1.1 Porphyrins - Friedrich-Alexander-Universität Erlangen-Nürnberg

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3 Discussion and Results 3.2.3.1 IR & UV/Vis Spectroscopy In the IR spectrum the characteristic carbonyl vibration is found at 1683 cm -1 being in the typical region for α,β-unsaturated or aromatic ketones. 46 This shows that the carbonyl group is indeed in conjugation with the porphyrin’s π-system and therewith lying more or less in the porphyrin plane fitting well with the assumed geometry. Other vibrations of the porphyrin appear nearly unaffected compared to the basic systems. As expected, the UV/Vis spectrum shows up quite different from the ones of the purple precursor systems since the obtained product is of olive-green color. To illustrate the difference, in Figure 15, the spectrum of 53 is opposed to the one of 51 being the direct non- annulated free base precursor. The exact values for the observed wavelengths and the corresponding extinction coefficients are given in Table 5. ε [M -1 cm -1 ] 3.0·10 5 2.5·10 5 2.0·10 5 1.5·10 5 1.0·10 5 5.0·10 4 44 0 SORET (B) Q I Q II Q IV Q III 500 550 600 650 700 400 500 600 700 λ [nm] Figure 15. UV/Vis spectra for 51 and 53 in CH2Cl2. Table 5. Absorption bands for 51 and 53 with given values for the band maxima (λmax) and corresponding extinction coefficients (ε) in CH2Cl2. 51 53 SORET (B) QI QII QIII QIV 420 313600 442 223000 516 13400 543 11300 a Band appeared not separated but as shoulder of QII. 551 7300 587 9000 592 4700 - a 647 3400 689 9000 λmax [nm] ε [M -1 cm -1 ] λmax [nm] ε [M -1 cm -1 ] Apparently, the annulation causes a huge bathochromic shift of all bands, whereby the SORET band is less shifted (∼22 nm) than the Q-bands (up to 42 nm). Concerning the extinction 51 53
Discussion and Results 3 coefficients, the behavior is not uniform as the ε value for the SORET band decreases by nearly 30 % while the ones for the Q-bands stay comparable or even increased. For example, the value for QIV appears surprisingly high – nearly triple the one observed in 51. Additionally, the whole Q-band region shows up quite badly resolved as if different band sets overlaid each other what might indicate the presence of different species like e.g. tautomers. To explain those observations, it seemed worth to compute the shapes of the molecule’s frontier orbitals. Calculations were performed on the PM3 level using Materials Studio® 99 and resulted amongst others the pictures presented in Figure 16. HOMO LUMO Figure 16. Calculated shapes of HOMO and LUMO in 53. Therewith, the explanation for the detected red-shift of all bands is straightforward since the ketone in the exocycle as well as the tethered phenyl ring become to some extend incorporated into to porphyrin’s π-system leading to the observed effect. The displayed dissymmetry of the orbitals hints to a loss of degeneracy being also deducible from the calculated orbital energies. As consequence, the number of energy levels and therewith the number of possible π → π * transitions should rise resulting in additional bands in close proximity to each other. That would explain the observed seemingly overlaid Q-bands. The increase in the corresponding extinction coefficients is considered to be due to a significant enhancement of the oscillator strengths of the Q-bands arising from the conjugated keto group. Computational studies on higher levels support these assumptions. 100 45
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Page 5 and 6: Table of Contents 1 Introduction 1
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3 Discussion and Results (75 eq.) w
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3 Discussion and Results 3.2.7.2 Sy
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3 Discussion and Results correspond
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3 Discussion and Results The remain
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3 Discussion and Results 3.2.8.1 Us
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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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