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Current interest in nanoparticle ensembles is motivated by their collective synergetic properties that are distinct from or better than those of individual nanoparticles and their bulk counterparts. These new advanced optical, electronic, magnetic, and catalytic properties can find applications in advanced nanomaterials and functional devices, if control is achieved over nanoparticle organization. Self-assembly offers a cost-efficient approach to produce ensembles of nanoparticles with well-defined and predictable structures. Nanoparticles functionalized with polymer molecules are promising building blocks for self-assembled nanostructures, due to the comparable dimensions of macromolecules and nanoparticles, the ability to synthesize polymers with various compositions, degrees of polymerization, and structures, and the ability of polymers to self-assemble in their own right. Moreover, polymer ligands can endow additional functionalities to nanoparticle assemblies, thus broadening the range of their applications.In this Account, we describe recent progress of our research groups in the development of new strategies for the self-assembly of nanoparticles tethered to macromolecules. At the beginning of our journey, we developed a new approach to patchy nanoparticles and their self-assembly. In a thermodynamically driven strategy, we used poor solvency conditions to induce homopolymer surface segregation in pinned micelles (patches). Patchy nanoparticles underwent self-assembly in a well-defined and controlled manner. Following this work, we overcame the limitation of low yield of the generation of patchy nanoparticles, by using block copolymer ligands. For block copolymer-capped nanoparticles, patch formation and self-assembly were "staged" by using distinct stimuli for each process. We expanded this work to the generation of patchy nanoparticles via dynamic exchange of block copolymer molecules between the nanoparticle surface and micelles in the solution. The scope of our work was further extended to a series of strategies that utilized the change in the configuration of block copolymer ligands during nanoparticle interactions. To this end, we explored the amphiphilicity of block copolymer-tethered nanoparticles and complementary interactions between reactive block copolymer ligands. Both approaches enabled exquisite control over directional and self-limiting self-assembly of complex hierarchical nanostructures. Next, we focused on the self-assembly of chiral nanostructures. To enable this goal, we attached chiral molecules to the surface of nanoparticles and organized these hybrid building blocks in ensembles with excellent chiroptical properties. In summary, our work enables surface engineering of polymer-capped nanoparticles and their controllable and predictable self-assembly. Future research in the field of nanoparticle self-assembly will include the development of effective characterization techniques, the synthesis of new functional polymers, and the development of environmentally responsive self-assembly of polymer-capped nanoparticles for the fabrication of nanomaterials with tailored functionalities.

Current interest in functional assemblies of inorganic nanoparticles (NPs) stems from their collective properties and diverse applications ranging from nanomedicines to optically active metamaterials. Coating the surface of NPs with polymers allows for tailoring of the interactions between NPs to assemble them into hybrid nanocomposites with targeted architectures. This class of building blocks is termed "hairy" inorganic NPs (HINPs). Regiospecific attachment of polymers has been used to achieve directional interactions for HINP assembly. However, to date anisotropic surface functionalization of NPs still remains a challenge. This Account provides a review of the recent progress in the self-assembly of isotropically functionalized HINPs in both the condensed state and aqueous solution as well as the applications of assembled structures in such areas as biomedical imaging and therapy. It aims to provide fundamental mechanistic insights into the correlation between structural characteristics and self-assembly behaviors of HINPs, with an emphasis on HINPs made from NPs grafted with linear block copolymer (BCP) brushes. The key to the anisotropic self-assembly of these HINPs is the generation of directional interactions between HINPs by designing the surrounding medium (e.g., polymer matrix) or engineering the surface chemistry of the HINPs. First, HINPs can self-assemble into a variety of 1D, 2D, or 3D nanostructures with a nonisotropic local arrangement of NPs in films. Although a template is not always required, a polymer matrix (BCPs or supramolecules) can be used to assist the assembly of HINPs to form hybrid architectures. The interactions between brushes of neighboring HINPs or between HINPs and the polymer matrix can be modulated by varying the grafting density and length of one or multiple types of polymers on the surface of the NPs. Second, the rational design of deformable brushes of BCP or mixed homopolymer tethers on HINPs enables the anisotropic assembly of HINPs (in analogy to molecular self-assembly) into complex functional structures in selective solvents. It is evidenced that the directional interactions between BCP-grafted NPs arise from the redistribution and conformation change of the long, flexible polymer tethers, while the lateral phase separation of brushes on NP surfaces is responsible for the assembly of HINPs carrying binary immiscible homopolymers. For HINPs decorated with amphiphilic BCP brushes, their self-assembly can produce a variety of hybrid structures, such as vesicles with a monolayer of densely packed NPs in the membranes and with controlled sizes, shapes (e.g., spherical, hemispherical, disklike), and morphologies (e.g., patchy, Janus-like). This strategy allows fine-tuning of the NP organization and collective properties of HINP assemblies, thus facilitating their application in effective cancer imaging, therapy, and drug delivery. We expect that the design and assembly of such HINPs with isotropic functionalization is likely to open up new avenues for the fabrication of new functional nanocomposites and devices because of its simplicity, low cost, and ease of scale-up.

Multicomponent nanoparticles (MCNs) composed of disparate inorganic colloidal components have attracted great attention from researchers in both the academic and industrial community, because of their unique properties and diverse applications in energy conversion and storage; heterogeneous catalysis; optics and electronics; and biomedical imaging, diagnosis, and therapy. Compared with single-component nanoparticles (NPs), new or advanced properties of MCNs arise from the synergistic effect between their constituent components and the presence of nanoscale interfaces between distinct materials within the particles. Consequently, the spatial arrangement of nanoscale domains of MCNs becomes equally important in property or function control of MCNs as their size, shape, and composition, if not more. In particular, compositionally asymmetric MCNs may outperform their symmetric counterparts in many of their applications. To this end, the seed-mediated growth (SMG) method, which involves depositing a second material onto seed NPs, has been considered as the most common strategy for the synthesis of asymmetric MCNs with desired complexity. In this approach, the control of symmetry breaking during MCN growth is usually achieved by manipulating the growth kinetics or using seed NPs with asymmetric shapes or surfaces. Although great progress has been made in the past decade, there remains a challenge to control the shape, orientation and organization of colloidal components of MCNs with a high yield and reproducibility. Recently, several unconventional methods have been developed as an important addition to the synthetic toolbox for the production of complex MCNs that otherwise may not be readily attainable. This Account summarizes recent advancements on the development of unconventional synthetic strategies for breaking the growth symmetry in the synthesis of asymmetric MCNs. We start with a brief discussion of the achievements and limitations of the conventional strategies for symmetry breaking synthesis. In the subsequent section, we present three unconventional approaches toward symmetry-breaking synthesis of asymmetric MCNs, namely, surface-protected growth, interface-guided growth, and welding-induced synthesis. First, we discuss how commonly used soft agents (e.g., collapsed polymer) and hard agents (e.g., silica) can be asymmetrically coated on seed NPs to template the asymmetric growth of secondary material, generating a broad range of MCNs with complex architectures. The unique features and key factors of this surface-protected synthesis are discussed from the viewpoints of the surface chemistry of seed NPs. We further discuss the use of a solid/liquid or liquid/liquid interface to guide the synthesis of Janus or more complex MCNs through two general mechanisms; that is, selective blocking or impeding the access of precursors to one side of seed NPs and interfacial reaction-enabled generation of asymmetric seeds for further growth. Finally, we discuss a symmetry-breaking method beyond the SMG mechanism, directed welding of as-synthesized single-component NPs. Moreover, we discuss how the unique structural symmetry and compositional arrangement of these MCNs significantly alter the physical and chemical properties of MCNs, thus facilitating their performance in exemplary applications of photocatalysis and electrocatalysis. We finally conclude this Account with a summary of recent progress and our future perspective on the future challenges.