1.1 Porphyrins - Friedrich-Alexander-Universität Erlangen-Nürnberg

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3 Discussion and Results other band stays at the same wavelength or even shows a blue shift of 18 nm for Ni(II)-53. That behavior is in good agreement with GOUTERMAN’s theories stating that more electropositive metal centers cause a more pronounced red shift of the spectrum. Also the observed extinction coefficients go in line with theory as the ε values for the Q-band of lowest energy increase with lowered EN. 47,48a Exact values are gathered in Table 9. 1.0 OD 0.8 0.6 0.4 0.2 64 Ni(II)-53 Cu(II)-53 Zn(II)-53 In(III)-53 0 300 400 500 600 λ [nm] 700 Figure 27. UV/Vis spectra of the alongside listed metal complexes of 53 normalized to the SORET absorption. Measurements conducted in DMF. Table 9. UV/Vis data for metal complexes of 53 in comparison to those for free base 53: Wavelengths of absorption maxima given in nm with corresponding extinction coefficients in parenthesis given in M -1 ·cm -1 . Band Ni(II)-53 Cu(II)-53 Zn(II)-53 In(III)-53 53 SORET (B) 443 (184000) 442 (246500) 450 (264600) 452 (226800) 442 (223000) QI 560 (9800) 571 (11000) 589 (10400) 592 (10200) 543 (11300) QII 605 (10600) 623 (12500) 655 (12400) 658 (16300) 587 (9000) QIV - - - - 689 (9000) Fluorescence measurements were performed within the group of our cooperators (AG RÖDER, Berlin) under the same conditions as for free base 53. The data show very low fluorescence quantum yields for Zn(II)-53 and In(III)-53 while Ni(II)-53 and Cu(II)-53 are non- fluorescent. An explanation therefore can again be found by following GOUTERMAN’s findings. 47,107c As both zinc(II), [Ar] 3d 10 , and indium(III), [Kr] 4d 10 , represent closed shell ions, they should behave like regular porphyrins being fluorescent while copper(II), [Ar] 3d 9 , and nickel(II), [Ar] 3d 8 , exhibit additionally appearing singlet and triplet states leading to an
Discussion and Results 3 effective quenching. The corresponding energy level diagrams depicting the different situations are shown in Scheme 35. S 1 S 0 S 1 T 1 T 1 T 1 S 0 regular porphyrin copper(II) porphyrin nickel(II) porphyrin Scheme 35. Energy levels in different metalloporphyrins. Red lines represent COULOMB exchange interactions (CEI), green lines stand for spin-orbit couplings whereat dotted lines resemble normal measures and straight lines depict enhanced effects. 47,104,107c In the copper(II) case, a low lying singlet state on the energy level of the corresponding T1 state evolves due to CEI and is strongly coupled with the S1 state above while it does not couple with T1. So the fluorescence is quenched as consequence of relaxation involving that singlet state. For nickel(II) porphyrins, low lying triplet states exist which enhance spin-orbit couplings and thus make relaxation via fluorescence or IC in the singlet system improbable. So the relaxation will majorly occur in the triplet system either by IC processes or by phosphorescence which is especially pronounced for other metalloporphyrins of that group (e.g. palladium species). 47,104,107c Hence, the following discussion on photophysical parameters will concentrate on the fluorescent derivatives Zn(II)-53 and In(III)-53 whose data are summarized in Table 10 104 . Measurements elucidated that both metalloporphyrins fluoresce at lower wavelengths (blue shifted compared to 53) while they show lowered fluorescence quantum yields and shorter decay times (see Table 10). These effects are comprehensible if one takes into account that metallation also affects the energies of the frontier orbitals and those of the excited singlet and triplet states in regular systems. Additionally, in both cases only one major fluorophore (proportion > 97 %) was detected serving as further proof for the presence of tautomeric structures in the free base. S 1 S 0 65
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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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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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