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|6 Experimental Section| Elemantal Analysis Elemental analysis was performed on a Euro Vector Euro EA. Mass spectrometry: The mass spectra were recorded with a SSQ 710 spectrometer (Finnigan MAT). Electrospray ionization spectra were recorded with a MAT 95 XL (Thermoquest-Finnigan MAT). NMR-Experiments: The NMR spectra were recorded on a Bruker 400 MHz spectrometer and on a Jeol EX-270 DELTA and no a Jeol EX-400 DELTA spectrometer (270/400 MHz), respectively. Crystal-structure Analysis: The intensity data for the compounds (Ru(bbip)) and (Ru(bbip)Ag) were collected on a Nonius Kappa-CCD diffractometer, using graphite-monochromated Mo-Kα radiation (λ = 0.71069 Å, graphite monochromator) at -140(2)°C. Data were corrected for Lorentz and polarization effects, but not for absorption effects. [199, 200] The structures were solved by direct methods (SHELXS [10.1107/S0108767390000277]) and refined by full-matrix least squares techniques against Fo 2 (SHELXL-97). [201, 202, 203] The hydrogen atoms were included at calculated positions with fixed thermal parameters. All nonhydrogen atoms were refined anisotropically. [201, 202, 203] XP (SIEMENS Analytical X-ray Instruments, Inc.) was used for structure representations. The data is freely available on the internet: www.ccdc.cam.ac.uk/data_request/cif (or can be required under the following address in Great Britain: Cambridge Crystallographic Data Centre, 12 Union Road, GBCambridge CB21EZ; Fax:(+44)1223-336-033; or deposit@ccdc.cam.ac.uk): Ru(bbip) (CCDC- 765499), Ru(bbip)Ag (CCDC-796734), Dynamic Light Scattering Experiments DLS data were obtained, using a Delsa Nano C particle analyzer from Beckman Coulter. As light source dual 30 mW laser diodes with a wavelength of 658 nm were used. All measurements were performed at 25°C. For the viscosity a value of 0.58 mPas and for the refractive index a value of |195|
|6 Experimental Section| 1.3648 was determined for the catalytic mixture. All size calculations were done with standard calculation methods. All measurements were performed applying 10×10 mm quartz SUPRASIL inert cuvettes from Hellma. All experiments were repeated with three identical solutions to ensure the reproducibility of the data. Before measuring, the cuvettes were cleaned with aqua regia, concentrated ammonia, distilled water and filtrated acetonitrile (syringe filter pore size 0.2 µm). After this procedure every cuvette was filled with filtrated acetonitrile and investigated by DLS to exclude any remaining particles. All solvents were degassed with nitrogen before use. The catalytic mixtures consisted of 1.2 ml acetonitrile (with the photo catalyst), 0.6 ml Et 3 N and 0.2 ml water. The final concentration of the photo catalyst in the catalytic solution was 50 µM. This mixture was filled into the cuvettes through a syringe filter (pore size 0.2 µm) under inert conditions. All solutions were measured immediately. In the beginning every solution was investigated without irradiation. Each experiment was repeated several times. Between the measurements the solutions were irradiated with the previously used led-arrays (λ = 470 nm). Catalysis Experiments The photohydrogen production experiments were carried out using a home-built air-cooling apparatus for maintaining room temperature (22°C) and constant irradiation of the sample. 5 ml GC vials (diameter = 13 mm, VWR) with a known headspace of 3 ml and a headspace/solution ratio of 3/2 were used as reaction vessels. Directly before the irradiation experiments, fresh stock solutions of the respective samples with solvent mixtures of acetonitrile, triethylamine and water in a 6:3:1 ratio (v:v:v) and with the desired concentrations of ruthenium complex (10 µM, 50 µM, 100 µM and 250 µM) were prepared in the dark. Then, the required number of GC vials was charged in the dark and under nitrogen atmosphere. For the dynamic light scattering experiments inert cuvetts (10×10 mm, quartz glass) were used instead of GC vials. Subsequently, the samples were irradiated with a LED-array (54 LEDs, exit angle 15°, luminous intensity 14.0 cd each, from Innotas Elektronik GmbH, Zittau, Germany) at a wavelength of (λ = 470 nm, suitable to excite in the MLCT-band). After the irradiation, 100 µl gas samples were drawn from the headspace and injected immediately into the GC apparatus. The concentration of evolved hydrogen was quantified by headspace GC on a GCMS-QP2010S chromatograph from Shimadzu, with a thermal conductivity detector and a Rtx®-5MS (fused silica) column (length 30 m, 0.25 mm inner diameter, |196|
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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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Page 156 and 157: |3.3 NN-NHC-Ligand bbip: Toward Sec
Page 170 and 171: |3.4 Outlook, Exploratory Investiga
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: |6 Experimental Section| Spectroele
Page 209 and 210: |6.1 Synthesis of the Organic Ligan
Page 223 and 224: |6.2 Synthesis of the Metal Complex
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.
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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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