Nanostar and nanonetwork crystals were prepared from fully conjugated polythiophene diblock copolymers, i.e., poly(3-(2-ethylhexyl)thiophene)-block-polythiophene (P3EHT-b-PT), via a simple in situ nanoparticlization of conjugated polymer (INCP) process. Various P3EHT-b-PTs were successfully synthesized by the quasi-living Grignard metathesis (GRIM) method; these block copolymers underwent spontaneous self-assembly during the polymerization. The self-assembly behavior of the polymers was initially analyzed using NMR and UV/vis techniques, and the formation of a well-ordered crystalline domain from the solvophobic PT core was further confirmed by the XRD and SAED analyses. The structural conformation of the nanocrystals was investigated in detail using AFM, TEM, and Cryo-TEM imaging techniques, revealing that with an increase in the block length of PT, the morphology of the nanocrystals changed from nanospheres and nanorods to nanostars, and then to nanonetworks. These branched nanoparticles were highly stable toward external stimuli such as heat and mechanical stress. Based on these observations, a plausible mechanism for the generation of various branched nanoparticles was proposed.

Branched hierachical nanocrystals fabricated by in situ nanoparticlization of fully conjugated polythiophene diblock copolymers

248th National Meeting (2014)

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