Polymeric Ligand-Mediated Regioselective Bonding of Plasmonic Nanoplates and Nanospheres

Abstract

Nanoparticle (NP) clusters are attractive for many applications, but controllable and regioselective assembly of clusters remains challenging. This communication reports a strategy to precisely assemble Ag nanoplates (NP-As) and Au nanospheres (NP-Bs) grafted with copolymer ligands into defined AB x clusters with controlled coordination number (x) and orientation of the NPs. The directional bonding of shaped NPs relies on the stoichiometric reaction of complementary reactive groups on copolymer ligands. The x value of NP clusters can be tuned from 1 to 4 by varying the number ratio of reactive groups on single NP-Bs to NP-As. The regioselective bonding of nanospheres to the edge or face of a central nanoplate is governed by the steric hindrance of copolymeric ligands on the nanoplate. The clusters exhibit distinctive plasmonic properties that are dependent on the bonding modes of NPs. This study paves a route to fabricating nanostructures with high precision and complexity for applications in plasmonics, catalysis, and sensing.

Controlled Assembly of Plasmonic Nanoparticles: From Static to Dynamic Nanostructures

“…Lin et al reported the regioselective self-assembly of Ag nanoplates (A) and Au nanospheres (B) by a polymershielding approach that does not require selective surface blocking (Figure 8a). [86] In this approach, the nanoparticles are first functionalized with a block copolymer composed of a noninteractive block and an interactive block containing acid and base functionalities. Subsequently, the interactive block drives c) Reproduced with permission.…”

“…Subsequently, the interactive block drives c) Reproduced with permission. [86] Copyright 2020, American Chemical Society. d,e) Reproduced with permission.…”

“…d,e) Use of single-stranded DNA to encode nanoparticles with bonding sites and their directional self-assembly into discrete molecule-like clusters d) and their chiroptic properties e). a-c) Reproduced with permission [86]. Copyright 2020, American Chemical Society.…”

Distinctive Dielectric Permittivity of Hierarchical Nanostructures with Ordered Nanoparticle Networks Self-Assembled from AB-g-NP/AC Block Copolymer Mixtures

“…But the homopolymer-grafted nanoparticles were not well organized in the block copolymer nanodomains and the improvement in the permittivity was limited. Recently, block copolymer-grafted nanoparticles (BNPs) have emerged as novel assembly building blocks. − For example, Leffler et al investigated the self-assembly of BNP thin films prepared from poly­(styrene- b -isoprene) (PS-PI) block copolymers and Cu 2 ZnSnS 4 nanoparticles . They found that the BNPs, unlike the homopolymer-grafted nanoparticles, can self-assemble into highly ordered stripes under the confinement of thin films.…”

Supramicellar Nanofibrils with End-to-End Coupled Uniform Cylindrical Micelle Subunits via One-Step Assembly from a Liquid Crystalline Block Copolymer

“…Nature utilizes an extraordinarily convoluted and delicately balanced interplay of orthogonal covalent and supramolecular interactions to construct highly organized and hierarchical architectures via site-specific interactions by virtue of which the assembly could be achieved at all different scales. , Collagen fibrillation, as one of the most fascinating and inspiring examples, combines the production of proteins via covalent bonding, the folding of protein chain through hydrogen bonding, and the subsequent spontaneous coupling or bundling of these monomeric precursors via site-specific hydrogen bonding and amphiphilic interactions. − These hierarchical structures and their intricate assembly process have captured the enthusiasm and imagination of scientists to emulate the intricacy, homogeneity, and versatility of the naturally occurring systems − and have represented a central challenge in contemporary materials and chemistry science. Many successful examples have been presented during the past decades toward this ultimate goal of artificial assembly systems, including the hierarchical organization of nanoparticles in a controlled manner, − exotic nanostructures from the designed assembly and epitaxial growth of crystalline block copolymers, − and directional attachment of patchy colloidal particles to build multidimensional hierarchical suprastructures, − and so forth. Although a site-specific design strategy has been applied in these studies and has been demonstrated to be successful in artificial assembly systems, all these achievements have unavoidably adopted multistep approaches.…”