Orthogonal Synthesis of Covalent Polydendrimer Frameworks by Fusing Classical and Onion-Peel Phosphorus-Based Dendritic Units

We report novel and new giant three-dimensional polymers having dendrimers as repeating units. The approach is illustrated here for macromolecular synthesis by polymeric condensation of well-defined single phosphorus dendrimers units. Specifically, classical and onion-peel phosphorus dendrimers, constructed by a divergent method from a cyclotriphosphazene core, were fused within the same tectonic nanostructure by several polymeric condensation approaches including hydrazine-to-aldehyde Schiff-base formation and amine-to carboxylic acid peptide-like coupling. These reticular, easy to run metal free routes afford a new library of hyperbranched macromolecular materials, featuring various phosphorus layers (both alternated and dissymmetrical), well-defined textured nanospheres, and controllable nanometric ordered substructures. The scope of the concept is successfully expanded to the integration of electro-redox viologen units resulting in the synthesis of new photoactive macromolecular materials.