1.1 Porphyrins - Friedrich-Alexander-Universität Erlangen-Nürnberg

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3 Discussion and Results phenyl substituents. For 53 and 57 those are clearly lowered since a significant line broadening is observed representing the presence of a coalescence-like state. Connatural situations are also found in non-annulated tetraarylporphyrins with distinguishable half- spaces but at higher temperatures. As for 58, the exocyclic structure seems to be flexible itself, no definite statement is possible according to the underlying data. Since the rising tilt of the tethered phenyl ring is supposed to affect the electronic structure of the porphyrin core by mingling with its orbitals, variations in the porphyrin’s ring current are to be observed resulting in significant shifts of resonances for protons inside or situated directly on the periphery of the macrocycle. And indeed, this is detected for all studied compounds whereas the shifts seem to be the more pronounced the more the tethered phenyl ring is tilted. Exemplarily, some observed signals are gathered in Table 13. Table 13. Chemical shifts δH of selected signals in compounds 53, 57 and 58 with given position number based on measurements at 400 MHz in CDCl3 at rt. a 86 Compound δH(2) δH(NH) dihedral angle a 53 8.96 -1.62 55° 57 9.16 -1.70 46° 58 9.24 -0.55 15° angle between the C meso -C α -bond and the plane of the tethered phenyl substituent (see also Figure 32, p. 84) a 3.2.6.5.3 UV/Vis Spectroscopy Just like the NMR spectra, also the UV/Vis spectra of 53 and 57 appear similar while 58 differs quite a lot (Figure 34). While for all compounds a huge bathochromic shift of all bands is observed compared to the precursors, it is most pronounced for 58 as the summarized data in Table 14 depicts. The rising bathochromic shift nicely reflects the more pronounced interaction of the tethered phenyl ring’s orbitals with those of the porphyrin macrocycle when the substituent becomes more tilted. The effect, being in full accordance to literature data of extended π- systems 46,48a , appears most pronounce for 58 where the tethered substituent is nearly coplanar and thus in significant conjugation. Since 53 and 57 do not differ that much in their torsion of the tethered phenyl ring it is also not surprising that their spectra are very similar. Interestingly, 58 shows a considerable shoulder on the SORET band which is also detectable
ε [M -1 ·cm -1 ] 2.0·10 5 1.5·10 5 1.0·10 5 0.5·10 5 0 300 400 500 600 λ [nm] 800 Discussion and Results 3 for 53 and 57 but much more less pronounced. That is considered to be due to the appearance of low lying A’’ states in the energy region of the SORET states arising from electronic excitation of an electron in an in-plane orbital of the keto group to π* orbitals of the porphyrin. 100 That effect appears more pronounced the more effective the conjugation between the 5-substituent and the macrocycle is. Furthermore, the highest Q-band absorption shows up more intense compared to those of lower wavelengths as the attached keto group enhances the Q-band oscillator strengths the more effective conjugation is possible. 100 Figure 34. UV/Vis spectra of compounds 53, 57 and 58 as solution in CH2Cl2. Table 14. UV/Vis data: maximum wavelengths (λmax) of compounds 53, 57 and 58 and their extinction coefficients ε opposed to those of precursor system 51. Compound SORET (B) a 53 442 (223000) 543 (11300) 57 438 (182000) 540 (8200) 58 465 (99500) 579 (5000) 51 420 (313600) 516 (13400) a † λmax with corresponding ε value given in parenthesis a band contains a shoulder at higher wavelength ‡ no separate corresponding band detectable 53 57 58 QI a QII a QIII a QIV a 587 † (9000) 584 † (7100) 644 (7700) 551 (7300) - ‡ - ‡ - ‡ 592 (4700) 689 (9000) 686 (5000) 745 (9300) 647 (3400) 87
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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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Page 46 and 47: 3 Discussion and Results Table 4. S
Page 48 and 49: 3 Discussion and Results 3.2.2.2 FR
Page 50 and 51: 3 Discussion and Results 3.2.2.3 Ac
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Page 54 and 55: 3 Discussion and Results 3.2.3.2 NM
Page 56 and 57: 3 Discussion and Results 3.2.3.3 Va
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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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Page 136 and 137: 3 Discussion and Results Table 25.
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Page 140 and 141: 4 Summary As the characterization d
Page 142 and 143: 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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