1.1 Porphyrins - Friedrich-Alexander-Universität Erlangen-Nürnberg

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3 Discussion and Results 30 E ½ Red2 -1.23 V E ½ Red1 -1.05 V E pc Ox1 5 μA +0.97 V E pc Ox2 +1.43 V -1.4 -1.2 -1.0 -0.8 -0.6 -0.4 E (V) 0.8 1.0 1.2 1.4 1.6 1.8 Figure 12. Cyclic voltammogram of Me-33 in CH2Cl2 with indicated half-wave potentials E½ and cathodic peak potentials Epc given in V vs. ferrocene E(Fc/Fc + ) = +0.53 V which served as internal standard. In the cathodic region, two reversible electron transfer processes are visible while in the anodic region only clear peaks are observed in forward direction. In the reverse direction, i.e. going to lower potentials, the corresponding peaks are not detectable or show a significantly lower anodic peak current. Thus, for those irreversible processes only cathodic peak potentials Epc were obtained. This is in well agreement with theory since Me-33 represents a chlorin which can be reversibly reduced but not oxidized. The oxidation would go in hand with the loss of two protons finally resulting in a porphyrin structure of different behavior. That is also the crucial point as those processes are easily happening by improvident handling of such substrates under oxygen in solution.
3.2 Synthetic Cycloketo-Porphyrin Systems Br Br Br Br Br Br c. d. O O Br Br Discussion and Results 3 This class of compounds can be regarded as distantly related to the previously presented chlorophyll derivatives based on the porphyrin building blocks introduced by JUX 69 (Scheme 17). Thus, a new class of substances had to be developed, beginning with a closer look on the already established building blocks themselves. 3.2.1 o-(Bromomethyl) Substituted Porphyrin Building Blocks Revisited Those substances, representing excellent starting materials as they are easily accessible and convertible into diverse functional porphyrinoid targets, arise from arylaldehydes 38a or 38b being not commercially available. Hence, they have to be synthesized from 5-t-butyl-m- xylene 34 by the multistep strategy depicted in Scheme 22. a. 34 35 b. 36a 36b c. O d. O O O 38a Scheme 22. Synthetic protocol used for arylaldehydes 38a and 38b: a. Br2, iron cuttings, CH2Cl2, rt, 3 h; b. Br2, CH2Cl2, hν, reflux, 0.5-6 h; c: Na, MeOH, reflux, 3 h; d. 1. n-BuLi, Et2O, -78 °C, 1 h; 2. add. DMF, -78 °C→rt, 2 h; 3. add. 2 M HCl, rt, 0.5 h. The first step, the bromination para to the t-butyl group in 34 89 , emerged efficient, whereas the subsequent functionalization of the benzylic position(s) in 35 by radical bromination 90 using N-bromosuccinimide (NBS) and dibenzoyl peroxide (DBPO) turned out to be inexpedient. On the one hand, the isolation of the desired targets was laborious due to multiple bromination on each methyl group in considerable amounts 75 and on the other hand the used solvent CCl4 is hazardous and only limitedly accredited. These disadvantages could be overcome by conducting the reaction in CH2Cl2 with elemental bromine under 37a 37b O 38b O 31
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
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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
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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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3 Discussion and Results 3.2.6.4 Sy
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3 Discussion and Results cyanomethy
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3 Discussion and Results 3.2.6.5 Co
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3 Discussion and Results phenyl sub
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3 Discussion and Results 3.2.6.5.4
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3 Discussion and Results 90 5 μA -
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3 Discussion and Results 3.2.7 Appr
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3 Discussion and Results (75 eq.) w
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3 Discussion and Results 3.2.7.2 Sy
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3 Discussion and Results of rotatio
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3 Discussion and Results Thus, the
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3 Discussion and Results Time-resol
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3 Discussion and Results first redu
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3 Discussion and Results correspond
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3 Discussion and Results The remain
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3 Discussion and Results 3.2.8.1 Us
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3 Discussion and Results With all t
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3 Discussion and Results The interm
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3 Discussion and Results 116 HO 2 C
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3 Discussion and Results nitro comp
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3 Discussion and Results The effect
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3 Discussion and Results 3.2.8.2.7
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3 Discussion and Results 3.2.9 Pote
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3 Discussion and Results peak at m/
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3 Discussion and Results Table 25.
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3 Discussion and Results 130
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4 Summary As the characterization d
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5 Zusammenfassung 5 Zusammenfassung
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5 Zusammenfassung Da in guten Ausbe
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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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1.1 Porphyrins - Friedrich-Alexander-Universität Erlangen-Nürnberg

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