Organotetrelchalkogenidcluster mit Heteroadamantanstruktur

Eike Dornsiepen, Dehnen, Stefanie (Prof. Dr.), Chemie
In the framework of this dissertation, the three sub-projects presented in the objective were investigated. In the first sub-project, the white light generation (WLG) first observed on [(StySn)4S6] for organotetrel chalcogenide clusters with an adamantane-type structure was investigated in more detail. For this purpose, the substance library was significantly extended, in particular in order to analyze necessary prerequisites for the white-light emission. By systematic variation of both the
more » ... ion of both the core composition and the organic substituents the understanding of the underlying mechanism was improved, and possible ways to selectively modify the emission spectra were found. In a first study, it could be shown by varying the tetrel element and the substituents that the amorphicity of the compounds is a basic requirement for the WLG, since otherwise emission occurs in phase as second harmonic generation (SHG). By further variation of the organic substituents and replacement of the sulfur atoms in the inorganic core by selenium atoms, it was further found that - opposing the initial hypothesis - no pi electron system, but only a cyclic organic substituent is required, and that the emission seems to be limited by the HOMO-LUMO gap of the compound. By this it can be ruled out that the WLG is caused by an excitation into real electronic states. Instead, the observed effect is to be understood as an excitation into extremely short-lived virtual states that lie within the gap. In the second part of the project, the reactivity of [(PhSn)4S6] towards transition metal complexes was investigated, whereby different ternary clusters were obtained. In reactions with coinage metal complexes with sterically less demanding phosphine ligands, clusters were synthesized in which the inorganic core of the starting material is retained and one of the phenyl substituents is replaced with a coinage metal complex fragment. The resulting clusters have the composition [f(R3P)3MSngfPhSng3S6] (M/R = Cu/Me, Ag/Et, Au/Me). However, by use of the more b [...]
doi:10.17192/z2019.0247 fatcat:3ug6onwb7rg5dkykxl47itrbva