<Abstract> Topologically intriguing polymer chain architectures have continuously been an attractive research subject. A class of multicyclic polymer topologies are particularly unique not only from the topological geometry viewpoint but also from their unprecedented topology effects. We have developed an electrostatic self-assembly and covalent fixation (ESA-CF) protocol, in which ion-paired polymer self-assemblies are employed as key intermediates. A variety of multicyclic polymer topologies of spiro-, bridged- fused-forms, including a triply-fused tetracyclic and a quadruply-fused pentacyclic forms (unfolded tetrahedron-graph, and “shippo”-form, respectively), as well as their hybrid analogues were subsequently constructed through the ESA-CF protocol in conjunction with a tandem alkyne-azide addition, i.e., click, and olefin metathesis, i.e., clip, reactions. With the ESA-CF protocol, the construction of a triply-fused tetracyclic macromolecular K3,3 graph topology has been completed, which is known as a geometrically unique non-planar graph, and remarkably, moreover, has been identified in cyclic polypeptides (cyclotides) produced through the intramolecular S-S bridging by their cysteine residues.
Keywords: Topological Polymer Chemistry / Multicyclic Polymers / Telechelic Polymers / ESA-CF Process / Click Process / Clip (Metathesis) Process / K3,3 Graph Polymer |