1.1 Porphyrins - Friedrich-Alexander-Universität Erlangen-Nürnberg

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3 Discussion and Results The remainder characterization data being summed up in the experimental section appeared well comparable to the ones for other porphyrin building blocks of that kind and will hence not be further discussed here. For the annulation, also 79 was initially transformed into its corresponding copper(II) complex by reaction via standard conditions in acidified CH2Cl2. 96,97 The conversion into the tetra-ethanoic acid chloride turned out to be difficult as Cu(II)-79 could not be solubilized in the usual CH2Cl2 / oxalyl chloride mixture. The conversion was finally conducted in pure oxalyl chloride, C2O2Cl2, at room temperature over a period of 6 h. After complete evaporation of the reagent being also the solvent, the activated derivative of Cu(II)-79 could be taken up in CH2Cl2 and reacted with the tin tetrachloride catalyst, SnCl4. Thereby the color did not change to green as it was observed in all other cycloketo-porphyrin syntheses but the brownish solution brightened up to get a salmon-like color. TLC monitoring indicated the formation of two species as it was expected (see Scheme 49). HO 2 C 108 CO 2 H N N Cu N N HO 2 C CO 2 H O O N NH HN N O O + O O N NH HN N Cu(II)-79 80 81 Scheme 49. Synthesis of tetra-annulated cycloketo-porphyrins 80 and 81 from Cu(II)-79. Applied conditions: 1. C2O2Cl2, rt, 6h; 2. SnCl4, CH2Cl2, rt, 20 min; 3. TFA, H2SO4, rt, 1h. After work-up, the crude product mixture was complete evaporated to subject it to the demetallation procedure already described 96 , but the material could not be solubilized under these conditions. Thus, the reaction was repeated, the obtained product mixture concentrated and demetallated as it is known that the free-base system exhibit a higher solubility. But also then, it was not possible to obtain soluble products. So it has to be concluded that multiple annulation to poly-exocyclic compounds seems possible but does not deliver soluble compounds to be purified and characterized. Hence, the study of other poly-annulated compounds was set aside and it was further focused on the implementation of an additional functional group to mono-annulated systems. O O
O N NH HN N O N NH HN N Discussion and Results 3 3.2.8 Cycloketo-Porphyrin Systems with Additional Functionality To exploit the properties of the synthesized cycloketo-porphyrin systems for applications in terms of PDT or any other technical device, it was necessary to modify the structure of 53 to gain the ability of attaching it covalently to antibodies, multiplying units or functional surfaces. 68 Based on the aforementioned findings, it was decided to leave the exocycle as well as the remaining β-positions untouched since the electrochemical and photophysical behavior might else be negatively affected. Also the oppositely lying methyl substituent should not be changed as an enlargement would raise the steric hindrance hampering the closure of the exocyclic ring. So modifications are to be carried out on one of the three peripheral t-butyl phenyl substituents. Therefore two approaches were taken into account. Firstly, already known bis-functional system like 42 or 43 could serve as basis since those can be mono-functionalized to achieve the ring closure whilst the residual functionality could finally be converted into the desired anchor. Secondly, the porphyrin architecture could be changed from an AB3-type to AB2C in which the A substituent provides the appropriate functionality for the formation of the exocycle while the C substituent possesses the desired anchor or a precursor for that. These approaches are sketched in Scheme 50 and discussed in the following paragraphs. X 53 O N NH HN N Scheme 50. Possible approaches to modified cycloketo-porphyrins derived from basic structure 53 via dissymmetric functionalization of e. g. 42 (left) or by construction of an AB2C-type system (right) where in both cases -X represents a coupleable group like -NH2, -OH or -CO2H. X 109
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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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Page 140 and 141: 4 Summary As the characterization d
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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 6.2.5.3 5 4
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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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1.1 Porphyrins - Friedrich-Alexander-Universität Erlangen-Nürnberg

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