1.1 Porphyrins - Friedrich-Alexander-Universität Erlangen-Nürnberg

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6 Experimental Section 6.2.5.11 αα-5 4 ,10 4 ,15 4 ,20 4 -Tetra-t-Butyl-[3,5 2 ],[13,15 2 ]-Diethano-5 6 ,15 6 -Dimethyl-3 1 ,13 1 - O 172 Dioxo-5,10,15,20-Tetraphenylporphyrin, 68 Pure 68 arises from the same reaction setup as 67, but it elutes as first major fraction in doing FC and appears as green powder in 29 mg (31 μmol) yield, equiv. to 12 % based on 77. 1 H NMR (400 MHz, rt, CDCl3): δ [ppm] = -0.94 (s, 2 H, NH), <strong>1.1</strong>7 (s, 6 H, CH3), 1.49 (s, 18 H, t- BuH), 1.57 (s, 18 H, t-BuH), 4.09 (d, 2 J = 11.2 Hz, 2 H, CH2), 5.45 (d, 2 J = 11.2 Hz, 2 H, CH2), 7.34 (d, 4 J = 1.7 Hz, 2 H, Ar’H), 7.64 (dd, 3 J = 8.1 Hz, 4 J = 1.7 Hz, 2 H, ArH), 7.67 (d, 4 J = 1.7 Hz, 2 H, Ar’H), 7.69 (dd, 3 J = 8.1 Hz, 4 J = 1.7 Hz, 2 H, ArH), 7.81 (dd, 3 J = 8.0 Hz, 4 J = 1.8 Hz, 2 H, ArH), 8.29 (dd, 3 J = 8.0 Hz, 4 J = 1.8 Hz, 2 H, ArH), 8.72 (d, 3 J = 4.9 Hz, 2 H, β-H), 8.78 (d, 3 J = 4.9 Hz, 2 H, β-H), 8.86 (s, 2 H, β-H). 13 C NMR (100.5 MHz, rt, CDCl3): δ [ppm] = 22.5, 31.4, 31.6, 34.7, 34.9, 53.5, 115.9, 124.2, 124.4, 124.8, 125.6, 128.5, 129.7, 130.4, 134.0, 135.7, 136.9, 137.3, 140.9, 141.5, 151.3, 152.6, 192.2. MS (FAB+, NBA): m/z (%) = 947 (100) [M] +· . IR (ATR): 𝜈� [cm -1 ] = 3030, 2953, 2899, 2864, 1683, 1602, 1559, 1509, 1475, 1459, 1393, 1363, 1339, 1262, 1235, 1193, 1150, 1108, 1011, 984, 869, 799, 722. UV/Vis (CH2Cl2): λ [nm] (ε [M -1 ·cm -1 ]) = 452 (163000), 469 (10900), 572 (9080), 620 (9500), 734 (11500). N NH HN N 68 C 66 H 66 N 4 O 2 M = 947.26 g·mol -1 O EA: C66H66N4O2·H2O·0.5 C6H14. Calc.: C 82.19, H 7.50, N 5.56; found: C 82.16, H 7.50, N 5.14.
Experimental Section 6 6.2.5.12 αα - 5 4 , 10 4 , 15 4 , 20 4 - Tetra - t - Butyl - 5 6 , 15 6 - Dimethyl - 5 , 10 , 15 , 20 - HO 2 C Tetraphenylporphyrinato-5 2 ,15 2 -Diethanoic Acid-Nickel(II), Ni(II)-77 Porphyrin diethanoic acid 77 (200 mg, 203 μmol) is suspended in toluene and acidified with some drops of glacial HOAc until a clear solution is obtained. Then, 261 mg (1.02 mmol, 5 eq.) of Ni(acac)2 are added and the mixture is stirred under reflux conditions for 3 h before the solvents are evaporated completely and the residue is subjected to FC (silica, toluene : THF = 9 : 1) to furnish 182 mg (175 μmol) of pure Ni(II)-77 as red powder equiv. to 86.2 % based on 77. 1 H NMR (400 MHz, rt, THF-d8): δ [ppm] = -1.55 (2s, 18+18 H, t-BuH), 1.76 (s, 3 H, CH3), 3.19 (s, 2 H, CH2), 7.50 (d, 4 J = 1.4 Hz, 2 H, Ar’H), 7.62 (d, 4 J = 1.7 Hz, 2 H, Ar’H), 7.74 (d, 3 J = 8.5 Hz, 4 H, ArH), 7.96 (d, 3 J = 8.2 Hz, 4 H, ArH), 8.56 (d, 3 J = 4.9 Hz, 4 H, β-H), 8.69 (d, 3 J = 4.9 Hz, 2 H, β-H), 10.2 (s br, 2 H, COOH). 13 C NMR (100.5 MHz, rt, THF-d8): δ [ppm] = 21.8, 31.9, 35.4, 35.5, 40.2, 117.1, 119.7, 124.7, 125.5, 125.8, 132.8, 133.1, 134.5, 137.0, 138.4, 139.2, 139.8, 143.6, 144.0, 151.4, 151.9, 172.5. N N Ni N N Ni(II)-77 C 66 H 68 N 4 NiO 4 M = 1039.96 g·mol -1 CO 2 H MS (FAB+, NBA): m/z (%) = 1038 (100) [M] +· , 993 (10) [M-CO2H] +· . IR (ATR): 𝜈� [cm -1 ] = 3030, 2964, 2905, 2869, 1726, 1694, 1605, 1554, 1509, 1461, 1422, 1394, 1352, 1267, 1205, 1074, 1004, 817, 799, 738, 715. UV/Vis (CH2Cl2): λ [nm] (ε [M -1 ·cm -1 ]) = 415 (247500), 528 (20100). EA: C66H68N4NiO4·THF. Calc.: C 75.60, H 6.89, N 5.04; found: C 75.53, H 7.04, N 5.01. 173
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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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1.1 Porphyrins - Friedrich-Alexander-Universität Erlangen-Nürnberg

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