1.1 Porphyrins - Friedrich-Alexander-Universität Erlangen-Nürnberg

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6 Experimental Section 6.2 Studied Compounds – Syntheses & Characterization 6.2.1 Preliminaries Compounds which have been obtained by application of procedures according to literature are listed below together with the references the corresponding protocols were taken from. • 4-t-butyl-2,6-dimethyl-bromobenzene 35 89 • 4-t-butyl-2-(methoxymethyl)-6-methyl-bromobenzene 37a and 4-t-butyl-2,6-bis- 140 (methoxymethyl)-bromobenzene 37b 90 • 4-t-butyl-2-(methoxymethyl)-6-methyl-benzaldehyde 38a and 4-t-butyl-2,6-bis- (methoxymethyl)-benzaldehyde 38b 90 • 5 4 -t-butyl-5 2 -(methoxymethyl)-5 6 -methyl-5-phenyldipyrromethane 39a and 5 4 -t-butyl- 5 2 ,5 6 -bis-(methoxymethyl)-5-phenyldipyrromethane 39b 36,75,92 • 5 4 , 10 4 , 15 4 , 20 4 -tetra-t-butyl-5 2 -(methoxymethyl)-5 6 -methyl-5, 10, 15, 20-tetraphenylporphyrin 40; 5 4 , 10 4 , 15 4 , 20 4 -tetra-t-butyl-5 2 ,5 6 -bis-(methoxymethyl)-5, 10, 15, 20- tetraphenylporphyrin 41; αβ-5 4 ,10 4 ,15 4 ,20 4 -tetra-t-butyl-5 2 ,15 2 -bis-(methoxymethyl)- 5 6 ,15 6 -dimethyl-5,10,15,20-tetraphenylporphyrin 42; αα-5 4 ,10 4 ,15 4 ,20 4 -tetra-t-butyl- 5 2 ,15 2 -bis-(methoxymethyl)-5 6 ,15 6 -dimethyl-5,10,15,20-tetraphenylporphyrin 43 and 5 4 , 10 4 , 15 4 , 20 4 -tetra-t-butyl-5 2 ,5 6 ,15 2 ,15 6 -tetrakis-(methoxymethyl)-5, 10, 15, 20-tetraphenylporphyrin 44 69,70b • 5 2 -(bromomethyl)-5 4 , 10 4 , 15 4 , 20 4 -tetra-t-butyl-5 6 -methyl-5, 10, 15, 20-tetraphenylporphyrin 45; 5 2 ,5 6 -bis-(bromomethyl)-5 4 , 10 4 , 15 4 , 20 4 -tetra-t-butyl-5, 10, 15, 20-tetraphenylporphyrin 46; αβ-5 2 ,15 2 -bis-(bromomethyl)-5 4 ,10 4 ,15 4 ,20 4 -tetra-t-butyl-5 6 ,15 6 - dimethyl-5,10,15,20-tetraphenylporphyrin 47; αα-5 2 ,15 2 -bis-(bromomethyl)-5 4 , 10 4 , 15 4 , 20 4 -tetra-t-butyl-5 6 ,15 6 -dimethyl-5,10,15,20-tetraphenylporphyrin 48 and 5 2 ,5 6 ,15 2 ,15 6 - tetrakis-(bromomethyl)-5 4 , 10 4 , 15 4 , 20 4 -tetra-t-butyl-5, 10, 15, 20-tetraphenylporphyrin 49 69,70b • 5 4 -nitro-5-phenyldipyrromethane 85 137 The applied nomenclature is according to the IUPAC recommendations. 18 In paragraph 6.2.3, some general procedures will be introduced being later referred to as GP’s while the exact scheduled amounts of solvents and reagents will be given in each paragraph for the corresponding compound.
6.2.2 Semi-Natural Cycloketo-Porphyrin Systems 6.2.2.1 Methyl Pyropheophorbide a, Me-33, from Spirulina Platensis N NH HN N Me-33 O C 34 H 36 N 4 O 3 M = 548.67 g·mol -1 O O Experimental Section 6 In a 500 mL beaker, 100 g of dry spirulina platensis are suspended in 300 mL of water and allowed to soak for 3 h. The obtained algal pulp is then homogenized with a commercial hand blender and slowly poured into liquid nitrogen furnishing small pellets. Those are transferred into a 2 L round bottom flask, which is then filled with acetone. This reaction mixture is stirred at rt for 20 h. Upon filtration, the separated cellular material is washed with acetone and the combined washings are evaporated to dryness to give an oily dark brown residue. To isolate pheophytin a 31, that material is subjected to FC on silica whereat the polarity of the eluent is risen stepwise: 1 st hexanes, 2 nd hexanes : CH2Cl2 (1 : 1), 3 rd CH2Cl2, 4 th CH2Cl2 : ethyl acetate (9 : 1). Finally, 31 elutes in black purple color. That solution is then evaporated to dryness before a N2 saturated methanolic solution of H2SO4 (100 mL, 5 wt% H2SO4) is added. After stirring at rt for 15 h under N2, the reaction mixture is concentrated and washed with water, a saturated aqueous solution of NaHCO3 and water, dried over Na2SO4 and again evaporated to dryness. In a 250 mL round bottom flask, the thus obtained methyl pheophorbide a 32 is dissolved in 100 mL of 2,4,6-collidine and degassed with N2 for 20 min before the reaction mixture is refluxed for 5 h (∼ 180 °C). Subsequently, the solvent is removed by vacuum distillation and the crude product is washed with 6 M aqueous HCl, water, a saturated aqueous solution of NaHCO3 and water and finally dried over Na2SO4. Purification is finally accomplished by FC (silica, CH2Cl2 : ethyl acetate = 9 : 1) to give 600- 800 mg pure methyl pyropheophorbide a Me-33 as dark purple powder. 1 H NMR (400 MHz, rt, CDCl3): δ [ppm] = -1.77 (s, 1 H, NH), 0.37 (s, 1 H, NH), 1.64 (t, 3 J = 7.6 Hz, 3 H, 8 2 ), 1.80 (d, 3 J = 7.2 Hz, 3 H, 18 1 ), 2.27, 2.55, 2.68 (3m, 2+1+1 H, 17 1 & 17 2 ), 3.16 (s, 3 H, 7 1 ), 3.37 (s, 3 H, 2 1 ), 3.60 (s, 3 H, 17 4 & q, 3 J = 7.6 Hz, 2 H, 8 1 ), 3.61 (s, 3 H, 12 1 ), 4.27 (m, 1 H, 17), 4.46 (m, 1 H, 18), 5.09, 5.24 (2d, 2 J = 19.6 Hz, 1+1 H, 13 2 ), 6.13 (dd, 2 J = 1.6 Hz, 3 J = 11.6 Hz, 1 H, 3 2 cis), 6.24 (dd, 2 J = 1.6 Hz, 3 J = 17.6 Hz, 1 H, 3 2 trans), 7.94 (dd, 3 J = 11.6 Hz, 3 J = 17.6 Hz, 1 H, 3 1 ), 8.52 (s, 1 H, 20), 9.29 (s, 1 H, 5), 9.40 (s, 1 H, 10). 141
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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 Obviously,
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3 Discussion and Results Like Figur
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3 Discussion and Results utilizatio
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3 Discussion and Results has been d
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3 Discussion and Results other TPP
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3 Discussion and Results (being sup
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3 Discussion and Results other band
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3 Discussion and Results Table 10.
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3 Discussion and Results voltammogr
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3 Discussion and Results 3.2.5 Inhe
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3 Discussion and Results effects 12
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3 Discussion and Results 74 Δθ [m
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3 Discussion and Results 3.2.6.2 10
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3 Discussion and Results vibration
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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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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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