Design of Uniform Polymer Nanoparticles via Living Crystallization Driven Self‐Assembly

Living crystallization-driven self-assembly (CDSA), employing a seeded growth method, has emerged as a pivotal strategy for achieving precise control of anisotropic nanoparticles over the dimensions and structure, which enables the fabrication of 1D cylinders and 2D platelets with low dispersity. This versatile and robust approach, characterized by linearly tunable dimensions and programmability of structural sequences, has been widely applied in the construction of nanoparticles exhibiting uniform size and controlled architecture. A critical aspect of this technique lies in heteroepitaxial crystallization, which transcends the chemical composition constraints of conventional homoepitaxy and enables the design of segmented structures with spatially distinct core components. Building upon this foundation, we elucidate the key aspects of living CDSA seed growth, with a particular emphasis on exploring the mechanism of governing heteroepitaxial growth from crystalline seeds with distinctly chemical compositions. Elucidating the intricate mechanisms of heteroepitaxial crystallization allows access to broaden the design possibilities for segmented nanoparticles with spatially defined core compositions and functionalities. Moreover, the new developing methods for facile synthesis of uniform particles with high solid concentrations are also reviewed, which are promising for the real applications of these advanced nanomaterials.