1.1 Porphyrins - Friedrich-Alexander-Universität Erlangen-Nürnberg

More documents

Recommendations

Info

3 Discussion and Results has been delivered by theoretical simulations which were done in the group of C. MARIAN using the combined density functional theory / multi-reference configuration interaction (DFT/MRCI) method. 100 Those confirmed our assumed geometry and delivered values for the vertical excitation energies (Table 7). Table 7. Calculated vertical excitation energies based on excitation from the ground state geometry (E(S0) = 0 eV). 104 singlet system ΔE [eV] triplet system ΔE [eV] S1 1.7866 T1 1.5635 S2 2.1681 T2 1.9183 Since the T1 state is lying curtly below the S1 state energetically, the intersystem crossing is possible in principle. Taking into account the also calculated value for the corresponding spin-orbit coupling matrix element of 0.92 cm -1 being significantly higher than in planar free base porphin 2 (0.04 cm -1 ), the distortion of the porphyrin core indeed results into an enhanced spin-orbit coupling between S1 and T1 leading to increased probabilities of related processes. 104 3.2.3.4.4 Singlet Oxygen Luminescence The data being already discussed imply an effective population of the first excited triplet state (T1) in 53 being considered a crucial state for photodynamic action. By energy transfer via collision with present triplet oxygen, 3 O2, this state of a sensitizer can be quenched while singlet oxygen ( 1 O2, 1 Δg) is produced. 110 The effectiveness of such a process can be described in terms of the corresponding quantum yield of singlet oxygen generation, ΦΔ, accessible by measurements of the 1 O2 luminescence at 1270 nm. 111 Corresponding experiments were done using TPP 15 (ΦΔ = 0.65 88 ) as reference system. The obtained value of 0.85 ± 0.03 for ΦΔ is very close to ΦISC and therewith suggests that the efficiency of the energy transfer T1 → 3 O2 is to be estimated close to 1 for 53. 96 58
3.2.3.5 Cyclic Voltammetry -1.6 5 μA Discussion and Results 3 Also the electrochemical behavior of the novel system 53 was investigated in comparison to precursor system 40 and methyl pyropheophorbide a Me-33. The voltammograms are assorted Figure 25. 53 40 Me-33 -1.4 -1.2 -1.0 -0.8 -0.6 -0.4 E (V) 0.8 1.0 1.2 1.4 1.6 1.8 Figure 25. Cyclic voltammograms of 53, its precursor 40 and methyl pyropheophorbide a Me-33 in CH2Cl2 solution. Dashed-dotted lines stand for the positions of the half-wave potentials of TPP 15 112 representing a standard 5,10,15,20-tetraphenylporphyrin. The measurements were performed in CH2Cl2 (c = 10 -3 M) using tetra-n-butyl ammonium hexafluorophosphate (c = 0.1 M) as supporting electrolyte at 25 °C in a three electrodes arrangement with a gold disc electrode (0.07 cm 2 ), a platinum wire as counter electrode and a Ag/AgCl-electrode (3 M NaCl) as reference. As scan rate 50 mV/s was chosen and ferrocene was added as internal standard with E(Fc/Fc + ) = 0.53 V (see also paragraph 6.1). The thus resulting half-wave potentials are included in Table 8. 96 The voltammogram of 53 clearly shows that both, two-step oxidation as well as two-step reduction, are fully reversible as it is also the case for non-annulated standard porphyrin systems like e.g. 15. The obtained half-wave potentials (E½) in the cathodic region are shifted by approx. 0.3 V to higher values compared to 40, a non-annulated precursor of 53, or to 59
Page 1 and 2:
Semi-Natural and Synthetic Chiral C
Page 3 and 4:
Die vorliegende Arbeit entstand in
Page 5 and 6:
Table of Contents 1 Introduction 1
Page 7:
n J j-coupling (constant) with n in
Page 10 and 11:
1 Introduction characteristics. For
Page 12 and 13:
1 Introduction 1.1 Porphyrins - A G
Page 14 and 15:
1 Introduction Especially interesti
Page 16 and 17: 1 Introduction 8 [H] 4 + 4 O H O H
Page 18 and 19: 1 Introduction complexes are usuall
Page 20 and 21: 1 Introduction transitions as it is
Page 22 and 23: 1 Introduction 1.2 Photodynamic The
Page 24 and 25: 1 Introduction Certainly, Photofrin
Page 26 and 27: 1 Introduction intact membranes bei
Page 28 and 29: 1 Introduction components, the limi
Page 30 and 31: 2 State of The Art & Aims They were
Page 32 and 33: 2 State of The Art & Aims 2.2 Aim o
Page 34 and 35: 3 Discussion and Results encapsulat
Page 36 and 37: 3 Discussion and Results diastereot
Page 38 and 39: 3 Discussion and Results 30 E ½ Re
Page 40 and 41: 3 Discussion and Results irradiatio
Page 42 and 43: 3 Discussion and Results 34 R 1 O N
Page 44 and 45: 3 Discussion and Results 3.2.2.1.2
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
Page 52 and 53: 3 Discussion and Results 3.2.3.1 IR
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
Page 60 and 61: 3 Discussion and Results Obviously,
Page 62 and 63: 3 Discussion and Results Like Figur
Page 64 and 65: 3 Discussion and Results utilizatio
Page 68 and 69: 3 Discussion and Results other TPP
Page 70 and 71: 3 Discussion and Results (being sup
Page 72 and 73: 3 Discussion and Results other band
Page 74 and 75: 3 Discussion and Results Table 10.
Page 76 and 77: 3 Discussion and Results voltammogr
Page 78 and 79: 3 Discussion and Results 3.2.5 Inhe
Page 80 and 81: 3 Discussion and Results effects 12
Page 82 and 83: 3 Discussion and Results 74 Δθ [m
Page 84 and 85: 3 Discussion and Results 3.2.6.2 10
Page 86 and 87: 3 Discussion and Results vibration
Page 88 and 89: 3 Discussion and Results 3.2.6.4 Sy
Page 90 and 91: 3 Discussion and Results cyanomethy
Page 92 and 93: 3 Discussion and Results 3.2.6.5 Co
Page 94 and 95: 3 Discussion and Results phenyl sub
Page 98 and 99: 3 Discussion and Results 90 5 μA -
Page 100 and 101: 3 Discussion and Results 3.2.7 Appr
Page 102 and 103: 3 Discussion and Results (75 eq.) w
Page 104 and 105: 3 Discussion and Results 3.2.7.2 Sy
Page 106 and 107: 3 Discussion and Results of rotatio
Page 108 and 109: 3 Discussion and Results Thus, the
Page 110 and 111: 3 Discussion and Results Time-resol
Page 112 and 113: 3 Discussion and Results first redu
Page 114 and 115: 3 Discussion and Results correspond
Page 116 and 117:
3 Discussion and Results The remain
Page 118 and 119:
3 Discussion and Results 3.2.8.1 Us
Page 120 and 121:
3 Discussion and Results With all t
Page 122 and 123:
3 Discussion and Results The interm
Page 124 and 125:
3 Discussion and Results 116 HO 2 C
Page 126 and 127:
3 Discussion and Results nitro comp
Page 128 and 129:
3 Discussion and Results The effect
Page 130 and 131:
3 Discussion and Results 3.2.8.2.7
Page 132 and 133:
3 Discussion and Results 3.2.9 Pote
Page 134 and 135:
3 Discussion and Results peak at m/
Page 136 and 137:
3 Discussion and Results Table 25.
Page 138 and 139:
3 Discussion and Results 130
Page 140 and 141:
4 Summary As the characterization d
Page 142 and 143:
5 Zusammenfassung 5 Zusammenfassung
Page 144 and 145:
5 Zusammenfassung Da in guten Ausbe
Page 146 and 147:
6 Experimental Section UV/Vis spect
Page 148 and 149:
6 Experimental Section 6.2 Studied
Page 150 and 151:
6 Experimental Section 13 C NMR (10
Page 152 and 153:
6 Experimental Section (cyanomethyl
Page 154 and 155:
6 Experimental Section 6.2.4 AB3-Ty
Page 156 and 157:
6 Experimental Section 6.2.4.3 5 4
Page 158 and 159:
Page 160 and 161:
Page 162 and 163:
Page 164 and 165:
6 Experimental Section 6.2.4.11 10
Page 166 and 167:
6 Experimental Section EA: C57H56N4
Page 168 and 169:
6 Experimental Section 6.2.4.15 10
Page 170 and 171:
6 Experimental Section 6.2.5 A2B2-T
Page 172 and 173:
Page 174 and 175:
6 Experimental Section 6.2.5.5 αβ
Page 176 and 177:
6 Experimental Section 6.2.5.7 αβ
Page 178 and 179:
6 Experimental Section 6.2.5.9 αα
Page 180 and 181:
6 Experimental Section 6.2.5.11 α
Page 182 and 183:
6 Experimental Section 6.2.5.13 α
Page 184 and 185:
Page 186 and 187:
6 Experimental Section 6.2.6 AB2C-T
Page 188 and 189:
Page 190 and 191:
6 Experimental Section UV/Vis (CH2C
Page 192 and 193:
Page 194 and 195:
6 Experimental Section UV/Vis (CH2C
Page 196 and 197:
6 Experimental Section broad signal
Page 198 and 199:
7 References 16 H. Fischer, K. Zeil
Page 200 and 201:
7 References 57 S. Schwartz, K. Abs
Page 202 and 203:
7 References 89 (a) R. C. Fuson, J.
Page 204 and 205:
7 References 131 (a) J. Perdew, Phy
Page 206 and 207:
S. Jasinski, N. Jux, “Investigati
Page 208 and 209:
Ein großer Dank gilt auch den Ange
Page 210 and 211:
Cirruculum vitae Stefan Jasinski Ge
Page 212 and 213:
204 56 57 58 59 60 61 62 63 64 65 6
show all

1.1 Porphyrins - Friedrich-Alexander-Universität Erlangen-Nürnberg

Create successful ePaper yourself

Delete template?

Save as template?