Dissertation

|Contents|
3.1.7 Concluding Remarks to phenBr-Ligands . . . . . . . . . . . . . . . . . . . . . 82
3.2 Bisphenanthroline: A Suitable Molecular Bridge? . . . . . . . . . . . . . . . . . . . . . 83
3.2.1 Preparation of phenphen and Related Complexes . . . . . . . . . . . . . . . 85
3.2.2 Identification and Characterization . . . . . . . . . . . . . . . . . . . . . . . . 87
3.2.3 Structural Analysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 94
3.2.4 Photophysical Behavior . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 97
3.2.5 Excited State Dynamics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 99
3.2.6 Electrochemical Characterization . . . . . . . . . . . . . . . . . . . . . . . . . 104
3.2.7 Application in Light Driven Catalysis . . . . . . . . . . . . . . . . . . . . . . . 106
3.2.8 Concluding Remarks on phenphen-Bridged Complexes . . . . . . . . . . . . 108
3.3 NN-NHC-Ligand bbip: Toward Second Generation Catalysts . . . . . . . . . . . . . . 110
3.3.1 NHCs and NHC Complexes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 111
3.3.2 Imidazophenanthrolines: Toward Redox Stable Bridges . . . . . . . . . . . . 115
3.3.3 Structural Characterization of ip-Type Ligands . . . . . . . . . . . . . . . . . 118
3.3.4 N,N’-Coordinated ip-Type Complexes . . . . . . . . . . . . . . . . . . . . . . . 122
3.3.5 NHC-Coordinated ip-Type Complexes . . . . . . . . . . . . . . . . . . . . . . . 124
3.3.6 Structural Characterization of Ruthenium ip-Type Complexes . . . . . . . . 130
3.3.7 Preparation of bbip-Bridged Catalysts . . . . . . . . . . . . . . . . . . . . . . 134
3.3.8 Spectroscopic Characterization . . . . . . . . . . . . . . . . . . . . . . . . . . 138
3.3.9 Excited State Dynamics of the bbip-Containing Ruthenium Complexes . . . 145
3.3.10 Electrochemical Characterization . . . . . . . . . . . . . . . . . . . . . . . . . 148
3.3.11 Application in Catalysis: Prove of Concept . . . . . . . . . . . . . . . . . . . . 151
3.4 Outlook, Exploratory Investigations and Perspectives . . . . . . . . . . . . . . . . . . 159
3.4.1 Manipulations, Involving the bbip-System . . . . . . . . . . . . . . . . . . . . 159
3.4.2 Electron Deficient bbip-Systems . . . . . . . . . . . . . . . . . . . . . . . . . . 161
3.4.3 NHC-Ligand edip: Further Development of Improved Catalysts . . . . . . . 164
3.4.4 Concluding Remarks . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 173
4 Summary 174
5 Zusammenfassung 183
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