This thesis investigates the functionalization of 4H-imidazolato-Cu(I) complexes for heterogeneous immobilization methods and for increasing their charge-accumulation capabilities. Commercially available Amberlyst resins were successfully employed to immobilize Cu(I)(Im)₂⁻ cuprates, which were characterized by diffuse reflectance spectroscopy. For the non-commercial block copolymer PS-b-P(DMAEMA-co-4VP), an anion-exchange reaction was found to immobilize the cuprates. A ligand-exchange strategy using Cu(I)(Im)(PPh₃)₂ complexes as transfer reagents was developed, allowing substitution of the labile PPh₃ ligands by chelating ligands such as nixantphos. This approach enables the potential introduction of the 4H-imidazole chromophore into soft-matter systems. Further strategies to modify the 2-position of 4H-imidazoles were explored, aiming to retain their optical and electronic properties. The introduction of organic bridging units led to five dinuclear complexes, two of which feature an additional bipyridine coordination pocket, providing a useful tool for incorporating various metal fragments. The subseqent investigations focused oh the application of 4H-imidazolato-Cu(I) complexes in light-driven reactions and on studying the increased charge accumulation of the previously prepared complexes by cyclic voltammetry. A thorough investigation of the Cu(I)(Im)(xantphos) single redoxophores revealed structure–property relationships governing their electrochemical behavior. The double redoxophores were found to accumulate up to four charges, depending on the nature of the bridging unit. Finally, an important knowledge gap was closed by identifying 4H-imidazolium cations as emissive species, thereby correcting previous misinterpretations.
Jens H. Tran (Wed,) studied this question.