1.1 Porphyrins - Friedrich-Alexander-Universität Erlangen-Nürnberg

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3 Discussion and Results (being supposed to appear around +40 ppm) are expected to be terribly broadened (up to 48 kHz) and hence impossible to detect. 114 The 1 H NMR spectra for the remainder compounds, abstracts of which are being depicted in Figure 26, appear diamagnetic and nicely reflect the characteristic impacts of the implemented metal ions. 9.2 9.0 8.8 8.6 8.4 8.2 8.0 7.8 7.6 δ [ppm] 7.2 Figure 26. Aromatic regions of the 1 H NMR spectra of selected metal complexes measured at room temperature in CDCl3 (*) at 400 MHz in comparison to free base system 53. The signals for the β-pyrrolic positions within the studied diamagnetic metal complexes appear as resolved as it is the case for free base 53 but experience significant shifts to lower field except those situated on non-annulated pyrrolic units in the nickel(II) complex being shifted upfield. More drastic changes are observed for the arylic signals not only being shifted but also affected in their line broadening. While for Ni(II)-53 a huge line broadening effect is found, the signals appear better resolved for the indium(III) complex In(III)-53. For Zn(II)-53 nearly every position is providing a clear signal being comparable to spectra of the free base system at lowered temperatures (see Figure 19). 62 * * * * 53 Ni(II)-53 In(III)-53 Zn(II)-53
Discussion and Results 3 To explain this behavior, electronic and structural effects of the metal centers have to be taken into account. Nickel(II) being the most electronegative metal center (EN(Ni) = 1.91) 115 and also the smallest one (rNi(II) = 0.63 Å) 116 is thus perfectly fitting within the macrocycle allowing an efficient orbital overlap and therewith a pronounced electronic communication leading to the huge shifts observed for the signals of the β-protons. Due to the filled dz2 orbital, axial ligands are repelled and such complexes exist as bare metal species in mostly square planar coordination geometry while distortions of the usually planar macrocycle are common to provide saddled or ruffled conformations. 40 As this eases rotational processes, the intense line broadening for the arylic resonances becomes well comprehensible. Indium(III) and zinc(II) being less electronegative (EN(In) = 1.65, EN(Zn) = 1.78) 115 represent larger ions (rIn(III) = 0.74 Å, rZn(II) = 0.82 Å) 116 which adopt out-of-plane conformations when they form porphyrin complexes being five-coordinate in a square pyramidal fashion. This is leading to differentiable half-spaces within the porphyrin molecule affecting the rotational barriers of the meso-phenyl substituents and also the chemical shifts of the protons lying in those half-spaces. With rising rotational barriers, the signals become sharper while the then differentiable chemical surroundings above and below the macrocycle’s plane provide larger signal differences (Δδ). These facts explain the better resolution observed in those spectra whereas the effects appear strongest for zinc(II) complex Zn(II)-53. That fact becomes plausible by taking into consideration that indium(III) is smaller and that the additional ligand in indium(III) porphyrin complexes is very labile (binding constants too small to be measured in most cases) leading to fast exchange processes on the NMR timescale. 40 In connection with the photophysical properties, UV/Vis and steady-state fluorescence spectra were recorded and investigations were conducted concerning the different relaxation pathways from the first exited singlet state and singlet oxygen generation. The UV/Vis spectra have the typical shape for metallated porphyrins consisting of the SORET absorption in the blue region and two Q-band absorptions in the red region of the spectrum (Figure 27). For Zn(II)-53 and In(III)-53, the whole spectra are significantly bathochromically shifted by 8 and 10 nm, respectively, for the SORET band and between 32 and 49 nm for the Q-bands. In the spectra obtained for Ni(II)-53 and Cu(II)-53 the corresponding shifts are non- uniform as only the QI-band depicts a red shift by 17 and 28 nm, respectively, while the 63
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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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Page 22 and 23: 1 Introduction 1.2 Photodynamic The
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Page 26 and 27: 1 Introduction intact membranes bei
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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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