Particle fusion is well-recognized as an important spontaneous process to produce higher-order nanostructures during morphology transition in polymerization-induced self-assembly (PISA). However, to our knowledge, the directional contact, adhesion, and fusion of adjacent nanoparticles have been rarely elucidated in PISA. Herein, a directional fusion of ellipsoidal morphologies was demonstrated during PISA of semi-fluorinated liquid-crystalline (SFLC) block copolymers. The ellipsoidal nanostructures, including micelles and vesicles, preferred to undergo a directional fusion in a head-to-head model, leading to the formation of nanorods and nanotubes, respectively. We believe the directional fusion will offer insightful guidance in PISA to the preparation of complicated functional nanostructures.
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