Dipodal Ferrocene Derivatives for Nanostructured Redox-Functionalised Surfaces

Self-assembled monolayers (SAMs) on solid surfaces are of great current interest in science and nanotechnology. This thesis describes the preparation of several symmetrically 1,1’-substituted ferrocene derivatives that contain anchoring groups suitable for chemisorption on gold and may give rise to SAMs with electrochemically switchable properties. The binding groups are isocyano (-NC), isothiocyanato (-NCS), phosphanyl (-PPh2), thioether (-SR) and thienyl. In the context of SAM fabrication, isothiocyanates and phosphanes are adsorbate systems which, surprisingly, have remained essentially unexplored. SAMs on gold have been fabricated with the adsorbates from solution and investigated primarily by X-ray photoelectron spectroscopy and near-edge X-ray absorption fine structure spectroscopy. The results of these analytical investigations are presented and discussed in matters of the film quality and possible binding modes. The quality of self-assembled monolayers fabricated from 1,1’-diisocyanoferrocene and 1,1’-diisothiocyanatoferrocene turned out to be superior to that of films based on the other adsorbate species investigated. Films of those absorbates as well as of dppf afforded well-defined SAMs of good quality. All other films of this study based on sulfur containing anchoring groups exhibit chemical inhomogeneity and low orientational order of the film constituents and therefore failed to give rise to well-defined SAMs. Surface coordination chemistry is naturally related to molecular coordination chemistry. Since all SAMs described in this thesis were prepared on gold (111) surfaces, the ferrocene-based ligands of this study have been investigated in their ability for complexation towards gold(I). The sulfur-based ferrocene ligands [fc(SR)2] failed to give stable gold(I) complexes. In contrast, 1,1’-diisocyanoferrocene (1) proved to be an excellent ligand for the complexation of gold(I). Several complexes were prepared and characterised utilising a series of gold(I) acetylides. These complexes show interesting structural motifs in the solid state, since intramolecular aurophilic interactions lead to a parallel orientation of the isocyano moieties, combined with an antiparallel alignment of neighbouring units. The reaction of 1 with the gold(I) acetylide [Au(C≡C–Fc)]n turned out to be very unusual, since the two chemically equivalent isocyano groups undergo a different reaction. One group shows an ordinary coordination and the other one undergoes an extraordinary 1,1-insertion into the Au-C bond. As a sideline of the research of this thesis several ferrocene derivatives have been tested for their suitability for potential surface reactions. Copper(I) mediated 1,3-dipolar cycloadditions of azidoferrocene derivatives with terminal alkynes appeared very promising in this context, but failed to a certain extent in terms of ‘click’ chemistry, since the formation of the triazoles depended on the strict exclusion of oxygen and moisture and yields were only moderate. Staudinger reactions between dppf and azidoferrocene derivatives were also tested. The nucleophilic additions of secondary amines to 1,1’-diisothiocyanatoferrocene led to the respective thiourea derivatives in quantitative yields.

Auswirkungen des Überganges von der Grundschule in die Sekundarstufe I auf das Wohlbefinden und Selbstkonzept von Schülerinnen und Schülern

Ausgehend von der Annahme, dass der Übergang von der Grundschule in die Sekundarstufe 1 umfassende Auswirkungen auf Wohlbefinden und Selbstkonzept von Kindern haben kann und der geringen Anzahl qualitativer Studien zum Thema, ging die Arbeit der Frage nach, wie der Schulübergang von Kindern selbst diesbezüglich bewertet wird. Ziel waren individuelle Einzelfallanalysen und eine Typisierung unterschiedlicher Bewältigungstypen des Schulübergangs, um Gemeinsamkeiten und Unterschiede in der Einschätzung dieses Transitionsprozesses aus Sicht der Betroffenen darzustellen. Mittels qualitativer Leitfadeninterviews mit acht Kindern vor und nach dem Schulübergang wurden die Ausgangsdaten erhoben und mithilfe eines Diktiergeräts aufgenommen. Diese Aufnahmen wiederum wurden nach dem „TiQ“-Verfahren transkribiert und anschließend in Anlehnung an Mayring und Schmidt kategorisiert und ausgewertet. Die Ergebnisse wurden in einzelnen Fallinterpretationen und in drei unterschiedlichen Bewältigungstypen (positiv, neutral, negativ) dargestellt. Die Untersuchung führte zutage, dass der Schulübergang von den Kindern kritisch reflektiert wird und sowohl Hoffnungen als auch Befürchtungen mit ihm verbunden werden. Wie die drei Bewältigungstypen zeigen, überwiegen teilweise Sorgen, Ängste und Unsicherheit, teils halten sich die verschiedenen Aspekte die Waage und in anderen Fällen wird der Transitionsprozess mehrheitlich positiv bewertet. Das besondere Merkmal der Untersuchung stellt dabei der Vergleich zwischen den Aussagen vor und denen nach dem Schulübergang dar, mittels dessen Bestätigungen bzw. Widerlegungen von Anfangsaussagen deutlich werden.

Individuals' (re-)action in the face of global warming

Climate change remains a major challenge for today’s and future societies due to its immense impacts on human lives and the natural environment. This thesis investigates the extent to which individuals are willing and prepared to voluntarily contribute to climate protection and to adjust to new climatic conditions in order to cope with the consequences of climate change and reduce the severity of potential negative impacts. The thesis thereby combines research in the fields of the private provision of environmental public goods and adaptation to climate change, which is still widely unconnected in the existing literature. The six contributions of this thesis mainly focus on microeconometric analyses using data from international surveys in China, Germany, and the USA. The main findings are: (i) A substantial share of individuals is willing to voluntarily contribute to climate protection and to adapt to climatic change. The engagement in both strategies is positively interrelated at the individual level and the analyses reveal hardly any evidence that adaptation activities crowd out individuals’ incentives to engage in climate protection. (ii) The main determinants of individuals’ adaptation activities seem to be the subjective risk perception as well as socio-economic and socio-demographic characteristics like age, gender, education, and income, while their climate protection efforts are found to be broadly motivated by financial advantages from these activities and additional immaterial benefits. (iii) The empirical findings also suggest a significantly positive relationship between certain climate protection activities. Substitutions are found to occur merely if one measure is perceived to be more effective in providing climate protection or if individuals have high environmental preferences. (iv) This thesis further reveals a common understanding of a (normatively) fair burden-sharing in international climate policy across citizens in China, Germany, and the USA. The highest preferences are found for the accountability principle.