1.1 Porphyrins - Friedrich-Alexander-Universität Erlangen-Nürnberg

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3 Discussion and Results 74 Δθ [mdeg] 18 9 0 Peak A t [min] 4 6 8 t [min] 4 6 8 -9 exp. CD -18 Peak A 300 400 500 λ [nm] 600 Δθ [mdeg] 18 9 0 Peak B HPLC-UV 435 nm HPLC-CD 435 nm -9 exp. CD -18 Peak B 300 400 500 λ [nm] 600 Figure 29. Top: Elugrams obtained by HPLC (analytical level, Phenomenex® Lux column, isocratic solvent system iso-propanol:hexane = 3:97, flow 0.8 mL·min -1 ) for 53 utilizing detection via UV/Vis absorption (HPLC-UV) or via the absorption of circularly polarized light (HPLC-CD) at a wavelength of 435 nm. Bottom: online circular dichroism spectroscopy (online CD) of the resolved fractions. Thus, cycloketo-porphyrin 53 represents the first example of an inherently chiral porphyrin system due to a distorted π-system being perfectly stable and resolvable without the need of external stabilizers.
3.2.6 Studying the Structure-Properties-Relations O N NH HN N O N NH HN N Discussion and Results 3 As it has been a great surprise that such a kind of simple system like 53 can disclose the previously presented extraordinary features, it needed further investigations on the structure-properties-relationship (SPR) to reveal how characteristic features in the cycloketo-porphyrin might be caused. So the next part of the work is strongly connected to the study of similar systems with just minor changes and to investigate their behavior. 3.2.6.1 Possible Influences & Choice of Reference Systems In principle, two features present in 53 are considered to have significant influence on the chiral and photophysical behavior: On the one hand the seven-membered ring structure in the keto-exocycle and, on the other hand, the opposite lying methyl group ortho in respect to the porphyrin core. In order to figure out in how far these features contribute to the overall performance of that system, two models (Scheme 41 middle and right) were chosen lacking one or both of that structural features. The t-butyl substituent on the tethered phenyl ring was also left out in the model compounds since it is not considered to have any observable impact and as that eased the synthetic access to systems 57 and 58. Both were then obtainable from methyl 2-formylbenzoate. leave out leave out O N NH HN N Scheme 41. Mother compound 53 and simplified model compounds 57 and 58 with changes marked with arrows. The synthesis of the shown model compounds will be discussed within the following paragraphs. 53 57 58 75
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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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Page 54 and 55: 3 Discussion and Results 3.2.3.2 NM
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Page 76 and 77: 3 Discussion and Results voltammogr
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Page 86 and 87: 3 Discussion and Results vibration
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Page 90 and 91: 3 Discussion and Results cyanomethy
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Page 124 and 125: 3 Discussion and Results 116 HO 2 C
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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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4 Summary As the characterization d
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5 Zusammenfassung 5 Zusammenfassung
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5 Zusammenfassung Da in guten Ausbe
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6 Experimental Section UV/Vis spect
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6 Experimental Section 6.2 Studied
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6 Experimental Section 13 C NMR (10
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6 Experimental Section (cyanomethyl
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6 Experimental Section 6.2.4 AB3-Ty
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6 Experimental Section 6.2.4.3 5 4
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6 Experimental Section 6.2.4.11 10
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6 Experimental Section EA: C57H56N4
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6 Experimental Section 6.2.4.15 10
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6 Experimental Section 6.2.5 A2B2-T
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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 6.2.6 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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204 56 57 58 59 60 61 62 63 64 65 6
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1.1 Porphyrins - Friedrich-Alexander-Universität Erlangen-Nürnberg

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