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In this article, we describe the synthesis of a perfluoro-tagged polyglycerol dendron and its aggregation behavior in the presence of polyglycerol dendrimers with perfluorinated shells in water. The perfluoro-alkyl–perfluoro-alkyl interactions between the perfluorinated shells of the dendrimers and the perfluorinated tags of the dendrons lead to highly stable supramolecular architectures, due to self-assembly of the perfluorinated moieties. Furthermore, we show that the size of the resulting supramolecular complexes can be tuned by simple variation of the dendrimer–dendron ratio. Complexes at various ratios are characterized by optical microscopy, DLS, and TEM. In general, the results presented herein demonstrate that perfluoro-alkyl–perfluoro-alkyl interactions are applicable for the formation of stable supramolecular structures in water and thus provide a new tool for the design of supramolecular architectures in addition to traditional non-covalent interactions.
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