Dendrimer-like polymers: a new class of structurally precise dendrimers with macromolecular generations

A new class of highly branched polymers referred to as dendrimer-like polymers has been developed in the last decade, the first synthetic example dating back to 1995. Dendrimer-like polymers exhibit molecular features similar to those of regular dendrimers, such as the presence of a central core, a precise number of branching points and terminal functions, but comprise of generations of macromolecular size between their branching junctions. In this highlight article synthetic strategies to dendrimer-like polymers are reviewed as well as some of their characteristic properties. A special emphasis is placed on synthetic methodologies designed in our group to generate dendrimer-like homopolymers and block copolymers by iterative divergent approaches based on anionic ring-opening polymerization of ethylene oxide and atom transfer radical polymerization. Are also thoroughly described the methods used for selectively branching polymeric chain-ends and introducing ω-geminal functionalities from which further macromolecular generations could be grown.