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|6.2 Synthesis of the Metal Complexes| 137.34 (2C (2,3,5,6-Durol) ), 131.49 (2C (4-ip) ), 130.74 (2C (11-ip) ), 129.38 (2C (1,4-Durol) ), 127.50 (2C (3’) ), 127.14 (2C (5) ), 126.96 (2C (11”) ), 126.74 (2C (10) ), 124.82 (4C (5-bpy) ), 124.58 (4C (5’-bpy) ), 121.75 (8C (6/6’-bpy) ), 121.66 (2C (3”-ip) ), 121.03 (2C (11’-ip) ), 51.00 (2C (CH2 -Ar)), 46.42 (2C (CH2 -Al)), 35.48 (2C (C-tBu) ), 35.37 (2C (C-tBu) ), 29.58 (12C (CH3 - t Bu)), 29.49 (12C (CH3 - t Bu)), 16.19 (4C (CH3 -Ar)), 14.33 (2C (CH3 -Al)) ppm. MS (ESI): m/z = 1110.2 (10%, [M - 2 PF 6 ] 2+ ) 1031.1 (100%, [Ru(eip)+ PF 6 ] + ). 6.2.25 [{(tbbpy) 2 Ru} 2 (µ-edip){AgCl} 2 ]Cl 4 - Ru 2 (edip)Ag 2 According to method C2, 200 mg (93 µmol) of the chloride salt of Ru 2 (edip), 25.0 mg (220 µmol) of silver(I) oxide and 2 g of dry molecular sieves were suspended in 20 ml of dry dichloromethane under argon atmosphere. This solution was stirred for 16 hours at room temperature. After the reaction time, the remaining solids were removed by filtration through oven dried celite. Remaining product was washed from the celite with dichloromethane and acetonitrile. The pure product is obtained after removal of the solvent under reduced pressure. Yield: 190 mg (80 µmol, 86%) of a red powder which is sensitive to air and moisture. CH 3 -bpy 1 H-NMR (CD 3 CN, N N N 9-ip 10-ip CH 11-ip CH 3 2 N N N Ru 2+ Ag Cl N N Cl Ag N N 6-ip 4-ip 5-ip Ar Ru 2 (edip)Ag 2 5-bpy 6-bpy N N N Ru 2+ N 3-bpy 3'-bpy N 5'-bpy 6'-bpy N CH 3 '-bpy 400 MHz): δ= 9.50 (d, 2H (C) , 3 J = 8.4Hz), 9.03 (d, 2H (C’) , 3 J = 8.6Hz), 8.58 (d, 2H (3-bpy) , 4 J = 1.8Hz), 8.58 (d, 2H (3’-bpy) , 4 J = 1.8Hz), 8.54 (d, 2H (3”-bpy) , 4 J = 2.0Hz), 8.54 (d, 2H (3”’-bpy) , 4 J = 1.8Hz), 8.20 (dd, 2H (A) , 3 J = 5.3Hz, 4 J = 0.7Hz), 8.18 (dd, 2H (A’) , 3 J = 5.4Hz, 4 J = 0.8Hz), 7.91 (dd, 2H (B) , 3 J = 8.8Hz, 3 J = 4.8Hz), 7.90 (dd, 2H (B’) , 3 J = 8.7Hz, 3 J = 5.1Hz), 7.72 (d, 2H (6-bpy) , 3 J = 6.1Hz), 7.70 (d, 2H (6’-bpy) , 3 J = 6.1Hz), 7.49 (m, 2H (5,5’,6”-bpy) ), 7.45 (d, 6H (6”’-bpy) , 3 J = 6.1Hz), 7.26 (m, 4H (5”,5”’-bpy) ), 6.10 (d, 2H (CH2 -Ar), 2 J = 13.1Hz), 6.05 (d, 2H (CH2 -Ar), 2 J = 14.3Hz), 5.06 (q, 4H (CH2 -Al), 3 J = 6.8Hz), 2.30 (dd, 12H (CH3 -Ar), J = 23.9Hz, J = 6.2Hz), 1.70 (t, 6H (CH3 -Al), 3 J = 7.1Hz), 1.46 (s, 36H (tBu) ), 1.38 (s, 36H (tBu) ) ppm. MS (ESI): m/z = 1143.8 (25%, [M – 2 Cl] 2+ ), 751.1 (50%, [M – 3 Cl] 3+ ), 715.1 (50%, [M – 3 Cl – Ag] 3+ ), 554.7 (100%, [M – 3 Cl] 4+ ). |237|
|7 Appendix| 7 Appendix dd ddd DEI DMF DMSO DNA dppz dqp EI edip eip em. ESI eT ET et al. EtOH F FAB Fc Fd FeS ff. FNR FTIR GC GS * excited state covalently linked photocatalytic system A acceptor abs. absorption, absolute ACN acetonitrile AP antenna pigment a.u. arbitrary units b broad B bridge bbip 1,3-dibenzyl-1H-imidazo[4,5- f][1,10]phenanthrolinium bromide (bbip)Ag [Ag(bbip)Br] bbipBEt 3 triethylborane adduct of 1,3-dibenzyl-1H-imidazo[4,5- f][1,10]phenanthroline-2-ylidene bip 1-benzyl-1H-imidazo[4,5- f][1,10]phenanthroline bpy 2,2’-bipyridine Br 2 bip 1-benzyl-5,10-dibromo-1H-imidazo[4,5- f][1,10]phenanthroline Br 2 phen 3,8-dibromo-1,10-phenanthroline C catalyst COD cyclooctadiene COSY correlation spectroscopy conc. concentrated CT charge transfer cyt f cytochrome f d dublett D donor DCM dichloromethane dublett of dubletts dublett of dubletts of dubletts desorption electron ionization N,N-dimethlyform-amide dimethylsulfoxide deoxyribonucleic acid dipyrido[3,2-a:2,3-c]phenazine 2,6-bis(8’-quinolinyl)pyridine electronic ionization 3,3’-(2,3,5,6-tetramethyl-1,4- phenylene)bis(methylene)bis-(1-ethyl-1Himidazo[4,5-f][1,10]phenanthrolinium) dibromide 1-ethyl-1H-imidazo[4,5- f][1,10]phenanthroline emission electro-spray ionization electron transfer energy transfer et alii ethanol fluorescence fast atom bombardment ferrocene ferredoxin membrane bound iron sulfur protein and the following ferredoxin-NADP reductase fourier transform infrared gas chromatography ground state |238|
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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
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|1.5 Photosynthesis| Figure 9: Mole
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|1.6 Photocatalyzed Reactions| 2 NA
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|1.6 Photocatalyzed Reactions| (1)
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|1.7 Mimicking Photosynthesis| So t
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|1.8 Formalisms of Photocatalytic S
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|1.9 Multicomponent Systems from Fu
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|1.10 Intramolecular Photoredoxcata
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|2 Scope of the Thesis| motifs with
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|3.1 Brominated Phenanthrolines - A
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|3.2 Bisphenanthroline: A Suitable
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f f f f f f |3.2 Bisphenanthroline:
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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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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
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