Results 3.2.2.1.2
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3 Discussion and Results Table 4. S
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3 Discussion and Results 3.2.2.2 FR
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3 Discussion and Results 3.2.2.3 Ac
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3 Discussion and Results 3.2.3.1 IR
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3 Discussion and Results 3.2.3.2 NM
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3 Discussion and Results 3.2.3.3 Va
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3 Discussion and Results 3.2.3.3.2
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3 Discussion and Results Obviously,
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3 Discussion and Results Like Figur
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Page 140 and 141: 4 Summary As the characterization d
Page 142 and 143: 5 Zusammenfassung 5 Zusammenfassung
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6 Experimental Section 6.2.4.11 10
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6 Experimental Section EA: C57H56N4
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6 Experimental Section 6.2.4.15 10
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6 Experimental Section 6.2.5 A2B2-T
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6 Experimental Section 6.2.5.3 5 4
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6 Experimental Section 6.2.5.5 αβ
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6 Experimental Section 6.2.5.7 αβ
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6 Experimental Section 6.2.5.9 αα
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6 Experimental Section 6.2.5.11 α
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6 Experimental Section 6.2.5.13 α
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6 Experimental Section 6.2.6 AB2C-T
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6 Experimental Section UV/Vis (CH2C
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6 Experimental Section UV/Vis (CH2C
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6 Experimental Section broad signal
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7 References 16 H. Fischer, K. Zeil
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7 References 57 S. Schwartz, K. Abs
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7 References 89 (a) R. C. Fuson, J.
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7 References 131 (a) J. Perdew, Phy
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S. Jasinski, N. Jux, “Investigati
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Ein großer Dank gilt auch den Ange
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Cirruculum vitae Stefan Jasinski Ge
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1.1 Porphyrins - Friedrich-Alexander-Universität Erlangen-Nürnberg

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