1.1 Porphyrins - Friedrich-Alexander-Universität Erlangen-Nürnberg

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4 Summary As the characterization data showed, the systems contain a distorted π-system arising from the structural features being analogous to those already known for dodeca-substituted porphyrins. But in contrast, the ones under investigation here turned out to be outstandingly stable in configuration, as VT NMR spectroscopy demonstrated, and therewith represent stable inherently chiral systems. The racemic mixtures which arose from synthesis have been resolvable by chiral HPLC so that it was possible to characterize the individual enantiomers by CD spectroscopy in cooperation with the group of G. BRINGMANN. Thus, for the first time, we were able to describe stable inherently chiral porphyrin systems whose chirality is due to a distorted π-system. Via temperature-dependent NMR spectroscopy, it was also possible to show that the lowering of symmetry is leading to the presence of distinguishable tautomers within mono- exocyclic cycloketo-porphyrin system 53. Interestingly, those tautomers turned out to be differentiable by photophysical means. So, in cooperation with the group of B. RÖDER, a novel spectroscopic methodology for the detection and characterization of tautomeric porphyrin structures could be developed. Furthermore, the conducted photophysical experiments showed that the structural elements and the thus arising deviation from planarity within the π-system is leading to an enhanced spin-orbit-coupling providing a high intersystem crossing probability and hence, an efficient excitation into triplet states. It was shown further on that the excitation energy can be transferred onto present triplet oxygen nearly quantitatively and it was demonstrated that the corresponding performance of the systems can be effectively tuned via variations in the architecture of the exocycle as well as by degree and regiochemistry of poly-annulation. Thus, novel singlet oxygen generators were made accessible captivating through their high stability and outstanding quantum yields. Such systems are of great interest for hygiene applications (e.g. for detoxification of water or air) and also for medicinal means (foremost for applications in terms of the photodynamic therapy of cancer) as, in comparison to pheophorbides, they exhibit a far higher stability, a better solubility and an increased efficiency. Also corresponding metal complexes (e.g. In(III)-53) and coupleable derivatives with additional amino functionality (92) were made accessible without significant changes in the photophysical performance. Those systems allowed investigations on completely novel concepts of application. For example, it has been shown that the FÖRSTER resonance energy 132
Summary 4 transfer (FRET) can be utilized within photosensitizing concepts as the results on conjugate 94 of pyropheophorbide a 33 and cycloketo-porphyrin 92 illustrated. Thus, excitation wavelengths and the „active window“ can be effectively tuned. Furthermore, the investigations on In(III)-53 implied that novel combinational therapies could be opened up. The implementation of a radioactive metal center (like e.g. In-111) could then be used for tumor localization while the ligand, being an effective photosensitizer, would allow for an in situ treatment by PDT. Both approaches show promise but need further investigations for which the results, achieved within this thesis, lay foundation to. 133
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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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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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Page 142 and 143: 5 Zusammenfassung 5 Zusammenfassung
Page 144 and 145: 5 Zusammenfassung Da in guten Ausbe
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6 Experimental Section UV/Vis (CH2C
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6 Experimental Section 6.2.6.7 5 4
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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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