1.1 Porphyrins - Friedrich-Alexander-Universität Erlangen-Nürnberg

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3 Discussion and Results 90 5 μA -1.6 -1.4 -1.2 -1.0 -0.8 -0.6 -0.4 -0.2 E [V] 0.6 0.8 1.0 1.2 1.4 1.6 Figure 36. Cyclic voltammograms of 53, 57 and 58 in CH2Cl2 solution with potentials given versus ferrocene E(Fc/Fc + = +0.53 V). See paragraph 6.1 for experimental details. As the cathodic region of the voltammograms depicts, also here the behavior of 53 and 57 is almost similar and the half-wave potentials are comparable although 57 shows a reduction step at -0.84 V which seems to be not fully reversible. This partial irreversibility might be connected with a partial radical character of the ketone moiety showing up in the DFT/MRCI calculations, but the real origin is not yet understood. 96,100 Although the measured half-wave potentials appear already high compared to non-annulated systems, compound 58 again shows a quite different behavior being even more easy to reduce (E½ values are much higher than for 53 or 57). That is again reflecting the enhanced impact of the conjugation to the electron withdrawing ketone moiety and the tethered phenyl ring. The anodic region is well contrasting those finding, since here, all systems show the typical values for tetraphenylporphyrins of that kind meaning that the annulation itself as well as the increasing enhancement of conjugation does not significantly affect the oxidation potentials. 53 57 58
Discussion and Results 3 3.2.6.5.6 Conclusions from Investigations on the Structure-Properties-Relations The investigations on variations of the fundamental structural elements elucidates that a seven-membered exocycle is of significant relevance whereas oppositely lying substituents, like e.g. the methyl group in 53, seem to be less relevant. That particular kind of annulation seems to provide a sufficient distortion level in the porphyrin macrocycle structurally and energetically while it stabilizes the systems configuration at the same time. A six-membered connection appears more flexible and too influencing on the porphyrin core due to enhanced conjugational effects. Thus, the second seven-membered ring structure 57 should also give rise to separable enantiomers while the six-membered ring analog 58 should not. For the latter, it is more likely that the flexibility of 58 leads to a dynamic equilibrium of enantiomeric structure being non-resolvable as it is the case for dodeca-substituted system 56. For clarification, investigations by chiral HPLC-CD coupling are currently in progress. Thus, for the further development on that kind of system in terms of PDT applications, the basic structure was to be preserved to a large extend since the performance can significantly change although only minor changes are implemented (57 and 58 only differ by one -CH2- group!). As then, the principle features of the kind of annulation have been investigated, it seemed worth to study the effect, a poly-annulation might cause on the system’s behavior. 91
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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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Page 56 and 57: 3 Discussion and Results 3.2.3.3 Va
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Page 86 and 87: 3 Discussion and Results vibration
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Page 90 and 91: 3 Discussion and Results cyanomethy
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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 6.2 Studied
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6 Experimental Section 13 C NMR (10
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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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204 56 57 58 59 60 61 62 63 64 65 6
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1.1 Porphyrins - Friedrich-Alexander-Universität Erlangen-Nürnberg

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