1.1 Porphyrins - Friedrich-Alexander-Universität Erlangen-Nürnberg

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3 Discussion and Results other TPP’s like e.g. 15 without any functional groups. That implies that a reduction of 53 is easier to achieve due to the electron withdrawing ketone substituent affecting the electron density of the porphyrin’s π-system. Interestingly, those potentials are pretty close to the one’s observed for chlorin Me-33 (methyl pyropheophorbide a, see Scheme 20, p. 25). In the anodic region, the behavior appears well comparable to other tetraarylporphyrins indicating the oxidation processes are not much affected by the annulation. In all can be stated that the annulation affects the HOMO-LUMO gap as it leads to enhanced electron acceptor properties. 49 Table 8. Half-wave potentials for the given compounds obtained by measurements in CH2Cl2 (c = 10 -3 M) vs. ferrocene E(Fc/Fc + ) = 0.53 V as internal standard. Compound E½ Red2 [V] E½ Red1 [V] E½ Ox1 [V] E½ Ox2 [V] 53 -1.23 -0.95 +1.02 +1.25 40 a 15 b,112 60 -1.53 -<strong>1.1</strong>9 +1.02 +1.37 -1.45 -<strong>1.1</strong>4 +1.05 +1.35 Me-33 -1.23 -1.05 (+0.97) c (+1.43) c a 4 4 4 4 2 6 5 ,10 ,15 ,20 -tetra-t-butyl-5 -(methoxymethyl)-5 -methyl-5,10,15,20-tetraphenylporphyrin (see Scheme 24, p. 33) . b literature data on 5,10,15,20-tetraphenylporphyrin (see Scheme 6, p. 7) c Ox1 Ox2 values for observed cathodic peak potentials Epc and Epc , due to irreversibility
Discussion and Results 3 3.2.4 Chemical Reactivity of Mono-Exocyclic Cycloketo-Porphyrin 53 As it has been dealt with a novel class of substances, also their chemical properties needed to be investigated. Majorly those investigations focused on two subjects, the abilities of the system to act as ligand and the opportunities the exocyclic ketone entails. 3.2.4.1 Metal Complexes Based on the knowledge that the ability to form metal complexes is a common general feature of porphyrins, it was tried to synthesize different metal derivatives of 53 by application of standard procedures. The results have throughout been excellent leading to the conclusion that the annulated structure is beneficial for the metallation process. Trials provided metal complexes of Cu(II), Ni(II), Fe(III), Mn(III/V), Sn(IV), Co(II/III), In(III) and Zn(II) serving as proof of principle that many metals independent on their size or oxidation state can be implemented. Aiming at the development of novel photosensitizing materials, only the zinc(II) and indium(III) complexes were subjected to further investigations, as those metal centers are known to enhance the corresponding characteristics. Additionally, the nickel(II) and copper(II) complexes, being of interest from the synthetic point of view, were included into those investigations. While the latter, Cu(II)-53 and Ni(II)-53, were directly obtained from the cyclization procedure as mentioned before, Zn(II)-53 was synthesized utilizing the acetate method from free base 53. Thereby the reaction of the free base in CH2Cl2 with zinc(II)acetate, Zn(OAc)2·2H2O, dissolved in methanol, led to quantitative conversion within one hour. 93,96 To obtain In(III)-53, free base 53 was reacted in benzonitrile with indium(III)chloride, InCl3, and sodium acetate as base. 70b,113 The reaction furnished the desired target in 83 % yield with an additional chloro ligand as counterion at the trivalent indium center as MALDI-TOF-MS proved (m/z = 1041 [Chloro-In(III)-53] + (100 %), m/z = 1006 [In(III)-53] + (83 %)). Those complexes have been characterized by NMR as accurately as possible whereas the obtained data for Cu(II)-53 is not very conclusive. Due to paramagnetism a significant broadening of signals is being observed in the quite narrow area between 9 and 1 ppm containing the resonances for the arylic and the aliphatic protons like it is summed up in the experimental section. For the β-pyrrolic protons, no signals are observable at all. This is not surprising as it is known that even for highly symmetric Cu(II)-porphyrins these resonances 61
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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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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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3 Discussion and Results 3.2.8.2.7
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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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1.1 Porphyrins - Friedrich-Alexander-Universität Erlangen-Nürnberg

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