Three kinds of well-defined topological azo-polymers with controlled molecular weights are prepared using an acrylate-functionalized cyclic polymeric azo-precursor by a selective head-to-tail acyclic diene metathesis (ADMET) polymerization. First, a multifunctional linear precursor bearing the terminal alkyne, hydroxyl, and azido groups were elaborately synthesized. A well-defined acrylate-containing monocyclic azo-polymer was then prepared via “click” ring closure and esterification, which can be considered a selective macromolecular chain stopper in the subsequent ADMET polymerizations of three different types of azo-functionalized monomers. Finally, azo-polymers with cyclic–linear, cyclic–linear–cyclic, and cyclic–hyperbranched topologies were successfully constructed, respectively. Interestingly, these prepared azo-polymers show distinct and unusual photoresponsive behaviors.

Conjugated polyacetylene segment-based monocyclic and bicyclic polymers were synthesized using metathesis polymerizations, and the visualized molecular topology of the cyclic polymers was directly observed.

Noncovalently connected polymers were prepared by one-pot efficient host–guest complexation between β-CD and adamantane moieties followed by acyclic diene metathesis polymerization or carried out simultaneously, and further self-assembled into supramolecular nanostructures with diverse morphologies.

Azobenzene-functionalized ABA triblock copolymers with controlled molecular weights are prepared first via a sequential ring-opening metathesis polymerization and acyclic diene metathesis polymerization in one-pot, which are readily converted, by a facile esterification, to the modified ABA triblock copolymers. Then, these reactive triblock copolymers can spontaneously self-assemble in a selective solvent to form reproducible and reversible polymeric core-shell nanoparticles. Finally, the stable and permanent shell-crosslinked nanoparticles are obtained by an intramolecular crosslinking reaction in dilute solution under UV light irradiation. These as-prepared polymeric nanoparticles and their precursor incorporating azobenzene chromophores exhibit distinct photoresponsive performance and morphological variation.