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 [3 4 ]­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.

Herein we report for the first time on the gram-scale synthesis of a four-arm cage-shaped poly(ethylene oxide) (PEO) and its pioneering application as polymer electrolyte. The well supressed crystallization by...

Dedicated to Rudolf Zentel on the occasion of his retirement.Researchers have dedicated their efforts for the creation of a wide choice of complex and precise macromolecular architectures over the past 100 years. Among them, cyclic polymers benefit from their absence of terminal chains and from their singular topology to minimize their hydrodynamic volume in solution, increase their chemical stability, limit their number of possible conformations as well as a reduce their propensity to crystallize or to form entanglements in comparison to their acyclic counterparts. While monocyclic structures have already been widely investigated and reviewed, reports on more complex polycyclic structures are rare. In this regard, cage-shaped polymers-consisting of at least three polymer chains covalently interconnected through strictly two junction points-have received little attention over the past two decades. Although their synthesis is a worthy challenge, only a few synthetic methodologies of polymer cages were successfully developed so far. Thus, this review intends to highlight the key concepts of the conception of cage-shaped polymers in addition to propose an actual and exhaustive state-of-art concept of their synthesis to rationally promote the next-generation synthesis strategies.

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