Complex Cage, Cage-Brush, and Lantern Polymers with Topological-Enhancing Phosphorescence

Cage polymers, a type of special cyclic polymer with an intriguing three-dimensional topology and internal cavity, have attracted increasing attention. However, because of the complicated topological structure, precise preparation of cage polymers is a formidable challenge. Herein, an effective and versatile synthetic strategy was developed to precisely construct complex topological polymers with a well-defined structure and high molecular weight, including three-arm cage, three-arm cage-brush, bi(three-arm) cage, and six-arm cage polymers, by a ring-opening metathesis polymerization-based blocking-cyclization technique using different short polymeric ladderphanes containing multiple living ends as the initial and end-cyclizing motifs, which was the key factor in simply tuning the polymer topology. Moreover, bi- and six-arm lantern polymers were readily derived from the corresponding cage polymers. By comparison of the performance differences between these novel polymers, the dependence of the properties on the topology was revealed. Therefore, this work provided a platform for constructing complex topological polymers with unique topological-enhancing phosphorescent performance and mechanical properties.