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|3.1 Brominated Phenanthrolines - A Gate to new Bridging Ligands| compounds and similar chemical properties, it was not possible to completely separate the brominated products neither by chromatography nor by recrystallization. Nevertheless, suitable crystals for X-ray diffraction experiments could be obtained by recrystallization from chloroform. Figure 42: Molecular structures of Me 2 phenBr 2 (left) and Me 2 phenBr 3 ) (right) with coordinated solvent, obtained via cocrystallization of the 90:10-mixture from chloroform. Ellipsoids were drawn at 50% level in this ORTEP representation (see table 3 for selected bond lengths and angles). A superposition of both compounds was found in the crystal lattice with phenMe 2 Br 3 occupying 10% and phenMe 2 Br 2 90% of the phenanthroline positions. Therefore, it was possible to confirm both structures by X-ray diffraction (see figure 42 and table 3). The monoclinic crystal system has the space group P2(1)/c. An alternating orientation of the phenanthrolines and weak π-stacking of the planar aromatic systems is prominent in the crystal lattice (not depicted). Again, coordinated chloroform with hydrogen bond distances of d (H1Cl-N1/N2) = 2.403/2.483 Å was present in the N,N’- coordination site of the phenanthroline derivatives. And again, no significant influence of the bromination upon the phenanthroline backbone was observed by comparison of the bond lengths and angles (see table 3). The important bond length and angles of the brominated phenanthroline ligands are presented in table 3 (page 62), for comparison with the prepared ruthenium complexes see table 4 (page 70). Comparison of the phenBr-type structures to each other revealed strong structural similarities in terms of bond lengths and angles. The phenanthroline systems remain almost unchanged upon bromination in the 5- and 6-position as a result of this. Therefore, N1-C1/N2-C10 bond |61|
|3.1 Brominated Phenanthrolines - A Gate to new Bridging Ligands| lengths (1.311(5) – 1.330(4) Å) as well as the N1-C12/N2-C11 bond lengths (1.352(4) – 1.368(4) Å) differ negligibly. The C5-C6 bond lengths (1.342(5) – 1.357(5) Å) remain completely unchanged and the Br-C bond lengths (1.886(3) – 1.899(3) Å) are in the range of typical values for this bond type. The packing of the ligands in the crystal exhibits π-stacking effects with differing π- π-distances in the range of 3.312(4) to 3.707(4) Å between the planes of the aromatic systems (given as π-π in table 3). Hydrogen bond formation with differing bond lengths between the phenanthroline nitrogen atoms and coordinated chloroform was observed in all crystal structures (d phenBr C1Cl-N1/N2 = 3.156/3.229 Å, d phenBr 2 C1Cl-N1/N2 = 3.132/3.191 Å, and d Me 2phenBr 3/3 C1A-N1/N2 = 3.225/3.249 Å). Table 3: Selected bond lengths [Å] and angles [°] of the brominated phenanthroline derivatives bond length [Å] / angle [°] phenBr phenBr 2 phenMe 2 Br 2 phenMe 2 Br 3 Br1 - C5 1.899(3) 1.886(3) 1.890(3) 1.890(3) Br2 - C6 - 1.891(3) 1.887(3) 1.887(3) Br3 - C2 - - - 1.837(3) N1 - C1 1.311(5) 1.327(4) 1.330(4) 1.330(4) N2 - C10 1.317(5) 1.324(4) 1.318(4) 1.318(4) N1 - C12 1.361(4) 1.358(4) 1.364(4) 1.364(4) N2 - C11 1.352(4) 1.352(4) 1.368(4) 1.368(4) C1 - C2 1.389(5) 1.400(5) 1.405(5) 1.405(5) C2 - C3 1.376(5) 1.364(5) 1.358(5) 1.358(5) C4 - C5 1.441(5) 1.439(5) 1.437(5) 1.437(5) C5 - C6 1.342(5) 1.354(5) 1.357(5) 1.357(5) C6 - C7 1.432(5) 1.441(5) 1.438(4) 1.438(4) C11 - C12 1.453(4) 1.464(4) 1.447(4) 1.447(4) π - π 3.408(4) 3.312(4) 3.707(4) 3.707(4) H1Cl - N1 2.429(5) 2.312(4) 2.483(4) 2.483(4) H1Cl - N2 2.493(4) 2.376(4) 2.403(4) 2.403(4) Cl2a - H13a/H1 - 3.236(4) 3.150(4) 3.150(4) C1 - C2 - C3 118.1(3) 119.1(3) 120.4(3) 120.4(3) C4 - C5 - C6 122.4(3) 121.0(3) 121.2(3) 121.2(3) C5 - C6 - C7 120.6(3) 121.3(3) 121.0(3) 121.0(3) C10 - N2 - C11 117.8(3) 117.4(3) 118.9(3) 118.9(3) N2 - C11 - C12 119.1(3) 117.3(3) 118.0(3) 118.0(3) C11 - C12 - N1 117.8(3) 117.5(3) 117.7(3) 117.7(3) C12 - N1 - C1 118.0(3) 117.6(3) 118.6(3) 118.6(3) |62|
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Development of Novel Catalysts for
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Diese Arbeit entstand auf Anregung
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Den Arbeisgruppen von Prof. Dr. U.
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Contents 1 Introduction 1 1.1 Fossi
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|Contents| 6 Experimental Section 1
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|1 Introduction| 1 Introduction The
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|1.1 Fossil Fuels and Nuclear Power
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|1.2 Renewable Fuels| of natural ga
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|1.3 Energy Transformation and Stor
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|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
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Page 66 and 67: |3.1 Brominated Phenanthrolines - A
Page 94 and 95: |3.2 Bisphenanthroline: A Suitable
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|3.3 NN-NHC-Ligand bbip: Toward Sec
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|3.4 Outlook, Exploratory Investiga
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|4 Summary| 4 Summary Against the b
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|4 Summary| The resulting complexes
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|4 Summary| 10 [TEA] + TEA visible
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|4 Summary| absorption between 430
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|4 Summary| additional NN- and NHC-
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|5 Zusammenfassung| Die Herstellung
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|5 Zusammenfassung| phenphen und Ru
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|5 Zusammenfassung| Fragment tragen
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|5 Zusammenfassung| [TEA] + TEA vis
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|5 Zusammenfassung| In einer abschl
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|6 Experimental Section| Spectroele
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|6 Experimental Section| 1.3648 was
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|6.1 Synthesis of the Organic Ligan
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|6.2 Synthesis of the Metal Complex
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|7 Appendix| 7 Appendix dd ddd DEI
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|7 Appendix| Ru(tpphz)Os [Ru(bpy) 2
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|References| [26] M. Chanon, M. Sch
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|References| [81] S. Tschierlei, M.
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|References| [138] L. Pazderski, J.
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|References| [194] C. Liu, J. Li, B
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Selbstständigkeitserklärung: Ich
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