Synthesis and Characterization of Linear, Hyperbranched, and Dendrimer-Like Polymers Constituted of the Same Repeating Unit

The synthesis of a linear polymer that includes both P=N and P=S double bonds, and P−O and P−C single bonds is reported by using two different paths that involve deprotection reactions and the Staudinger reaction. The preparation of hyperbranched polymers made up of OC6H4P(Ph)2=N−P=S repeating units is also described. Five generations of dendrimers originating from the same building blocks were prepared. The characterisation of all these phosphorus‐based macromolecular architectures (solution behaviour, size exclusion chromatography, intrinsic viscosity, thermal behaviour) revealed marked differences in their respective behaviour. Playing with deprotection reactions that involve phosphane‐boron adducts and Staudinger reactions which employ azides and free phosphanes provides access to linear or hyperbranched polymers and dendrimers which incorporate the same OC6H4P(Ph)2=N−P=S repeating building block (see figure).