We demonstrate ultrafine engineering of nanocrystal (NC) interfaces in an aqueous environment through supramolecular functionalization, which unlocks molecular recognition motifs revealing detailed insights into dynamic host-guest interactions at surface-confined binding centres. Highly luminescent semiconductor indium phosphide zinc sulfide core-shell NCs (InP/ZnS NCs) are decorated with cucurbit[n]uril macrocycles (CB[n]s) leading to self-limiting self-assembly of colloidally-stable dynamic hybrid aggregates. The resultant hybrids are utilized for interfacial encapsulation processes in which surface-bound CB[n] molecules work as a host system to spatially confine selected guest molecules (i.e., cobaltocenium and adamantylamine), facilitating interfacial electron transfer processes. This fundamental understanding of host-guest chemistry at NC interfaces paves the way to controlled binding of chemical species that exhibit low or even no affinity to nanoparticulate materials. We further employ the self-limiting character of CB[n]-mediated aggregation of the InP/ZnS NCs for the formation of controlled hybrid aggregates consisting of two types of NCs (i.e., semiconductor and plasmonic) through rapid self-assembly. InP/ZnS core-shell NCs (3 nm) are efficient assembly-modulators in CB[n]-triggered aggregation of plasmonic Au NCs (5-60 nm). These core-shell NCs act as both a functional nanoparticle surfactant and photocatalytic absorber, which adhere onto the surface of the larger Au NCs and kinetically arrest growth of emerging plasmonic aggregates. Within the described self-limiting assembly, the photoactive semiconductor NCs become an integral part of the overall structure and function of the resultant hybrid supraparticles. The CB[n]-mediated coupling of semiconducting NCs serves as an attractive tool to facilitate control of aggregation processes as well as optical and plasmonic properties of the resultant colloidal assemblies. The colloidally-integrated semiconductor/metal hybrids represent a powerful prototype multifunctional SERS-based assay for photochemical processes. Controlling the efficiency of supramolecular engineering of NC interfaces opens a plethora of possibilities for ultrafine nanoparticle functionalization and construction of hybrid systems for sensing applications as well as next-generation (photo)catalysis, optoelectronics and nanophotonics.

Molecular engineering of semiconductor and plasmonic nanocrystal interfaces through host-guest recognition motifs

Macromolecular Chemistry: The Second Century

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ACS Spring 2020 National Meeting & Expo

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