1.1 Porphyrins - Friedrich-Alexander-Universität Erlangen-Nürnberg

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6 Experimental Section 6.2.4.5 5 4 ,10 4 ,15 4 ,20 4 -Tetra-t-Butyl-[3 , 5 2 ]-Ethano-5 6 -Methyl-3 1 -Oxo-5,10,15,20- O 150 Tetraphenylporphyrinato-Nickel(II), Ni(II)-53 In a 100 mL round bottom flask with reflux condenser, porphyrin ethanoic acid 51 (100 mg, 110 μmol) and 282 mg (1.1 mmol, 10 eq.) of Ni(acac)2 are dissolved in 40 mL of toluene and heated under reflux (∼135 °C) for 3 h. After evaporation of the solvent, the crude product is filtered over a silica plug to remove residing metal salts (eluent: CH2Cl2, polarity can be adjusted by addition of ethyl acetate) and further subjected to step b. of GP III: CH2Cl2 (50 mL), C2O2Cl2 (2 mL); CH2Cl2 (30 mL), SnCl4 (1.0 mL, 8.54 mmol). Leaving out the acidic demetallation step, the crude product obtained after work-up is purified by FC (silica, hexanes and CH2Cl2 in a 1 : 1 ratio) to give 54 mg (56.8 μmol) of pure Ni(II)-53 as dark green powder, equiv. to 51.7 % yield based on 51. 1 H NMR (300 MHz, rt, CDCl3): δ [ppm] = 0.93 (s, 3 H, CH3), 1.43 (s, 9 H, t-BuH), 1.53 (2s, 9+9 H, t-BuH), 1.54 (s, 9 H, t-BuH), 4.16 (d, 2 J = 11.9 Hz, 1 H, CH2), 5.60 (d, 2 J = 11.9 Hz, 1 H, CH2), 7.17 (d, 4 J = 1.5 Hz, 1 H, Ar’H), 7.61 (d, 4 J = 1.5 Hz, 1 H, Ar’H), 7.67 (d, 3 J = 7.2 Hz, 6 H, ArH), 7.88 (br s, 4 H, ArH), 8.55 (d, 3 J = 4.9 Hz, 1 H, β-H), 8.62 (m, 5 H, β-H), 8.75 (d, 3 J = 4.9 Hz, 1 H, β-H), 9.15 (s, 1 H, β-H). 13 C NMR (75.5 MHz, rt, CDCl3): δ [ppm] = 22.3, 31.4, 31.6, 34.7, 34.9, 53.6, 112.0, 118.2, 120.4, 124.0 (two signals), 124.1, 124.6, 127.2, 127.8, 132.3, 132.7, 132.9, 133.0, 133.3, 133.4, 134.6, 135.8, 136.2, 136.6, 137.0, 137.1, 138.2, 140.0, 140.3, 141.1, 143.0, 143.2, 143.4, 143.8, 144.0, 144.5, 150.7, 150.8, 151.0, 152.1, 192.3. MS (MALDI-TOF, no matrix): m/z (%) = 951 (100) [MH] + . IR (ATR): 𝜈� [cm -1 ] = 3030, 2962, 2904, 2870, 1683, 1543, 1505, 1479, 1461, 1396, 1350, 1268, 1199, 1162, 1111, 1069, 1050, 1011, 842, 818, 795, 717. UV/Vis (CH2Cl2): λ [nm] (ε [M -1 ·cm -1 ]) = 443 (184000), 560 (9800), 605 (10600). EA: C63H62N4NiO·0.5 H2O·0.5 C6H14. Calc.: C 79.11, H 7.04, N 5.59; found: C 79.03, H 6.94, N 5.70. N N Ni N N Ni(II)-53 C 63 H 62 N 4 NiO M = 949.89 g·mol -1
Experimental Section 6 6.2.4.6 5 4 ,10 4 ,15 4 ,20 4 -Tetra-t-Butyl-[ 3,5 2 ]-Ethano- 5 6 -Methyl- 3 1 -Oxo-5, 10, 15, 20- O Tetraphenylporphyrinato-Copper(II), Cu(II)-53 The synthesis follows GP III. Scheduled amounts: porphyrin ethanoic acid 51 (100 mg, 110 µmol); a.: CH2Cl2 (30 mL), Cu(OAc)2·2 H2O (380 mg, 1.1 mmol, 10 eq.); b.: CH2Cl2 (50 mL), C2O2Cl2 (2 mL); CH2Cl2 (30 mL), SnCl4 (1.0 mL, 8.54 mmol). The demetallation step is left out and Cu(II)-53 is finally obtained in pure after FC over silica with CH2Cl2 and hexanes (ratio 1 : 1) as eluent. Yield: 68 mg (71 µmol) of Cu(II)-53 as dark green-purple powder, equiv. to 64.5 % based on 51. 1 H NMR (400 MHz, rt, CDCl3): δ [ppm] = 1.39 (s, t-BuH), 1.42 (s, t-BuH), 1.54 (s, CH3), 3.88 (br s, CH2), 5.11 (br s, CH2), 7.50 (br s, ArH+β-H). 13 C NMR: No results due to paramagnetism. MS (MALDI-TOF, no matrix): m/z (%) = 954 (100) [MH] + . IR (ATR): 𝜈� [cm -1 ] = 3030, 2959, 2906, 2869, 1685, 1561, 1538, 1505, 1463, 1395, 1363, 1343, 1302, 1260, 1199, 1160, 1110, 1087, 1074, 1049, 1002, 864, 814, 802. UV/Vis (CH2Cl2): λ [nm] (ε [M -1 ·cm -1 ]) = 442 (246500), 571 (11000), 623 (12500). EA: C63H62CuN4O·0.5 H2O·0.5 C6H14. Calc.: C 76.78, H 6.78, N 5.39; found: C 76.61, H 6.95, N 5.43. N N Cu N N Cu(II)-53 C 63 H 62 CuN 4 O M = 954.74 g·mol -1 151
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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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Page 198 and 199: 7 References 16 H. Fischer, K. Zeil
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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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