要旨
Extended-Arm Polyphenylene-Dendrimers: Synthesis and Characterization.
Abstract of the dissertaton submitted by Ekaterina V. Andreitchenko to the Fachbereich Chemie und Pharmazie der Universität Mainz, (16 March 2006).
In order to eliminate the de Gennes packing problem, which usually limits the attainable size of dendrimers, a new branching unit containing para-tetraphenylene ethynyl arms has been synthesized and utilized in the preparation of dendrimers of the Müllen type. The divergent principle of synthesis, based on the Dilthey reaction, could be carried up to sixth generation which contains 2776 benzene rings and possesses a diameter in the 27 nm range (‘‘exploded dendrimer’’). Monodispersity and dimensions of this and the lower generation species have been studied by MALDI-TOF MS (including the very recent superconducting tunnel junction detector), by size-exclusion chromatography, dynamic light scattering, transmission electron microscopy, and atomic force microscopy. Interesting features, apart from the huge dimension, are the low density and high porosity of these giant molecules which cause extensive aggregation in the gas phase, flattening on solid support (AFM) and the ready incorporation of guest molecules in the condensed phase.
Since the synthesis of the para-tetraphenylene arms is quite elaborate, similar dendrimers containing para-terphenylene arms have been prepared; they are accessible more economically (‘‘semi-exploded dendrimers’’). It has been shown that they in several aspects mimic the features of the ‘‘exploded dendrimers’’.
In order to take advantage of the presence of large internal cavities in this dendrimer type, dendrons containing -C≡C- triple bonds have also been incorporated. Surprisingly, they are readily hydrogenated under the condition of heterogeneous catalysis (Pd/C) which demonstrates the large size of the cavities. As revealed by a quartz microbalance study the post-hydrogenation dendrimers are less prone to incorporate guest molecules than before hydrogenation. Obviously, the more flexible nature of the former reduces porosity, it also leads to significant shrinkage. An interesting perspective is the use of homogeneous hydrogenation catalysts of variable size with the aim of determining the dimension of internal free space.
