1.1 Porphyrins - Friedrich-Alexander-Universität Erlangen-Nürnberg

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3 Discussion and Results Thus, the most drastic NH-shifts to lower field are observed for the 3-17 bis-annulated systems being around 2.5 ppm compared to the precursor, while those are around 1.7 and 1.3 ppm for the systems being 3-13 or 3-7 annulated, respectively. In this regard, the conjugational impact of the electron withdrawing ketone groups is of major importance. For example, in 68 (largest shift), the whole π-system is involved as the ketone groups sit on opposite sides while in 71 (lowest shift), only four bonds of that π-system might be directly affected. This explanation is also supported by the resonances of the carbonyl carbon atoms in the corresponding 13 C NMR spectra. Also here, the signals experience a shift to lower field when the size of the conjugated system between the ketone groups is increased 46 from 71 (190.1 ppm) over 67 & 69 (191.0 ppm) to 68 & 70 (192.2 ppm). 3.2.7.4 UV/Vis Spectroscopy The UV/Vis spectra of BCKPs 67-71 show up even more bathochromically shifted as the ones obtained for the mono-exocyclic compounds. The shifts range between approx. 40 nm for the SORET band and up to approx. 85 nm for the highest Q-band to higher wavelengths, i.e. about the doubled value compared to 53. The extinction coefficients thereby are slightly lower than for 53, but as they are in the same order of magnitude (1.3-1.9·10 5 M -1 ·cm -1 ), the spectra are presented in a normalized fashion for comparison in Figure 39. As also here, the spectra of 67 & 69 and 68 & 70 appear almost identical, only one of the pairs is displayed to sustain clarity. The whole datasets are included in the experimental section. 1.0 A [a.u.] 0.8 0.6 0.4 0.2 0 100 71 67 70 300 400 500 600 700 λ [nm] 800 Figure 39. Normalized UV/Vis spectra of selected BCKPs in DMF solution.
normalized fluorescence 1.0 0.8 0.6 0.4 0.2 0 650 700 750 800 850 900 λ [nm] 1000 Discussion and Results 3 A special feature of those spectra is represented by the appearance of split SORET bands observable as shouldered peaks in the spectra of 71 (462/483 nm) and of 68 & 70 (451/468 nm) while an almost separated band is detectable for 67 & 69 (454/490 nm and 455/489 nm). This seems to be again reflecting the regiochemistry as the spectral distance between those two absorption is equivalent for corresponding pairs. The diagonal positioning of the exocycles, providing the largest spectral distance of those two bands, seems to be somehow special, as those spectra show the SORET band of lowest wavelength (451 nm) but also the most red-shifted Q-band (731 nm). Thus, it can be concluded, that this diagonal coupling of two exocyclic ketone moieties results in different perturbations of the first and higher excited singlet states. That means, the S0 → S1 energy gap decreases (bathochromic shift of Q-bands) whereas the energy difference between the ground state and Sn states becomes bigger (hypsochromic shift of at least parts of the SORET region). 3.2.7.5 Photophysical Data These data were obtained in cooperation with the group of Prof. Dr. B. RÖDER at Berlin. The steady-state fluorescence spectra being depicted in Figure 40 are in good agreement with the previously presented absorption spectra. The fluorescence maxima are detected at 810 nm for 71, at 775 nm 68 and 774 nm for 70, respectively, and at 731 nm for both 67 and 69 (all upon excitation at 532 nm). The obtained spectra of the investigated compounds thereby not only show different bathochromic shifts but also different shapes. For 68, 70 and 71, the bands appear much broader than for the other two compounds being consistent with the corresponding band-shapes of the highest Q-bands. Additionally, for those latter ones, a vibronic shoulder at higher wavelengths is observed whereas that could not be resolved for 68, 70 and 71. 67 68 69 70 71 Figure 40. Fluorescence spectra of BCKPs 67-71 in DMF solution at an excitation wavelength of 532 nm. 101
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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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Page 142 and 143: 5 Zusammenfassung 5 Zusammenfassung
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6 Experimental Section 6.2.4.5 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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