A library of semifluorinated Janus dendrimers and dendronized polymers has been synthesized. Janus dendrimers are derived from twin tapered dendrons containing one dendron with semifluorinated and the other dendron with hydrogenated alkyl chains on the peripheries of the dendrons. Janus dendrimers are attached to the polymer backbone both from the hydrogenated and from the fluorinated parts of the Janus dendrimer. Structural analysis by a combination of differential scanning calorimetry, x-ray diffraction experiments, reconstruction of the electron density distributions, and molecular modeling have demonstrated that these Janus dendrimers and dendronized polymers self-assemble into supramolecular vesicular columns. The diameter of these vesicular columns is two times larger than that of the corresponding supramolecular columns assembled from the hydrogenated or fluorinated twin dendritic molecules. This vesicular columnar structure is generated by a mechanism that involves an intramolecular assembly of the Janus dendrimers into tapered dendrons followed by the self-assembly of the resulting dendronized polymer in a vesicular column. This new class of dendronized polymers exhibits a decrease in length of the self-assembled supramolecular columns with an increase in temperature and acts as reverse thermal actuators.

Self-assembly of semifluorinated Janus dendrimers and dendronized polymers into supramolecular vesicular columns

244th National Meeting (2012)

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