1.1 Porphyrins - Friedrich-Alexander-Universität Erlangen-Nürnberg

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3 Discussion and Results (75 eq.) was used. The subsequent acidic saponification 96 , conducted in complete analogy, furnished porphyrin di-ethanoic acids 75-77. While the reactions and the compounds are depicted in Scheme 47, the corresponding yields, being throughout good to excellent, are given in Table 18. R 1 94 Br N NH HN N R 3 46 R 1 =Br, R 2 =R 3 =H R 2 47 R 1 =H, R 2 =CH2Br, R 3 =CH3 48 R 1 =H, R 2 =CH3, R 3 =CH2Br a. R 1 CN N NH HN N R 3 R 2 b. R 1 CO 2 H N NH HN N Scheme 47. Synthetic access to porphyrin di-ethanoic acids 75-77 via cyanation and subsequent saponification. Applied conditions: a. 1. Zn(OAc)·2 H2O, CH2Cl2/MeOH, rt, 6h; 2. KCN, PEG400, rt, 24h; 3. aq. HCl, CH2Cl2, rt, 10 min; b. AcOH/H2SO4/H2O, 95 °C, 96h. Table 18. Overview on the isolated yields for the reactions depicted in Scheme 46. Pathway Yield of bis-cyanation Yield of full saponification Overall yield 46 → 75 95 % 88 % 83.6 % 47 → 76 88 % 83 % 73.0 % 48 → 77 95 % 85 % 80.8 % Thus, the direct precursors for the next step – the bis-annulation – were obtained providing the abovementioned pre-organization: 75, having both acid functionalities on the same phenyl substituent, one above one below the porphyrin plane, and 76 and 77 carrying those groups on trans-standing phenyl rings. Thereby, both side chains are situated in one half- space for 77 (αα-conformation) and oppositely for 76 (αβ-conformation). Both purity and conformation were verified by 1 H-NMR spectroscopy like it is depicted in Figure 37 before the bis-annulations were tackled. 72 R 1 =CN, R 2 =R 3 =H 73 R 1 =H, R 2 =CH2CN, R 3 =CH3 74 R 1 =H, R 2 =CH3, R 3 =CH2CN R 3 75 R 1 =CO2H, R 2 =R 3 =H R 2 76 R 1 =H, R 2 =CH2CO2H, R 3 =CH3 77 R 1 =H, R 2 =CH3, R 3 =CH2CO2H
8.8 8.6 8.4 8.2 8.0 7.8 7.6 δ [ppm] 7.2 Discussion and Results 3 HO 2 C HO 2 C N NH HN N N NH HN N HO 2 C N NH HN N Figure 37. Aromatic regions of the 1 H NMR spectra of 75 (top), 76 (middle) and 77 (bottom) arising from measurements at 400 MHz at rt in THF-d8 (75) or CDCl3(*)/THF-d8 (76 and 77). The pyrrolic protons, the protons on the functionalized aryl ring(s) and those on the nonfunctionalized aryls rings are highlighted in red, blue and green, respectively. The 1 H NMR spectrum of 75 shows the typical splitting pattern for AB3 systems. The pyrrolic protons appear as two doublets for the pyrrolic units close to the functionalized phenyl substituent and as one singlet for the more distant ones. This is well comprehensible, as the brake in symmetry is too distant to exert any impact. The resonances for the nonfunctionalized phenyl rings show up as pseudo-AB spin systems, i.e. as two sets of doublets, since the upper and the lower half-space are equivalent. While the resonances for the protons in meta position appear in exactly the same position (only one doublet for 6 H more upfield), the additional splitting of the corresponding ortho signal more downfield arises from the differentiability of the cis- (10, 20) and trans-standing (15) non-functionalized phenyl rings. A similar situation is found for 76, as also here the half-spaces are not distinguishable whereas they are in 77 providing the characteristic splitting pattern for an AA’BB’ spin system. * HO 2 C CO 2 H CO 2 H 95
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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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Page 82 and 83: 3 Discussion and Results 74 Δθ [m
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Page 86 and 87: 3 Discussion and Results vibration
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Page 120 and 121: 3 Discussion and Results With all t
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Page 124 and 125: 3 Discussion and Results 116 HO 2 C
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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
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6 Experimental Section (cyanomethyl
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6 Experimental Section 6.2.4 AB3-Ty
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6 Experimental Section 6.2.4.3 5 4
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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 6.2.5.5 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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