1.1 Porphyrins - Friedrich-Alexander-Universität Erlangen-Nürnberg

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3 Discussion and Results 116 HO 2 C O N N NH HN N N Cu N N NO 2 NO 2 a. O N N Cu N N b. NO 2 a. O N N Cu N N b. NH 2 O N NH HN N 90 Cu(II)-91 91 Scheme 55. Ring closing procedure applied to 90 to finally yield 91 via its copper(II) complex Cu(II)-91. Applied conditions: a.: 1. Cu(OAc)2·2 H2O, CH2Cl2/MeOH/AcOH, rt, 15 h; 2. C2O2Cl2, CH2Cl2, rt, 1.5 h; 3. SnCl4 , CH2Cl2, rt, 10 min; b. TFA/H2SO4, rt, 45 min. O N NH HN N Cu(II)-91 Cu(II)-92 92 Scheme 56. Reduction protocol leading to free base 15 4 -amino substituted cycloketoporphyrin 92 via its corresponding copper(II) complex. Applied conditions: a.: SnCl2 in EtOH/EtOAc/HCl, reflux, 3-5 h; 138 b.: TFA/H2SO4, rt, 45 min. While the abovementioned protocol gave rise to free base 15 4 -amino substituted system 92 in 81.8 % isolated yield without any further reduction of the exocyclic ketone, it was not possible to directly apply that reduction procedure to the free base nitro derivative as that led to the formation of the corresponding tin(IV) complex Sn(IV)-92. Also the reaction time and acidity of the reaction media in reducing Cu(II)-91 had to be carefully stuck to since else transmetallation occurred also leading to undesirable tin(IV) complex formation. All those compounds were fully characterized and investigated concerning their photophysical parameters what will be treated in the following paragraphs. NO 2 NH 2
3.2.8.2.4 Characterization of Free Base Cycloketo-<strong>Porphyrins</strong> 91 and 92 9.0 8.5 8.0 7.5 7.0 Discussion and Results 3 Both systems 91 and 92 were purified by FC and gave clear MALDI-TOF MS spectra exclusively showing the molecular peaks at m/z = 883 and 853, respectively. The 1 H NMR spectra being shown in Figure 45 appear well comparable to analog non- functionalized cycloketo-porphyrin 53. 2 β-H ‡ ‡ o-ArX ArH m-ArX 3 2 in 5 3 5 5 3 2 out ‡ ‡ NH 2 10 4 20 4 5 4 9 8 7 6 5 4 3 2 1 0 δ [ppm] -2 5 6 * * * * ‡ * CDCl 3 hexane 91 (-NO2) 92 (-NH2) Figure 45. 1 H NMR spectra of 91 and 92 measured at 400 MHz in CDCl3 at rt. Signals are numbered according to IUPAC recommendations. While the resonances for the β-pyrrolic protons give rise to the typical set of seven signals in between 8.70 and 8.97 ppm for 91 and 8.62 and 8.95 ppm for 92, respectively, they only appear well separated from each other for nitro derivative 91. This indicates that the functionality on the peripheral phenyl ring has an impact on the porphyrin macrocycle although it is situated quite far away of it. This feature should hence also be visible in the cyclic voltammograms which are being discussed later on. Not surprisingly, the signals of the phenyl ring carrying those functional groups are significantly affected. Like in 53, the signals for that substituent in 15 position are line-broadened due to changed rotational barriers. For NH 117
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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 3.2.3.3.2
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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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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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Page 86 and 87: 3 Discussion and Results vibration
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Page 132 and 133: 3 Discussion and Results 3.2.9 Pote
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Page 140 and 141: 4 Summary As the characterization d
Page 142 and 143: 5 Zusammenfassung 5 Zusammenfassung
Page 144 and 145: 5 Zusammenfassung Da in guten Ausbe
Page 146 and 147: 6 Experimental Section UV/Vis spect
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Page 166 and 167: 6 Experimental Section EA: C57H56N4
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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 6.2.5.15 5 4
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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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