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|4 Summary| According to X-ray analysis of the compounds, no significant influence of the imidazolium sphere on the phenanthroline binding properties was found. However, the imidazole unit displays similar changes as observed in ip, bip and bbip. Electrochemistry shows the typical reversible behavior of ruthenium complexes but absorption and emission studies exhibit a strong influence of the imidazolium system which possesses very high emission quantum yields and far red-shifted emission wavelengths. 7. Different attempts to access the NHC-coordination sphere of bbip or Ru(bbip), including deprotonation, complexation with [Mo(thf)(CO) 5 ] or formation of the NHC⋅BEt 3 adduct, were made. Finally, the preparation of the bridged complex Ru(bbip)Ag succeeded according to a modified literature procedure. Using this precursor, the P ∼ B ∼ C-type dyads Ru(bbip)Rh and Ru(bbip)Pd were exemplary prepared to demonstrate the potential of the carbene transfer agent. The characterization, including X-ray analysis of Ru(bbip)Ag, detailed MS and MS n studies as well as spectroscopic characterization of the bbip-bridged complexes was achieved. All Ru(bbip)-complexes display properties of the well known Ru(bpy) 3 -moiety, like 1 MLCT- |179|
|4 Summary| absorption between 430 nm and 500 nm, but surprisingly with very strong 3 MLCT-emission between 600 nm and 700 nm and corresponding redox properties. The comparison of the complexes with the ip-motif allowed conclusions about the orbital nature of the ligand. 8. Using with Ru(bbip)Pd, Ru(bbip)Rh and the reference compounds Ru(bbip)Ag and Ru(bbip) a number of intramolecular catalysis experiments were performed. The determined irradiation time and catalyst concentration dependencies of the hydrogen evolution prove the activity of the palladium and rhodium complexes. Both dinuclear complexes may be reviewed as tunable molecular photoredoxcatalysts. Interestingly, even the silver complex showed some activity, whereat the reference Ru(bbip) was inactive. Control experiments with intermolecular P ∼ B / C-type systems of Ru(bbip) and [Pd(ACN) 2 Cl 2 ] or [Rh(cod) 2 Cl] 2 also showed light-driven hydrogen formation, but gave very different catalysis kinetics, when compared to the intramolecular systems. [TEA] + TEA visible light e - e - e - N Cl 2 H 2 N 2+ N N Ru L Pd N N N 4 H N Cl + TON / mol(H 2 )/mol(cat.) 30 20 10 Ru(bbip)Pd Ru(bbip)Rh Ru(bbip)Ag Ru(bbip) 0 0 1 2 3 4 5 irradiation time / h 9. A number of dynamic light scattering measurements was performed with the intramolecular catalysts and the intermolecular control systems to evaluate the influence of the molecular structure on colloid formation and catalysis. It was demonstrated that Ru(bbip)Pd complexes act as model compounds for supramolecular photocatalysts, whilst in the case of Ru(bbip)Ag (photographic process) and Ru(bbip) + [Pd(ACN) 2 Cl 2 ] (Pd-black) formation and growth of particles was detected and a clear correlation between particle ripening and catalytic activity was demonstrated. |180|
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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 140 and 141: |3.3 NN-NHC-Ligand bbip: Toward Sec
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Page 185 and 186: |4 Summary| 4 Summary Against the b
Page 187 and 188: |4 Summary| The resulting complexes
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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
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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 223 and 224: |6.2 Synthesis of the Metal Complex
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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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