Polyphosphazenes – Synthetically Versatile Block Copolymers (“Multi‐Tool”) for Self‐Assembly

This microreview outlines recent advances on the synthesis and self-assembly of polyphosphazene diblock copolymers, a class of versatile polymers (Multi-Tool) able to generate a great variety of different well-defined nanomorphologies. Particular focus is placed on the synthesis of linear block copolymers composed of two polyphosphazene chains (PP-b-PP), or hybrid polymers combining one PP chain with a non-phosphazene segment [i.e. organic blocks such as poly(olefin)s, polyethers, polyesters, etc.]. We also survey the self-assembly of these macromolecules equipped with crystalline, rigid or chiral PP core-forming blocks, to show the morphological diversity and structural complexity of the nanostructures generated in thin films or in solution (selective solvent).