Synergy of Macrocycles and Macromolecular Topologies: An Efficient [3<sub><i>4</i></sub>]Triazolophane-Based Synthesis of Cage-Shaped Polymers
Martin Gauthier‐Jaques, Patrick Théato
Abstract
The development of complex topologies such as macromolecular cages constitutes a fascinating aspect of polymer chemistry. In the present work, a novel strategy involving self-closing bifunctional end-groups, which under specific conditions, are allowed to assemble themselves into a predefined thermodynamically favored macrostructure, was designed to fulfill the topological conversion of star-shaped polymers to their respective cage-shaped polymers. A series of four different well-defined four-arm star-shaped poly(ε-caprolactone) polymers varying in molar masses were successfully synthesized, end-functionalized, and closed into cage-shaped polymers by formation of [34]triazolophane macrocycle units. The obtained cage-shaped polymers feature interesting properties that depend drastically on the chain length of the arms and seem to differ from previous reported polymer cages.