title: Photochemistry and mobility of stilbenoid dendrimers in their neat phases.
abstract: Selectively deuterated, dodecyloxy substituted stilbenoid dendrimers of the first and second generation were synthesized by a convergent synthesis, using the Wittig-Horner reaction. The photochemistry and the fluorescence in the different crystalline and liquid crystalline phases were investigated. Molecules deuterated at the alpha-position of the alkoxy chains were used to study the photoreactions in the neat phases by 1H NMR. Reactions of the double bonds are exclusively observed in the liquid crystal phases. No photoreactions occur in the crystalline state. The mobility of the dendrimers was studied by means of 2H solid-state NMR spectroscopy. The onset of the photochemistry for dendrimer 1 [all-(E)-1,3,5-tris[2-(3,4,5-tridodecyloxyphenyl)ethenyl]benzene] corresponds to the increasing mobility at the Cr/LC transition. The first generation dendrimers still show large angle motion, whereas dendrimers of the second generation 2 [all-(E)-1,3,5-tris(2-[3,5-bis[2-(3,4,5-tridodecyloxyphenyl)ethenyl]phenyl]ethenyl)benzene] are restricted to librational motions. Photochemical conversion and fluorescence quenching for first and second generation dendrimers 1 and 2 increase with increasing molecular motion and reach a maximum in the isotropic phase.
authors.affiliation: Institut für Organische Chemie, University of Mainz, Duisbergweg 10-14, 55099 Mainz, Germany. matthias.lehmann@ulb.ac.be
authors.forename: Matthias
authors.initials: M
authors.lastname: Lehmann
authors.forename: Ingrid
authors.initials: I
authors.lastname: Fischbach
authors.forename: Hans Wolfgang
authors.initials: HW
authors.lastname: Spiess
authors.forename: Herbert
authors.initials: H
authors.lastname: Meier