One‐Pot Preparation of 3D Nano‐ and Microaggregates via In Situ Nanoparticlization of Polyacetylene Diblock Copolymers Produced by ROMP

Zero-dimensional (0D) nanospheres, 1D nanocaterpillars, and 3D aggregates are produced from simple diblock copolymers containing polyacetylene (PA) via in situ nanoparticlization of conjugated polymers. The diblock copolymers are prepared by ring-opening metathesis polymerization via one-pot sequential addition of an endo-tricyclo[4.2.2.0]deca-3,9-diene (TD) and cyclooctatetraene. Initially, they spontaneously form nanospheres consisting of a PA core and PTD shell, and increasing the length of the PA block leads to the direct nanoparticlization of the higher-dimensional structures such as 1D and 3D aggregates because of the decreased effective volume ratio of the rigid PTD shell to the solvophobic PA core.