ConspectusColloidal hybrid nanoparticles are solution-dispersible constructs that join together multiple distinct nanoscale materials through direct solid-solid interfaces. Given their multifunctionality and synergistic properties that emerge from interfacial coupling, hybrid nanoparticles are of interest for applications in biomedical imaging, solar energy conversion, heterogeneous catalysis, nanophotonics, and beyond. High-order hybrid nanoparticles, which incorporate three or more nanocrystal domains, offer greater tunability and functional diversity relative to one or two-component nanoparticles. The multiple heterojunctions within these structures can facilitate complex electromagnetic coupling as well as cooperative surface processes. Additionally, these materials can be used as model systems for studying fundamental structure-property relationships at the nanoscale that arise from particle coupling and interfacial exchanges. Limiting these advances is the inability to synthesize hybrid nanoparticles with precise morphologies and geometries. High-order hybrid nanoparticles can adopt more than one configuration, and each unique arrangement will have different heterointerfaces and, accordingly, different functions. Seeded-growth methods are among the most effective methods for producing high-quality hybrid nanoparticles. Engineering complex heterostructures using these stepwise reactions is in some ways conceptually analogous to the total synthesis of large organic molecules. However, unlike in molecular synthesis, the rules and guidelines that underpin the formation of hybrid nanoparticles are less understood. For example, when a third domain is added to a two-component heterodimer nanoparticle seed, several distinct types of hybrid nanoparticle products are possible, but only one is typically observed due to preferred growth at specific locations. The three-component heterotrimer products that preferentially form are not necessarily those that have the domain configurations and heterojunctions required to facilitate a targeted application. Different arrangements of the three nanoparticles that comprise a heterotrimer lead to distinct configurational isomers. Accordingly, understanding and controlling configurational isomerism in nanoparticle heterotrimers is foundational for engineering high-order hybrid nanostructures with targeted heterointerfaces, properties, and functionalities.This Account highlights recent insights into the pathways by which three-component nanoparticle heterotrimers form and how their configurations can be controlled and modified. In-depth microscopic investigations into the formation of heterotrimers by growing a third nanoparticle domain on a two-component heterodimer seed have revealed that in some cases indiscriminate nucleation first occurs on all exposed surfaces followed by surface-mediated migration and coalescence to the preferred interface. This insight helps to rationalize observed site-specific, chemoselective growth phenomena. Additionally, new approaches for directing growth in heterotrimer synthesis, such as protection-deprotection schemes inspired by organic chemistry, are becoming effective tools for constructing hybrid nanoparticles having nonpreferred domain configurations. Alternatives to traditional seeded-growth approaches are also emerging, including insertion reactions driven by saturation-precipitation processes and orthogonal transformations of preformed hybrid constructs using ion exchange. These and other recent advances are providing a powerful suite of synthetic tools that are anticipated to enable function-driven design of high-order hybrid nanoparticles having targeted properties and applications.
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