Photoisomerizable bipyridine ligands and macroligands: absorption, photoisomerization properties and theoretical study.

Two 2,2'-bipyridines, substituted at the 4,4'-positions by p-dialkylaminophenylazostyryl moieties p-R2N-C6H4-N=N-C6H4-CH=CH-[6 a, R2N=nBu2N; 6 b, R2N=(nBu)(C4H8OTHP)N; 6 c, R2N=(nBu)(C4H8OH)N], were successfully synthesized by using Wadworth-Emmons reactions. The X-ray structure of 6 a has been determined. Esterification of 6 c with 2-bromoisobutyroylbromide afforded 6 d. This ligand was used as an initiator for the living radical polymerization of methylmethacrylate (MMA) and gave rise to macroligand 6 e. Thin films of good optical quality were obtained by the spin-coating technique. Photoisomerization experiments were carried out on 6 a in solution and on 6 e in both solution and film, and the kinetics of photochemical (E/Z) and thermal (Z/E) isomerization were investigated. They were found to show Z-E back isomerization typical of aminoazobenzene-type rather than of push-pull-type molecules. Density functional theoretical (TD-DFT) calculations were performed on model compound 6 a' (R2N=Me2N) to understand the structural and electronic transitions of the corresponding E-E, E-Z and Z-Z isomers. It was found that the E-E isomer is almost planar as observed experimentally by X-ray diffraction, whereas the Z-Z isomer, which is 35.4 kcal mol(-1) less stable than the E-E isomer, is nonplanar. The theoretical studies also reveal that several transitions of pi-pi*, n-pi* and charge-transfer (CT) types, are involved in the long-wavelength transition of 6 a (E-E). The same observations can be made for the (Z-Z) isomer, and the TD-DFT simulated spectrum fits quite nicely to the experimental, reproducing and explaining the apparition of a blue-shifted charge-transfer band at 390 nm.     

Induced characters, Mackey analysis and primitive ideal spaces of nilpotent discrete groups

Let G be a nilpotent discrete group and Prim(C^*(G)) the primitive ideal space of the group C^*-algebra C^*(G). If G is either finitely generated or has absolutely idempotent characters, we are able to describe the hull-kernel topology on Prim(C^*(G)) in terms of a topology on a parametrizing space of subgroup-character pairs. For that purpose, we introduce and study induced traces and develop a Mackey machine for characters. We heavily exploit the fact that the groups under consideration have the property that every faithful character vanishes outside the finite conjugacy class subgroup.     

Ein Hebbarkeitssatz für Automorphismengruppen kompakter komplexer Mannigfaltigkeiten

Ohne Zusammenfassung     

Die Struktur der regulären Darstellung lokalkompakter Gruppen mit invarianter Umgebungsbasis der Eins

Ohne ZusammenfassungDies ist eine gekürzte Fassung einer Arbeit, die von der Fakultät für Allgemeine Wissenschaften der Technischen Universität München als Habilitationsschrift angenommen wurde.