1.1 Porphyrins - Friedrich-Alexander-Universität Erlangen-Nürnberg

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6 Experimental Section UV/Vis (CH2Cl2): λ [nm] (ε [M -1 ·cm -1 ]) = 421 (381000), 517 (20000), 553 (9300), 593 (5800), 648 (4200). EA: C59H56N6O2·H2O. Calc.: C 78.81, H 6.50, N 9.35; found: C 79.07, H 6.47, N 9.15. 6.2.6.5 5 4 ,10 4 ,20 4 -Tri-t-Butyl-5 6 -Methyl-15 4 -Nitro-5,10,15,20-Tetraphenylporphyrin-5 2 - HO 2 C 182 Ethanoic Acid, 90 According to GP II, 120 mg (136 μmol) of cyanomethyl porphyrin 89 are brought to reaction in glacial HOAc (15 mL), conc. H2SO4 (15 mL) and water (5 mL). Pure 90, obtained after FC over silica with CH2Cl2 and ethyl acetate as eluent (ratio: 7 : 3), appears as a violet powder in 113 mg (126 μmol) yield, equiv. to 92 % based on 89. 1 H NMR (400 MHz, rt, CDCl3): δ [ppm] = -2.74 (s, 2 H, NH), 1.50 (s, 18 H, t-BuH), 1.53 (s, 9 H, t-BuH), 1.80 (s, 3 H, CH3), 3.21 (s, 2 H, CH2), 7.50 (m, 4 H, ArH+Ar’H), 7.69 (d, 3 J = 7.8 Hz, 4 H, ArH), 7.94 (d, 3 J = 7.8 Hz, 2 H, ArH), 8.06 (d, 3 J = 7.8 Hz, 2 H, ArH), 8.35 (d, 3 J = 7.8 Hz, 2 H, Ar’’H), 8.61 (m, 4 H, Ar’’H+β-H), 8.68 (d, 3 J = 4.8 Hz, 2 H, β-H), 8.76 (d, 3 J = 4.6 Hz, 2 H, β-H), 8.86 (d, 3 J = 4.6 Hz, 2 H, β-H). 13 C NMR (100.5 MHz, rt, CDCl3): δ [ppm] = 22.0, 31.5, 34.7, 39.7, 116.6, 117.4, 120.6, 121.8, 123.7, 124.1, 125.5, 130.4 (br), 131.8 (br), 134.4, 134.5, 134.9, 135.2, 138.4, 138.7, 139.6, 147.7, 149.5, 150.7, 151.6, 176.0. MS (FAB+, NBA): m/z (%) = 900 (100) [M] +· . IR (ATR): 𝜈� [cm -1 ] = 3321, 2963, 2906, 2868, 1712, 1595, 1560, 1519, 1474, 1400, 1362, 1340, 1310, 1269, 1223, 1210, 1186, 1110, 1021, 993, 982, 968, 919, 849, 800, 738. UV/Vis (CH2Cl2): λ [nm] (ε [M -1 ·cm -1 ]) = 421 (369000), 518 (19600), 553 (10100), 593 (6300), 649 (4900). N NH HN N 90 C 59 H 57 N 5 O 2 M = 900.11 g·mol -1 NO 2 EA: C59H57N5O4·EtOAc·1.5 H2O. Calc.: C 74.53, H 6.75, N 6.90; found: C 74.15, H 6.61, N 7.15.
Experimental Section 6 6.2.6.6 5 4 , 10 4 , 20 4 -Tri-t-Butyl-[ 3,5 2 ]-Ethano- 3 1 -Oxo- 5 6 -Methyl- 15 4 -Nitro-5,10,15,20- O Tetraphenylporphyrinato-Copper(II), Cu(II)-91 Using GP III, porphyrin ethanoic acid 90 (100 mg, 111 μmol) is brought to reaction with: a.: Cu(OAc)2·H2O (222 mg, <strong>1.1</strong>1 mmol, 10 eq), CH2Cl2 (20 mL); b.: C2O2Cl2 (2 mL), CH2Cl2 (30 mL); SnCl4 (1 mL), CH2Cl2 (30 mL). Leaving out the acidic demetallation step, pure Cu(II)-91 is obtained upon FC (silica, CH2Cl2 : hexanes = 1 : 1) as green-violet crystalline solid in 72.7 mg (77 μmol) yield, equiv. to 69.4 % based on 90. 1 H NMR / 13 C NMR: No clear results due to paramagnetism. MS (FAB+, NBA): m/z (%) = 944 (100) [M] +· . IR (ATR): 𝜈� [cm -1 ] = 3032, 2960, 2928, 2904, 2868, 1733, 1686, 1598, 1558, 1524, 1462, 1396, 1362, 1340, 1270, 1254, 1196, 1161, 1111, 1073, 1049, 1001, 871, 858, 846, 817, 798. UV/Vis (CH2Cl2): λ [nm] (ε [M -1 ·cm -1 ]) = 442 (222000), 570 (14400), 620 (16200). EA: C59H53N5O3Cu·C6H14·0.5 H2O. Calc.: C 75.15, H 6.60, N 6.74; found: C 75.21, H 6.52, N 6.68. N N Cu N N Cu(II)-91 C 59 H 53 N 5 O 3 Cu M = 943.63 g·mol -1 NO 2 183
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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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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 3.2.9 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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Page 194 and 195: 6 Experimental Section UV/Vis (CH2C
Page 196 and 197: 6 Experimental Section broad signal
Page 198 and 199: 7 References 16 H. Fischer, K. Zeil
Page 200 and 201: 7 References 57 S. Schwartz, K. Abs
Page 202 and 203: 7 References 89 (a) R. C. Fuson, J.
Page 204 and 205: 7 References 131 (a) J. Perdew, Phy
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1.1 Porphyrins - Friedrich-Alexander-Universität Erlangen-Nürnberg

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