1.1 Porphyrins - Friedrich-Alexander-Universität Erlangen-Nürnberg

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3 Discussion and Results Table 10. Photophysical parameters for Zn(II)-53 and In(III)-53 in comparison to free base 53. 66 λfl [nm] a τ [ns] b Φfl c Zn(II)-53 702 0.6 0.02 0.08 0.90 0.86 In(III)-53 689 0.3 0.01 0.17 0.82 0.74 53 716/695 g 1.15/3.3 g ΦIC d ΦISC e ΦΔ f 0.03 0.09 0.88 0.85 a maximum in the fluorescence spectra in DMF at 532 nm excitation wavelength b fluorescence decay time determined in DMF via TCSPC at 532 nm excitation wavelength c d quantum yield of fluorescence in DMF with pyropheophorbide a 33 (Φfl = 0.28) as reference quantum yield of internal conversion in DMF e quantum yield of intersystem crossing in DMF determined via ps-TAS f quantum yield of singlet oxygen generation in DMF with 5,10,15,20-tetraphenylporphyrin 15 (Φfl = 0.65) as reference 88 g values for the two present tautomeric structures of 53 Measurements using the ps-TAS technique 96,109 and singlet oxygen luminescence 96,111 provided corresponding ΦISC and ΦΔ values being slightly lower for In(III)-53 compared to free base 53 while Zn(II)-53 gives rise to nearly identical values. Thus, no further enhancement of transition via intersystem crossing or singlet oxygen generation can be achieved by insertion of zinc(II) or indium(III) while both complexes still are well suited for PDT applications. The electrochemical behavior was studied for all metal complexes in focus by cyclic voltammetry analog to free base 53 (see paragraph 6.1). The obtained voltammograms are depicted in Figure 28 and determined half-wave potentials are given in Table 11. Table 11. Determined half-wave potentials, E½, for selected metal complexes of 53 in comparison to the free base system given in V vs. ferrocene E(Fc/Fc + ) = +0.53 V (see paragraph 6.1 for procedure details). Values in italics refer to literature data for metal complexes of TPP 15 or the free base. Compound E½ Red2 [V] E½ Red1 [V] E½ Ox1 [V] E½ Ox2 [V] Ref. Cu(II)-53 (-1.35) a -1.80 -0.99 -1.33 +1.01 +0.98 +1.37 +1.21 117 Ni(II)-53 - - b -1.01 -1.23 +1.09 +1.10 +1.39 +1.22 118 In(III)-53 -1.16 -1.48 -0.81 -1.09 +1.22 +1.16 +1.52 +1.45 119 Zn(II)-53 -1.39 -1.84 -1.04 -1.39 +0.90 +0.78 +1.13 +1.11 120 53 -1.23 -1.45 -0.95 -1.14 +1.02 +1.05 +1.25 +1.35 112 a not conclusive as peaks are only sparsely pronounced b no corresponding (quasi-)reversible process detected
10 μA Discussion and Results 3 -1.8 -1.6 -1.4 -1.2 -1.0 -0.8 -0.6 -0.4 -0.2 0 E [V] 0.8 1.0 1.2 1.4 1.6 1.8 Figure 28. Cyclic voltammograms for selected metal complexes of 53. Cu(II)-53 Ni(II)-53 In(III)-53 Zn(II)-53 In the anodic region of the spectra the usual behavior of porphyrin systems is detected with two reversible redox processes in each case. The determined values for the half-wave potentials are in good agreement with literature data for the corresponding metal complexes of TPP 15 although the potentials for the second oxidation step, E½ Ox2 , appear slightly higher for the copper(II) and the nickel(II) complex (shifts of 0.17 V and 0.16 V, respectively) indicating a more difficult second oxidation. This is to be seen in connection with the electron withdrawing ketone substituent on the macrocycle and thus plausible. In the cathodic region the same behavior is found as for free base system 53 since all observed half-wave potentials are strongly shifted to higher values by 0.22 to 0.44 V. This enhanced reducibility is also a result of the electron withdrawing ketone moiety in conjugation to the porphyrin core. While for the zinc(II) and indium(III) complexes two reduction processes are found, only one each can be resolved for the corresponding copper(II) and nickel(II) complexes being again in full accordance to literature. In the 67
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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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Page 30 and 31: 2 State of The Art & Aims They were
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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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