The redox-conversion reaction of metal-disulfide and metal-thiolate complexes are important, as they may shed light on electron-transfer reactions that often occur in Nature. Despite their... Show moreThe redox-conversion reaction of metal-disulfide and metal-thiolate complexes are important, as they may shed light on electron-transfer reactions that often occur in Nature. Despite their importance, very few examples have been reported. In addition to that, there is a limited understanding of how the coordination environment of the metal ion affects this reaction. In this thesis, our investigation was set based on the ligand-field theory to determine its correlation with the redox-conversion reactions in cobalt-based systems. Our experiments revealed that using an exogenous ligand with a strong ligand-field character may induce the redox conversion from cobalt(II)-disulfide complexes to cobalt(III)-thiolate complexes. Using this knowledge, the possibility of the redox-conversion reaction was also extended from cobalt(II)-diselenide to cobalt(III)-selenolate complexes.Finally, we have come up with several conclusions about the redox-conversion reactions of the cobalt(II)-dichalcogenide complexes. It was revealed that the conversion is affected by the ligand-field strength of the dichalcogenide ligand. The smaller ligand-field strength can be counterbalanced with the introduction of the strong auxiliary ligand. Lastly, the cleanliness of the conversion depends on the magnitude of the overall ligand-field splitting energy of the complex. Show less
Metal-based prodrugs based on ruthenium(II) polypyridyl complexes have proven to be very suitable for application in both photodynamic therapy (PDT) and photo-activated chemotherapy (PACT). As most... Show moreMetal-based prodrugs based on ruthenium(II) polypyridyl complexes have proven to be very suitable for application in both photodynamic therapy (PDT) and photo-activated chemotherapy (PACT). As most of these complexes unfortunately require poorly-penetrative, potentially-toxic blue light for their photo-activation, a lot of research effort has been dedicated to the development of prodrug systems that can be activated using near-infrared light, which is less harmful and penetrates deeper into human tissue. Thulium-doped upconverting nanoparticles (UCNPs) produce the desired blue light upon excitation with near-infrared light, allowing for the development of a drug delivery system in which ruthenium prodrugs are activated with near-infrared light. This thesis deals with the development of several new photo-activatable ruthenium polypyridyl complexes and the investigation of their photochemistry. Furthermore, a multicentre comparative study of the upconversion quantum efficiencies of LiYF4 UCNPs is reported. Finally, it describes the formation of water-dispersible UCNPs decorated with the newly-developed ruthenium complexes, as well as their stability in aqueous media and the successful photo-activation of the surface-bound ruthenium complexes using near-infrared light. The work has resulted in new insights into the design principles that are essential for the successful development of photo-activatable ruthenium-decorated upconverting nanoparticles. Show less
In the last decade, the redox interconversion between metal thiolate and disulfide compounds has been extensively investigated for copper, but not for other transition metal ions. In this... Show moreIn the last decade, the redox interconversion between metal thiolate and disulfide compounds has been extensively investigated for copper, but not for other transition metal ions. In this thesis, our investigations are described of the possibility to extend the metal thiolate/disulfide redox interconversion reactions to cobalt or iron compounds. A number of cobalt(II) disulfide and cobalt(III) thiolate compounds of different ligands and different anions are reported in this thesis. It was revealed that the anion of cobalt(II) salts, the structure of disulfide ligands, and the type of solvent influence the formation of either cobalt(II) disulfide or cobalt(III) thiolate compounds. However, a consistent trend cannot be provided to predict which of the species is generated. An important conclusion of this work is that the cobalt(II) disulfide to cobalt(III) thiolate interconversion reaction might be related to the ligand field strength of the ligand, and the binding strength and ligand field strength of the anions and solvent used. Apart from the cobalt compounds, two iron(II) disulfide compounds were reported in this thesis as well. However, so far we were not able to trigger the conversion of these compounds to their respective iron(III) thiolate compounds. Show less
The research described in this thesis focused on the preparation of S/N functionalized carbene ligands and their transition metal complexes, and the exploration of their application as... Show moreThe research described in this thesis focused on the preparation of S/N functionalized carbene ligands and their transition metal complexes, and the exploration of their application as electrocatalysts for proton reduction. Show less
Ording-Wenker, E.C.M.; Siegler, M.A.; Bouwman, E. 2015
