Topological Polymer Chemistry Designing Complex Macromolecular Graph Constructions.

The precision design of topologically intriguing macromolecular architectures has continuously been an attractive challenge in polymer science and polymer materials engineering. A class of multicyclic polymer topologies, including three subclasses of spiro, bridged, and fused forms, are particularly unique not only from a topological geometry viewpoint but also from their biochemical relevance to programmed folding structures. In this Account, we describe recent progress in constructing this class of macromolecules, in particular by means of an electrostatic self-assembly and covalent fixation (ESA-CF) protocol, in which ion-paired polymer self-assemblies are employed as key intermediates. All three dicyclic constructions having either 8 (spiro), manacle (bridged), or θ (fused) forms, as well as a tricyclic trefoil (spiro) graph, have been constructed by the ESA-CF process. Moreover, a triply fused-tetracyclic macromolecular K graph has been constructed using a uniform-size dendritic polymer precursor having six cyclic ammonium salt end groups carrying two units of a trifunctional carboxylate counteranion. Remarkably, the K graph is known in topological geometry as a prototypical nonplanar graph and has been identified as topologically equivalent to some multicyclic polypeptides (cyclotides) produced through the intramolecular S-S bridging with cysteine residues. A series of single cyclic (ring) polymers having one, two, and even three designated functional groups at the prescribed positions along their cyclic backbone segment (kyklo-telechelics) have also been obtained by the ESA-CF protocol. And in conjunction with a tandem alkyne-azide addition (i.e., click) and an olefin metathesis (i.e., clip) reaction, the precision design of complex multicyclic macromolecular architectures has been achieved. Thus, a series of tri-, tetra-, and even hexacyclic polymer topologies of spiro- and bridged-forms and three doubly fused-tricycle (β-, γ-, and δ-graph) forms, as well as a triply fused-tetracyclic and a quadruply fused-pentacyclic form (unfolded tetrahedron-graph, and "shippo"-form, respectively) were effectively constructed. Furthermore, the hybrid multicyclic polymer constructions comprised of three subclasses of spiro, bridged, and fused units have been produced using complementary pairs of single cyclic and dicyclic kyklo-telechelic precursors obtainable by the ESA-CF process. Upon these synthetic developments, we are now entering into an exciting new era of polymer science and polymer materials engineering based on the precision design of polymer topologies, which appears comparable to the "Cambrian explosion period" experienced in the evolution of life systems.