A monofunctional bottlebrush-shaped polymer terminated with an azide group and its oligomers (dimer, trimer) were synthesized in a controlled manner and directly visualized.

Polythiophene nanoparticles (PTNs), as one of the typical conjugated polymer nanoparticles (CPNs) with novel optical and electronic properties have won extensive attentions, especially their applications in electronics and bioimaging. However, PTNs obtained with traditional methods are usually nonuniform or unstable. Herein, we developed a novel method to prepare uniform and stable PTNs templated from star-like unimolecular micelles. Cyclodextrin-cored unimolecular micelles with tailored components were prepared through atom transfer radical polymerization, and PTNs with plain or hollow nanostructures can be obtained via crosslinking the suspended thiophene units in designed domain of unimolecular micelles. The unimolecular micelles and PTNs were characterized via nuclear magnetic resonance, Fourier transform infrared, transmission electron microscopy, atomic force microscopy, dynamic light scattering, ultraviolet-visible, and photoluminescence, indicating that the PTNs exhibit uniform size, controllable surface chemistry, and well-defined nanostructures. The obtained PTNs have potential applications in optics, electronics, and bioimaging. Also, this provides a new way to synthesize CPNs with tailored sizes, nanostructures, and surface chemistry.Additional supporting information may be found in the online version of this article.

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