Dissertation

More documents

Recommendations

Info

|3.1 Brominated Phenanthrolines - A Gate to new Bridging Ligands| lengths (d complexes (N1-C1/N2-C10) = [1.328(10) - 1.349(10)] Å) as well as the N1-C12/N2-C11 bond lengths (d complexes (N1-C12/N2-C11) = [1.360(5) - 1.370(6)] Å) are slightly elongated in the ruthenium complexes, when compared to the ligands (d lignds lignds (N1-C1/N2-C10) = [1.311(5) - 1.330(4)] Å and d(N1-C12/N2-C11) = [1.352(5) - 1.368(4)] Å). The C5-C6 bond lengths (d complexes (C5-C6) = [1.346(8)-1.368(8)] Å) and the Br-C bond lengths (d complexes (C-Br) = [1.881(6)-1.906(6)] Å) remain completely unchanged, fluctuations can be assigned to packing effects. Independent of the nature of the ligand, typically N-Ru-N’ bite angles of 78-80° can be observed within the series of ruthenium complexes. Due to the small bite angle which is considerably less than 90°, it is not possible to achieve perfect octahedral geometry around the ruthenium fragment, so that the ligands are somewhat flexible, which can be seen in a distortion (see figure 50). Figure 50: Coordination geometry around the ruthenium centers of the prepared complexes. View along the bisecting line of the N1-Ru-N2 angle. The two chloride ligands in Ru(phenBr 2 )Cl 2 are arranged in a 93.0° angle. In difference to the packing in the ligand crystals, generally no special packing effects upon π-stacking or hydrogen bond formation were observed in the ruthenium complexes. 3.1.4 Photophysical Behavior The following presented data arose from a cooperation project with K. Peuntinger of the group of Prof. Dr. D. Guldi (University of Erlangen). |71|
|3.1 Brominated Phenanthrolines - A Gate to new Bridging Ligands| A first analysis of the absorption and emission properties of the new complexes of the two series [Ru(tbbpy) 3-n (phenBr 2 ) n ] 2+ (n = 0, 1, 2, 3) and [Ru(tbbpy) 2 (phenBr m )] 2+ (m = 0, 1, 2, 4), the precursor Ru(phenBr 2 ) 2 Cl 2 was excluded, revealed a typical [Ru(bpy) 3 ] 2+ -like behavior (see table 5 for the obtained data and selected references). Table5:UV/vis absorption and emission data of selected references and the two series of ruthenium complexes [Ru(tbbpy) 3-n (phenBr 2 ) n ] 2+ (n = 0, 1, 2, 3) and [Ru(tbbpy) 2 (phenBr m )] 2+ (m = 0, 1, 2, 4). Complex Solvent λ max, abs ϵ λmax λ max, em Φ τ a τ b [nm] [l mol -1 cm -1 ] [nm] [ns] [ns] [Ru(tbbpy) 3 ] 2+ DCM 464 16 000 607 248 [90] 609 [90] ACN 458 17 900 615 107 [90] 730 [90] Ru(phen) c, [120, 125] DCM 455 19 000 602 0.03 272 ACN 454 16 000 610 211 1 423 Ru(phenCl) DCM 450 16 600 620 ACN 446 18 700 633 Ru(phenBr) DCM 451 13 500 621 452 ACN 449 17 800 630 139 Ru(Br 2 phen) [125] DCM 440 18 000 638 0.05 525 Ru(phenBr 2 ) DCM 452 17 500 621 438 ACN 449 14 300 631 140 1 347 Ru(phenBr 4 ) [108, 125] DCM 440 19 000 657 0.05 591 ACN 441 15 000 672 100 1 336 Ru(phenBr 2 ) 2 DCM 433 20 500 611 573 ACN 434 22 200 621 196 2 190 [108] Ru(phen) 3 DCM 448 17 000 578 460 ACN 450 18 200 593 150 Ru(phenBr 2 ) 3 DCM 451 19 000 587 353 ACN 450 18 200 600 247 1 380 [129] Ru(Br 2 phen) 3 ACN 424 8 700 599 126 a) aerated, b) deaerated, c) Ru(phen) = [Ru(tbbpy) 2 (phen)] 2+ All substances exhibit the relevant strong 1 MLCT-absorption band between 400 and 500 nm in acetonitrile and dichloromethane solutions as well as the typical strong emission between 600 and 800 nm in both solvents respectively (compare figures 51 – 53). In the series [Ru(tbbpy) 3-n (phenBr 2 ) n ] 2+ (n = 0, 1, 2, 3) all complexes exhibit a strong absorption |72|
Page 1 and 2:
Development of Novel Catalysts for
Page 3 and 4:
Diese Arbeit entstand auf Anregung
Page 5 and 6:
Den Arbeisgruppen von Prof. Dr. U.
Page 7 and 8:
Contents 1 Introduction 1 1.1 Fossi
Page 9 and 10:
|Contents| 6 Experimental Section 1
Page 12 and 13:
|1 Introduction| 1 Introduction The
Page 14 and 15:
|1.1 Fossil Fuels and Nuclear Power
Page 16 and 17:
|1.2 Renewable Fuels| of natural ga
Page 18 and 19:
|1.3 Energy Transformation and Stor
Page 20 and 21:
|1.4 Solar Energy Conversion| A fra
Page 22 and 23:
|1.5 Photosynthesis| Figure 9: Mole
Page 24 and 25:
|1.6 Photocatalyzed Reactions| 2 NA
Page 26 and 27:
|1.6 Photocatalyzed Reactions| (1)
Page 28 and 29:
|1.7 Mimicking Photosynthesis| So t
Page 30 and 31:
|1.8 Formalisms of Photocatalytic S
Page 32 and 33: |1.9 Multicomponent Systems from Fu
Page 52 and 53: |1.10 Intramolecular Photoredoxcata
Page 64 and 65: |2 Scope of the Thesis| motifs with
Page 66 and 67: |3.1 Brominated Phenanthrolines - A
Page 94 and 95: |3.2 Bisphenanthroline: A Suitable
Page 104 and 105: f f f f f f |3.2 Bisphenanthroline:
Page 122 and 123: |3.3 NN-NHC-Ligand bbip: Toward Sec
Page 132 and 133:
|3.3 NN-NHC-Ligand bbip: Toward Sec
Page 134 and 135:
Page 136 and 137:
Page 138 and 139:
Page 140 and 141:
Page 142 and 143:
Page 144 and 145:
Page 146 and 147:
Page 148 and 149:
Page 150 and 151:
Page 152 and 153:
Page 154 and 155:
Page 156 and 157:
Page 158 and 159:
Page 160 and 161:
Page 162 and 163:
Page 164 and 165:
Page 166 and 167:
Page 168 and 169:
Page 170 and 171:
|3.4 Outlook, Exploratory Investiga
Page 173 and 174:
Page 175 and 176:
Page 177 and 178:
Page 179 and 180:
Page 181 and 182:
Page 183 and 184:
Page 185 and 186:
|4 Summary| 4 Summary Against the b
Page 187 and 188:
|4 Summary| The resulting complexes
Page 189 and 190:
|4 Summary| 10 [TEA] + TEA visible
Page 191 and 192:
|4 Summary| absorption between 430
Page 193 and 194:
|4 Summary| additional NN- and NHC-
Page 195 and 196:
|5 Zusammenfassung| Die Herstellung
Page 197 and 198:
|5 Zusammenfassung| phenphen und Ru
Page 199 and 200:
|5 Zusammenfassung| Fragment tragen
Page 201 and 202:
|5 Zusammenfassung| [TEA] + TEA vis
Page 203 and 204:
|5 Zusammenfassung| In einer abschl
Page 205 and 206:
|6 Experimental Section| Spectroele
Page 207 and 208:
|6 Experimental Section| 1.3648 was
Page 209 and 210:
|6.1 Synthesis of the Organic Ligan
Page 211 and 212:
Page 213 and 214:
Page 215 and 216:
Page 217 and 218:
Page 219 and 220:
Page 221 and 222:
Page 223 and 224:
|6.2 Synthesis of the Metal Complex
Page 225 and 226:
Page 227 and 228:
Page 229 and 230:
Page 231 and 232:
Page 233 and 234:
Page 235 and 236:
Page 237 and 238:
Page 239 and 240:
Page 241 and 242:
Page 243 and 244:
Page 245 and 246:
Page 247 and 248:
Page 249 and 250:
|7 Appendix| 7 Appendix dd ddd DEI
Page 251 and 252:
|7 Appendix| Ru(tpphz)Os [Ru(bpy) 2
Page 253 and 254:
|References| [26] M. Chanon, M. Sch
Page 255 and 256:
|References| [81] S. Tschierlei, M.
Page 257 and 258:
|References| [138] L. Pazderski, J.
Page 259 and 260:
|References| [194] C. Liu, J. Li, B
Page 261:
Selbstständigkeitserklärung: Ich
show all

Dissertation

Create successful ePaper yourself

Delete template?

Save as template?