Nature controls the assembly of complex architectures through self-limiting processes; however, few artificial strategies to mimic these processes have been reported to date. Here we demonstrate a system comprising two types of nanocrystal (NC), where the self-limiting assembly of one NC component controls the aggregation of the other. Our strategy uses semiconducting InP/ZnS core–shell NCs (3 nm) as effective assembly modulators and functional nanoparticle surfactants in cucurbit[n]uril-triggered aggregation of AuNCs (5–60 nm), allowing the rapid formation (within seconds) of colloidally stable hybrid aggregates. The resultant assemblies efficiently harvest light within the semiconductor substructures, inducing out-of-equilibrium electron transfer processes, which can now be simultaneously monitored through the incorporated surface-enhanced Raman spectroscopy–active plasmonic compartments. Spatial confinement of electron mediators (for example, methyl viologen (MV2+)) within the hybrids enables the direct observation of photogenerated radical species as well as molecular recognition in real time, providing experimental evidence for the formation of elusive σ–(MV+)2 dimeric species. This approach paves the way for widespread use of analogous hybrids for the long-term real-time tracking of interfacial charge transfer processes, such as the light-driven generation of radicals and catalysis with operando spectroscopies under irreversible conditions.
Bibliographical noteFunding Information:
We acknowledge financial support from EPSRC grant nos. EP/L027151/1 (NOtCH) and EP/R020965/1 (RaNT). J.H. is thankful for support from the Chinese Scholarship Council and Cambridge Commonwealth, European and International Trust. B.d.N. acknowledges support from the Leverhulme Trust and Isaac Newton Trust. R.C. acknowledges support from Trinity College, Cambridge. S.M.C. thanks Girton College, Cambridge, for a Henslow Research Fellowship. We thank S. J. Barrow, A. S. Groombridge and I. Szabó for helpful discussions. We acknowledge use of the research computing facility at King’s College London, Rosalind (https://rosalind.kcl.ac.uk).
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ASJC Scopus subject areas
- Atomic and Molecular Physics, and Optics
- Biomedical Engineering
- Materials Science(all)
- Condensed Matter Physics
- Electrical and Electronic Engineering