The past several decades have witnessed substantial advances in synthesis and self-assembly of inorganic nanocrystals (NCs) due largely to their size- and shape-dependent properties for use in optics, optoelectronics, catalysis, energy conversion and storage, nanotechnology, and biomedical applications. Among various routes to NCs, the nonlinear block copolymer (BCP) nanoreactor technique has recently emerged as a general yet robust strategy for crafting a rich diversity of NCs of interest with precisely controlled dimensions, compositions, architectures, and surface chemistry. It is notable that nonlinear BCPs are unimolecular micelles, where each block copolymer arm of nonlinear BCP is covalently connected to a central core or polymer backbone. As such, their structures are static and stable, representing a class of functional polymers with complex architecture for directing the synthesis of NCs. In this review, recent progress in synthesizing NCs by capitalizing on two sets of nonlinear BCPs as nanoreactors are discussed. They are star-shaped BCPs for producing 0D spherical nanoparticles, including plain, hollow, and core-shell nanoparticles, and bottlebrush-like BCPs for creating 1D plain and core/shell nanorods (and nanowires) as well as nanotubes. As the surface of these NCs is intimately tethered with the outer blocks of nonlinear BCPs used, they can thus be regarded as polymer-ligated NCs (i.e., hairy NCs). First, the rational design and synthesis of nonlinear BCPs via controlled/living radical polymerizations is introduced. Subsequently, their use as the NC-directing nanoreactors to yield monodisperse nanoparticles and nanorods with judiciously engineered dimensions, compositions, and surface chemistry is examined. Afterward, the intriguing properties of such polymer-ligated NCs, which are found to depend sensitively on their sizes, architectures, and functionalities of surface polymer hairs, are highlighted. Some practical applications of these polymer-ligated NCs for energy conversion and storage and drug delivery are then discussed. Finally, challenges and opportunities in this rapidly evolving field are presented.
Keywords: controllable architectures; controlled/living radical polymerization; dimension-dependent properties; nanoreactors; nonlinear block copolymers; polymer-ligated nanocrystals; surface chemistry.