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.

Different forms of life satisfaction and their relation to affectivity

Aims: The present study is aimed at studying the research question whether high satisfaction levels achieved through either (1) the fact that one's quality of life is truly satisfactory (i.e., stabilized life satisfaction) or through (2) adapting a more favorable perception of one's quality of life by lowering standards (i.e., resigned life satisfaction) are associated with different levels of positive affect (PA) and negative affect (NA) when compared to each other but also when compared to dissatisfied individuals. Case Report: A sample of 104 adults completed measures assessing stabilized and resigned life satisfaction, PA and NA, and global life satisfaction (i.e., no explicit consideration of differences in standards) in an online survey. Participants were not paid for participation but received feedback on results of the study if interest was expressed. Results: Stabilized life satisfaction and global life satisfaction showed highly similar correlation pattern with PA and NA. Resigned satisfaction was negatively associated with PA and positively correlated with NA. Stabilized and resigned satisfied individuals showed more favorable levels of PA and NA compared with dissatisfied individuals, but did not differ from each other with regard to their levels of PA and NA. Conclusion: Although showing a less favorable correlation pattern with PA and NA, adopting a resigned form of satisfaction (i.e., taking a more favorable view of one's quality of life by lowering individual standards) seemed to prevent individuals from experiencing the same high levels of NA like dissatisfied ones. This has not been studied in detail so far, and therefore, the present paper opens a further area of research within the context of life satisfaction.