1.1 Porphyrins - Friedrich-Alexander-Universität Erlangen-Nürnberg

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3 Discussion and Results of rotational or mirror symmetry thereby also gives rise to symmetrical distortions of the non-annulated pyrrolic units hence providing NMR spectra only differentiable by knowledge of the precursor. With that in mind, however, the classification was achieved by taking into account the spectral data displayed in Figure 38 and computational models of those systems. For both 67 and 69, four doublets are observed with characteristic three-bond couplings of 8.1-8.6 Hz resembling the appearance of two different pseudo-AB spin systems – one for each “free” phenyl ring. This indicates that the two present half-spaces in the systems are identical. While this is straightforward as 69 is concerned, the situation for 67 needs further explanation. On the one side, based on computed structural models, the ketone functionality is nearly perfectly coplanar with the porphyrin so that a pseudo-AB spin system for the 20-phenyl substituent becomes feasible. On the other side, only the ortho methyl groups are able to deliver a differentiation between the half-spaces. But, based on our experience (see discussion on p. 38-39), those are too small to be capable of that which explains the second pseudo-AB spin system. Together with the 13 C NMR spectra, where the t-butyl groups appear as two sets of three signals in a 1:1:2 ratio – two differentiable signals for the “free” phenyl rings and one combined for the tethered ones – the assignment was accomplished. Thus, 67 is to be of Cs symmetry while 69 appears C2 symmetric. In 68 and 70, the situation is different as the corresponding resonances are observed as four doublets of doublet of corresponding couplings of 3 J ∼ 8.1 Hz and 4 J ∼ 1.7 Hz, respectively, being in compliance with the appearance of ABCD spin systems. That means, upper and lower half-space represent different surroundings close to the regarded phenyl rings causing different chemical shifts. But as additionally each signal stands for 2 H, both ABCD systems appear identical, telling that the situation is exactly the same for both “free” phenyl rings. That is corroborated by the 13 C NMR spectra, where only one signal for both rings is observed instead of the two signals in a 1:1 ratio for 67 and 69. Thus, taking also the precursor’s symmetry into account, 68 is to be C2 symmetric while 70 appears to be of Ci symmetry. Compound 71, in contrast, represents a far easier example as only a C2 symmetric conformation appears reasonable. That assumption can be confirmed by the corresponding NMR data as for the two cis-standing phenyl substituents (positions 10 and 20) signals are 98
Discussion and Results 3 detected as two doublets standing for pseudo-AB spin systems like in 67 & 69. This indicates the presence of identical half-spaces like it can be expected. Furthermore, the analogy to mono-functionalized 53 96 is visible as the signals for the 15-phenyl substituent are concerned, which show a significant line broadening. Thus, the system seemingly becomes more flexible in the most distant areas in respect to the annulation sites. In the 13 C NMR spectrum, unfortunately, the signals appear non-resolvable as the “free” phenyl rings seem too similar. Alike the aromatic region, the remainder areas of the 1 H NMR spectra show up swayed by the positioning of the two exocycles influencing the chemical shifts of the methylene protons therein as well as the one of the inner ring amine protons (Table 20). Table 20. Comparison of the chemical shifts δ of the resonances for the exocyclic methylene groups and the inner ring amines in 67-71 as resulted from measurements at 400 MHz in CDCl3 at rt. δ values given in ppm. Compound Annulated positions δH(CH2) ΔδH(CH2) δH(NH) 67 3 & 17 5.15/4.05 <strong>1.1</strong>0 -0.17 68 3 & 13 5.45/4.09 1.36 -0.94 69 3 & 17 5.16/4.04 <strong>1.1</strong>2 -0.15 70 3 & 13 5.46/4.10 1.36 -0.93 71 3 & 7 4.37/3.85 0.52 -1.36 Concerning the methylene bridges, the corresponding signals are shifted more downfield as the distance between the annulated positions grows. This effect is going in hand with an augmentation in the spectral distance ΔδH of the corresponding doublets. All this implies an enhancing distortion which seems to be logic as the more distance is in between the rigid ketone moieties, the more impact can be exerted. For example, the ketones in 71 influence each other due to their close proximity as those in 68 or 70 have more or less independently impact on the core system. The deviation from planarity is also affecting the resonances of the inner ring amine protons even though not in exactly the same fashion since now, also conjugational effects have to be taken into consideration. That was not applicable on the discussion before as the peripheral phenyl substituents appear electronically decoupled in computational analyses. 100 99
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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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Page 60 and 61: 3 Discussion and Results Obviously,
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Page 68 and 69: 3 Discussion and Results other TPP
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Page 76 and 77: 3 Discussion and Results voltammogr
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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
Page 126 and 127: 3 Discussion and Results nitro comp
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Page 136 and 137: 3 Discussion and Results Table 25.
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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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Page 150 and 151: 6 Experimental Section 13 C NMR (10
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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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